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CROSS REFERENCE TO RELATED APPLICATIONS The present application is related to the following U.S. patent application: provisional patent application No. 60/799,236 titled “Methods and apparatus for an active shoe cleat system” filed on May 10, 2006, which is hereby incorporated by reference as if fully set forth herein. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT Not Applicable DESCRIPTION OF ATTACHED APPENDIX Not Applicable BACKGROUND OF THE INVENTION This invention relates generally to the field of athletic shoes and more specifically to system for active and controlled shoe cleats. There are a variety of prior art systems for extending cleats from a shoe but none have used the innovative combination of active electronic sensing and active drive control of the present invention. There are a number of patents that disclose a variety of retractable and extendable cleats, including U.S. Pat. No. 5,740,619 entitled “Retractable Stud”; U.S. Pat. No. 5,313,718 entitled “Athletic Shoe With Bendable Traction Projections”; and U.S. Pat. No. 4,873,774 entitled “Shoe Sole With Retractable Cleats.” None of these patents shows the innovative combination of the present invention and its use of ambient sensors and active systems for deploying traction enhancing elements on the shoe. Other patents such as U.S. Pat. No. 6,182,381 entitled “Sole of baseball spiked shoe and method of measuring shearing stress distribution of baseball spiked shoe” discuss means for measuring stresses on shoes using accelerometers and other sensors to provide information that can be used in enhancing shoe design but do not show the innovative combination of the present invention. The use of accelerometers and other sensors in ambient conditions has been disclosed in U.S. Pat. No. 5,456,027 to Tecchio et al. entitled “Athletic Shoe With A Detachable Sole Having An Electronic Breakaway System” but does not disclose an active cleat system whose purpose is to actively enhance traction of the shoe according the present invention. These types of sensors and control circuitry may be employed in a new and different application according to the present invention by activating cleats or other surface traction devices based on readings provided by the sensors and other circuitry. In accordance with a preferred embodiment of the invention, there is shown an active shoe cleat system with a shoe having a sole portion for supporting the wearer's foot, at least one chamber provided in the sole portion, a processor in the chamber operably connected to a plurality of cleats on the bottom of the shoe, at least one sensor in the shoe that measures at least one parameter pertaining to movement of the shoe, a projection within the cleat that is deployed in response to a control signal from the processor, the control signal is generated in response to data processed by the processor from information provided in part by the sensor and means for urging the projection outward from within the cleat. In accordance with a preferred embodiment of the invention, there is also shown an active shoe cleat system with a shoe having a sole portion for supporting the wearer's foot, at least one chamber provided in the sole portion, a processor in the chamber operably connected to a generator of fluid pressure that engages at least one cleat on the bottom of the shoe, at least one sensor in the shoe that measures at least one parameter pertaining to the movement of the shoe, a projection within the cleat that is deployed in response to fluid pressure from the generator in response to a control signal from the processor where the control signal is generated in response to data processed by the processor from information provided in part by the sensor. In accordance with a preferred embodiment of the invention, there is shown an athletic shoe for increasing traction as well as speed and efficiency of manuverability with a sole member having a plurality of ground-contacting cleats, the cleats operably connected to a central processing unit, the cleat being movable between an extended position and a retracted position in response to sensing means, means for holding the cleats in the extended position and means for releasing the members to the retracted position, control means for releasing the holding means and for allowing the release means to move the cleat to the release position when a force exceeds a preset level in response to sensing means, and sensing means for sensing the force applied to the lower sole member and for signaling the control means for moving the cleats to the extended position. BRIEF SUMMARY OF THE INVENTION The primary advantage of the invention is to provide improved tractions as well as speed and efficiency of maneuverability through an active cleat system. Another advantage of the invention is to provide cleats that are activated depending on ambient user conditions. Another advantage of the invention is to provide a cleat system that projects the cleats outward from the shoe based on a function whose inputs include but are not limited to acceleration, force, weight, temperature etc. Another advantage of the invention is to provide an active system for widening the shoe bottom surface area in real time to enhance traction. Another advantage of the invention is that it makes use of various microelectronics to achieve full implementation of the system. Other objects and advantages of the present invention will become apparent from the following descriptions, taken in connection with the accompanying drawings, wherein, by way of illustration and example, an embodiment of the present invention is disclosed. BRIEF DESCRIPTION OF THE DRAWINGS The drawings constitute a part of this specification and include exemplary embodiments to the invention, which may be embodied in various forms. It is to be understood that in some instances various aspects of the invention may be shown exaggerated or enlarged to facilitate an understanding of the invention. FIG. 1 shows an exploded cross sectional view of a preferred embodiment of a portion of a shoe according to a preferred embodiment of the invention. FIG. 2 shows a block diagram of a control unit according to a preferred embodiment of the invention. FIG. 3 shows a schematic perspective view of a control apparatus according to a preferred embodiment of the invention. FIG. 4 shows a plan view of a shoe and cleat system according to a preferred embodiment of the invention. FIG. 5 shows a side cross sectional view of a cleat system according to a preferred embodiment of the invention. FIG. 6 shows a side cross sectional view of a cleat system according to a preferred embodiment of the invention. FIG. 7 shows a side cross sectional view of a cleat system according to a preferred embodiment of the invention. FIGS. 8A and 8B show side cross sectional views of a cleat system employing hydraulic action according to a preferred embodiment of the invention. FIG. 9 shows a side cross sectional view of a cleat system according to a preferred embodiment of the invention. FIGS. 10A , 10 B and 10 C show side cross sectional views of a cleat system according to a preferred embodiment of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Detailed descriptions of the preferred embodiment are provided herein. It is to be understood, however, that the present invention may be embodied in various forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in virtually any appropriately detailed system, structure or manner. Turning now to FIG. 1 , there is shown a cross section of a cleated shoe sole 10 with layers 12 , 14 16 and 20 that form the sole of the shoe. Arch 24 contains space under the arch to facilitate locating a central processing unit (CPU) 18 in the sole. With sensors 28 located along a bottom surface inside the shoe, CPU 18 is preferably located in the arch and various motors, transmission gears, and drive shafts or cables (not shown) are located at strategic locations about the active cleats 22 for controlled responsive activation of the cleats. The sensors may be of any of a variety including piezoelectric crystals, magnetics, temperature, force, weight and solid state accelerometers or other device that could sense an external effect and convert said effect into a usable signal for the CPU to give a control output in the shoe. The drive mechanism may be through a mechanical shaft or cable, hydraulic pressure based on a function of different factors including but not limited to speed, weight, terrain, acceleration, lateral acceleration and vertical acceleration as more fully described herein. FIG. 2 shows a block diagram 50 of the potential sensors and their relation to the CPU and motor. Sensors 52 , 54 , 56 and 58 are shown including impact sensor 52 which may be magnetic, weight, temperature, piezoelectric crystals or solid state accelerometers, and/or a three dimensional accelerometers as shown in the X, Y and Z orientations as accelerometers 54 , 56 and 58 respectively. CPU 60 preferably has a sampling rate of several thousands of samples per second but may be of any a variety of rates to achieve the desired goals. Motor 62 which may one or a series of motors controlled by CPU 60 in response to sensor data electronically fed into CPU 60 by sensors 52 , 54 , 56 and 58 . As data is collected from the sensors, CPU 60 processes the data and based on either pre-determined criteria or other algorithm or program, activates the motor or motors to in turn activate cable tension, shaft work, hydraulics or other electronics to power the motors on the various cleat locations based on a function of the three one dimensional accelerometers or single three dimensional accelerometer, or based on other factors such as weight, velocity, temperature, force and other factors. FIG. 3 shows a schematic diagram of control 30 where CPU 44 is connected via ribbon conductor 46 to input sensors, including Y axis accelerometer 42 , Z axis accelerometer 40 and X axis accelerometer 34 maintained in housing 49 . Also included in housing 49 operatively connected to CPU 44 is impact sensor 32 and power generator and supply 38 . Housing 49 also includes a mechanical connection between the motor and transmission 48 to the active elements in the shoe cleat to activate the cleat according to a preferred embodiment of the invention. Control 30 is designed to be housed in the sole portion of a shoe or boot but in other embodiments may be in other portions of the shoe. Alternatively, the user may have access to a control to change the sensing parameters or control the cleats according to desired specifications while in use. FIG. 4 shows a bottom view of cleat system 70 with engine 76 in the arch portion of the shoe having a motor, transmission, and control with drive cables 77 or shaft 79 and gear boxes 74 and 75 (for example) for activation of each individual cleats 78 . Each cleat may be individually controlled by cables 79 or be activated through gear box 75 as shown with cleat 73 . The mechanical system for engaging the ground may include extendable flaps, spikes, stubs, frictional coefficient enhancers and surface area enhancers all controlled by the CPU and responsive to the various inputs from the sensors as more fully described herein. FIG. 5 shows a side cross sectional view of cleat system 80 with sensor 84 connected to CPU 82 that in turn drives cleat activation. Each cleat has its own actuator 92 that drives the projections 90 outward from cleat 89 when activated. In this embodiment, each individual cleat is connected through wire 85 that received control signals from CPU 82 to activate each individual cleat according to cleat specific torque conditions and other factors all operating independently from the other cleats. Cleat 88 is shown in a non-deployed state whereas cleat 89 has been engaged and projections 90 are deployed to engage the ground and increase traction. As the system is operating, each individual cleat engages the ground as controlled by the CPU. The projections are deployed and retracted depending on the control signals from the CPU to best increase traction in a real time basis. Deployment may be of any of a variety of extensions since each projection may be individually controlled and may be fully or partially extended. FIG. 6 shoes an embodiment of retractable spikes 104 that are driven by elemental shaft 102 that is engaged in each of the cleats by telescoping outward from the cleat upon a signal from the control circuit. Upon activation, element shaft 102 is pushed downward by action of the gearbox 103 on spike 104 which is in turn pushed downward and projects beyond the outer periphery of the cleat. The deployed cleat is shown as deployed spike 106 with elemental shaft 105 pushed downward. Each cleat is separately controllable through the main CPU and drive transmission or electrical signals to gearboxes 103 . FIG. 7 shows another embodiment using a hydraulic drive 112 that is connected via tubes 113 to activate individual cleats 115 by engaging projection 116 and pushing it outward in response to a control signal that deploys as shown in projection 118 . FIGS. 8A and 8B show another surface area enhancer 120 whereby the individual cleat is a three part mechanism driven by a gearbox 121 that upon actuation from a signal from the control circuit, expands the cleat by spreading legs 125 outward against biasing springs 126 and projecting center leg 127 downward. As the cleat is engaged, the three components of the cleat push outward creating greater surface area and hence a greater degree of traction. In an alternative embodiment, one could employ radio frequency wireless or intra red wireless or other electromagnetic frequency for control and actuation for cleat command in conjunction with feedback from the sensors and actuation system working in unison. This would allow for a smaller profile and permit systems to be placed in various positions throughout the shoe. The wireless system could also be adapted to transmit data regarding ambient conditions and permit a third party to adjust or control the reaction profile of the shoe system while in use. FIG. 9 shows another embodiment using a hydraulic drive system 130 to deploy any of a number of traction enhancers 134 already discussed. By using standard hydraulics of a piston and worm gear and master cylinder arrangement, hydraulic fluid can be used to actively drive the various cleat enhancers in real time in response to the sensors and calculation of the CPU. FIG. 9 shows a retractable spike system with individual control and gearboxes that activate the active element for extending and retracting the element. FIG. 10A shows a reservoir 140 operably connected through tube 141 to a motor (not shown) or other drive mechanism for activation through hydraulic tube 142 . Reservoir 140 may also be gas or air filled and be operably connected to a pneumatic drive system using pressure to engage individual cleats as discussed herein. FIG. 10B shows an alternative cleat mechanism with a circumferential extension 152 placed about cleat 150 that is engaged through any of a number of mechanisms for control of the cleat activation such as hydraulics, pneumatics, mechanical pulley or shaft and spring operations, or electromechanical devices. Extension 152 is spring biased by spring 156 in the upward or non-deployed position. Upon activation as heretofore described, drive bellow 155 is compressed against spring 156 which in turn pushes drive shaft 158 downward which is connected to extension 152 thereby deploying the active cleat element. The extension 152 creates greater surface area for the individual cleat and in turn increases traction. Each cleat may be separately operated as described herein to increase traction as needed. Alternatively, the various cleat systems described herein may deploy a plurality of cleats at the same time to reduce processing and control demands. It is well known in the art of control how to manage a number of deployments based on sensor data and achieve the optimal combination of deployment for the particular circumstance. While the invention has been described in connection with several preferred embodiments, it is not intended to limit the scope of the invention to the particular form set forth, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the following claims.
An active shoe cleat system with a shoe having a processor in the shoe operably connected to cleats on the bottom of the shoe, at least one sensor that measures at least one parameter pertaining to ambient conditions on the shoe, a projection within the cleats that are deployed in response to control signals from the processor generated in response to data from information provided in part by the sensor, and means for urging the projection outward from within the cleat. In a preferred embodiment, the cleat may be activated by hydraulics or pneumatics or have a direct motor driven cable, gear or shaft work system. The sensors may monitor a variety of ambient conditions such as speed, torque, acceleration, force, water presence or other factors affecting traction and performance.
0
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates generally to the field of oilfield exploration, production, and testing, and more specifically to additives for oil-based drilling fluids for filtration control, suspension, lubrication and lost circulation, and their uses in such applications. [0003] 2. Description of Relevant Art [0004] A drilling fluid or mud is a specially designed fluid that is circulated through a wellbore as the wellbore is being drilled to facilitate the drilling operation. The various functions of a drilling fluid include removing drill cuttings from the wellbore, cooling and lubricating the drill bit, aiding in support of the drill pipe and drill bit, and providing a hydrostatic head to maintain the integrity of the wellbore walls and prevent well blowouts. [0005] An important property of the drilling fluid is its rheology, and specific rheological parameters are intended for drilling and circulating the fluid through the well bore. The fluid should be sufficiently viscous to suspend barite and drilled cuttings and to carry the cuttings to the well surface. However, the fluid should not be so viscous as to interfere with the drilling operation. [0006] Specific drilling fluid systems are selected to optimize a drilling operation in accordance with the characteristics of a particular geological formation. Oil based muds are normally used to drill swelling or sloughing shales, salt, gypsum, anhydrite and other evaporate formations, hydrogen sulfide-containing formations, and hot (greater than about 300 degrees Fahrenheit (“°F”) holes, but may be used in other holes penetrating a subterranean formation as well. [0007] An oil invert emulsion-based drilling fluid may commonly comprise between about 50:50 to about 95:5 by volume oil phase to water phase. Such oil-based muds used in drilling typically comprise: a base oil comprising the external phase of an invert emulsion; a saline, aqueous solution (typically a solution comprising about 30% calcium chloride) comprising the internal phase of the invert emulsion; emulsifiers at the interface of the internal and external phases; and other agents or additives for suspension, weight or density, oil-wetting, fluid loss or filtration control, and rheology control. Invert emulsion-based muds or drilling fluids (also called invert drilling muds or invert muds or fluids) comprise a key segment of the drilling fluids industry. [0008] When drilling wellbores in hydrocarbon-bearing formations to recover hydrocarbons worldwide, there is a continuing and growing desire to enhance efficiencies. Minimizing the number of different additives needed for a drilling fluid and minimizing the variation in such additives from well to well, field to field, country to country, is helpful in realizing the efficiency goal. Preventing loss of drilling fluid is also important. Many times, wells are drilled through lost circulation-prone zones prior to reaching a potential producing zone, requiring use of lost circulation materials to reduce losses of drilling fluids in such zones. Typical lost circulation materials for drilling operations, however, have been directed to water-based solutions. [0009] Increasingly, invert emulsion-based drilling fluids are being subjected to ever greater performance and cost demands as well as environmental restrictions. Consequently, there is a continued need and industry-wide interest in new drilling fluids and additives that provide improved performance while still affording environmental and economical acceptance. SUMMARY OF THE INVENTION [0010] The present invention provides a method for modifying or enhancing one or more properties of a drilling fluid used in drilling a wellbore in a subterranean formation for the recovery of hydrocarbons. According to the method, an oil absorbing material is used with the drilling fluid, particularly an oil or invert emulsion based fluid, as a viscosifier, rheology modifier, suspension agent and/or filtration control agent. The oil absorbing material may also be used to minimize mud losses by gelling at a desired location in the formation. The oil absorbing material may also be added prior to or with cement or during cementing of the wellbore, to absorb any excess oil and enhance the bond strength of the casing. Although the focus of the invention is with the oil absorbing material as an additive to oil based drilling fluid, the oil absorbing material may also increase lubricity of an aqueous based drilling fluid. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS [0011] The present invention meets the need of enhancing efficiency of oil well drilling and completion by providing an oil absorbent material having global utility for a variety of functions in drilling and completing wellbores in subterranean formations. In one embodiment, the oil absorbent material of the invention is a homopolymer or copolymer comprising styrene, butadiene, acrylate, phthalate, and carbonate salts. In another embodiment, the oil absorbent material is an elastomeric polymer comprising isoprene, isobutylene, ethylene, acrylonitrile, hydrogenated nitrile, norbornene, fluorinated, perfluorinated, ether block amides, or the halogenated congeners of any of these above listed materials. Commercially available oil absorbent materials that may be used in the invention include: NORSOREX® APX1, available from Astrotech in Vienna, Austria; ENVIRO-BOND® 403, available from Petroleum Environmental, L.L.C. in Rapid City, Mich.; A610, A611, A650, available from Nochar Inc. in Indianapolis, Ind.; PETROBOND™ N-910, N-990, also available from Nochar Inc. in Indianapolis, Ind.; WASTE-SET™ 3200, 3400, available from Environmental and Fire Technology, L.L.C. in Grand Rapids, Mich. [0012] According to the invention, the oil absorbent material may be added to the drilling fluid as a viscosifier and/or a suspension agent, and/or as a rheology modifier that can increase low end rheological properties. Low end rheology corresponds to shear rates of 10.2 sec-1 or less on a Fann 35A rheometer with a R1 rotor and B1 bob at 6 rpm. The oil absorbent material may further be used to maintain suitable viscosity of the drilling fluid during transportation. That is, the oil absorbent material may be used to impart a higher viscosity to the drilling fluid for transport and then may be depleted so as to allow the drilling fluid to have a lower viscosity for use as a drilling fluid. This rheology modification for transport may also help the drilling fluid maintain suspension of solids until the time of use as a drilling fluid. [0013] The oil absorbent material may also be used according to the invention as a lost circulation material. In one embodiment, the oil absorbent material may be deployed in a pill or spacer at concentrations sufficiently high as to provide a firm, non-flowable gelled matrix in the treated zone of the subterranean formation. The oil absorbent material can form a completely gelled matrix in as little as about 30 seconds or can take 5 hours or more to completely form a gelled matrix, depending on the concentrations of the oil absorbent material added. For gelation, the oil absorbent material may be used with linear, cyclic, aliphatic, aromatic, olefinic, or esterified base oils. In another embodiment, the oil absorbent material may be deployed as an aqueous dispersion to the desired location in the subterranean formation and then chased with a suitable base oil for gelation at that location for a rapid set and to provide a type of reverse gunk squeeze. [0014] The oil absorbent material of the invention may further be used in cementing a well drilled with oil based fluid. According to the invention, the oil absorbent material is used prior to addition of cement or with cement to absorb excess oil down hole and to increase the bond strength between the formation and the casing in completing the well. As used herein, the term “cementing” shall be generally understood to include operations for casing a borehole as well as operations for cementing a borehole unless stated otherwise. EXPERIMENTAL [0015] Tests of an oil absorbent material with commonly used base oils for drilling fluids were conducted to determine the effect and compatibility. Mixtures of 1 g Nochar A610 oil absorbent material were prepared with 40 ml of each of the following base oils: ENCORE® isomerized olefin base oil, available from Halliburton Energy Services, Inc. in Houston, Tex. and Duncan, Okla., ACCOLADE® ester/internal olefin blend oil, available from Halliburton Energy Services, Inc. in Houston, Tex., ESCAID® 110 dearomatized light hydrocarbon oil, available from ExxonMobil in Houston, Tex., SARALINE® 185V synthetic oil, available from Shell in Houston, Tex., and diesel. A non-flowable gel formed with the ENCORE® sample, with some syneresis. Different concentrations were then tested, specifically, 3.5 g of Nochar A610 additive in 50 ml of ENCORE® oil and 1.0 g of Nochar A610 additive in 35 ml of ENCORE® oil, simulating >25 lb/bbl to 10 lb/bbl. A concentration of 1.0 g of Nochar A 610 additive in 40 ml of ENCORE® oil, simulating 9 lb/bbl was also tested. A firm, non-flowable gel was formed at concentrations ranging from 25 lb/bbl to 10 lb/bbl. The gel structure formed at 9 lb/bbl but with syneresis. [0016] Tests with Nochar A611 at 70 lb/bbl indicated that the oil absorbent material increased the viscosity of the oils, namely ENCORE® base oil, ACCOLADE® base oil and diesel, at room temperature. The oils continued to increase in viscosity over time to form only slightly flowable gels. Nochar A611 formed a transparent gel at a slower rate than Nochar A610 at room temperature. For example, Nochar A610 at 23 lb/bbl concentration in a base oil formed a flexible gel in less than one minute, while Nochar A611 at 23 lb/bbl concentration in a base oil formatted a flowable gel after greater than thirty minutes. Thus, the time for a desired degree of gelation may be tuned to account for temperature by using a mixture, such as a mixture of both Nochar A610 and A611 in this example. [0017] Oil based mud (OBM) or drilling fluid was prepared according to the following composition in Table 1 resulting in a 13.6 lb/gal OBM. The water phase salinity for the calcium chloride brine used was 250,000 ppm. Nochar A611 was added at varying concentrations ranging from 4 to 9 lb/bbl. The rheology and gel strengths of the prepared samples A-C were then tested. [0000] TABLE 1 Oil Based Mud Compositions with Oil Absorbant Additive SAMPLE OBM A B C Mineral oil, bbl 0.52 0.52 0.52 0.52 Emulsifier, lb/bbl 10 10 10 10 Lime, lb/bbl 1 1 1 1 Calcium chloride brine, bbl 0.20 0.20 0.20 0.20 Filtration Control Agent, lb/bbl 2 2 2 2 Suspension Agent, lb/bbl 1 1 1 1 Nochar A611, lb/bbl — 4 6 9 Barite, lb/bbl 324.1 324.1 324.1 324.1 WPS, ppm 250,000 250,000 250,000 250,000 Fluid Density, lb/gal 13.6 13.6 13.6 13.6 [0000] TABLE 2 Fann 35 Rheology at 120° F. and Gel Strength Data SAMPLE OBM A B C 600 rpm 30 141 172 232 300 rpm 17 89 110 132 200 rpm 12 70 86 96 100 rpm 8 48 60 57  6 rpm 2 12 22 13  3 rpm 1 9 18 10 Plastic Viscosity, cP 13 52 62 100 Yield Point, lb/100 ft 2 4 37 48 32 Tau 0 0 6 14 7 10 s/10 m gel 2/2 15/16 19/21 12/14 [0018] The rheology of the base OBM of Table 1, as shown in Table 2, was poor, with ineffective suspension of the barite and no gel strength, leading to barite settling, without addition of any additive according to the present invention. The viscosity of Sample A, which contained 4 lb/bbl of Nochar A611 according to the invention, significantly increased to provide an OBM with improved solids suspension. Samples B and C containing 6 and 9 lb/bbl of Nochar A611, respectively, according to the invention, further modified the rheology by increasing the overall fluid viscosity. Nochar A611 readily viscosified the OBM. However, the gel strengths of each sample remained relatively flat despite the fluid viscosity increase. [0019] A representative ship out synthetic based fluid (SBF) or ship out drilling fluid was prepared according to the following compositions in Table 3 using a water phase salinity of 280,000 ppm for the calcium chloride brine, which gave a fluid density of 10.1 lb/gal. Nochar A611 was added at concentrations ranging from 0.5 to 2 lb/bbl. The rheology and gel strengths of the prepared samples D-F were then tested using a Fann 35 viscometer. [0000] TABLE 3 Representative Ship Out Synthetic Based Mud Compositions with Oil Absorbant Additive SAMPLE SBF D E F Internal olefin base fluid, bbl 0.60 0.60 0.60 0.60 Emulsifier, lb/bbl 6 6 6 6 Lime, lb/bbl 1 1 1 1 Calcium chloride brine, bbl 0.28 0.28 0.28 0.28 Filtration Control Agent, lb/bbl 2 2 2 2 Suspension Agent, lb/bbl 1 1 1 1 Nochar A611, lb/bbl — 0.5 1 2 Barite, lb/bbl 121.0 121.0 121.0 121.0 WPS, ppm 280,000 280,000 280,000 280,000 Fluid Density, lb/gal 10.1 10.1 10.1 10.1 [0000] TABLE 4 Fann 35 Rheology at 120° F. and Gel Strength Data for Ship Out Fluid SAMPLE SBF D E F 600 rpm 64 73 83 105 300 rpm 43 49 56 70 200 rpm 33 41 45 58 100 rpm 24 30 34 42  6 rpm 8 11 12 15  3 rpm 6 8 10 12 Plastic Viscosity, cP 21 24 27 35 Yield Point, lb/100 ft 2 22 25 29 35 Tau 0 4 5 8 9 10 s/10 m/30 m gel 7/8/9 9/9/11 9/9/10 11/11/12 [0020] The synthetic based fluid samples were aged while rolling at 150° F. for 16 hours. The viscosity of compositions D-F increased with respect to the synthetic based fluid formulation with increasing A611 concentration (Table 4). The Tau 0 value also increased with increased A611 concentrations thus providing further indication of the viscosity increase. However, the fluid viscosity increase was attained within 2 hours after A611 addition as there was not a significant viscosity change when comparing the base samples to the aged samples. The gel strengths remained flat in the formulations containing A611, which could help maintain the viscosity profile over time during transportation. [0021] The exemplary additives disclosed herein are not expected to have any direct or indirect effect on equipment associated with the preparation, delivery, recapture, recycling, reuse, and/or disposal of the disclosed additives. The disclosed additives are also not expected to have any direct or indirect effect on any transport or delivery equipment used to convey the additives to a well site or downhole. The disclosed additives are also not expected to directly or indirectly affect the various downhole equipment and tools that may come into contact with the additives such as, but not limited to, drill string, coiled tubing, drill pipe, drill collars, mud motors, downhole motors and/or pumps, floats, MWD/LWD tools and related telemetry equipment, drill bits (including roller cone, PDC, natural diamond, hole openers, reamers, and coring bits), sensors or distributed sensors, downhole heat exchangers, valves and corresponding actuation devices, tool seals, packers and other wellbore isolation devices or components, and the like. [0022] The foregoing description of the invention is intended to be a description of preferred embodiments. Various changes in the details of the described fluids and methods of use can be made without departing from the intended scope of this invention as defined by the appended claims.
A method using a single additive to modify or enhance one or more properties of a drilling fluid for drilling a wellbore in a subterranean formation, prevent lost circulation during the drilling, and/or increase bonding strength during cementing of the wellbore. The additive comprises an oil absorbent material comprising homopolymers or copolymers comprising styrene butadiene, acrylate, phthalate, and carbonate salts.
2
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a reaction block assembly capable of accommodating round bottom flasks, of different sizes, and is for use upon a magnetic stirrer integrated with a hot plate. Such stirrers generate a magnetic field, and various sizes of round bottom flasks are easily accommodated by this device for effective rotating the magnetic stir bars in the flask. The base of the assembly is aluminum and is configured to provide excellent heat transfer land and not to interfere with the magnetic field, being generated from below the hot plate surface. [0003] 2. Brief Description of the Prior Art [0004] In the field of organic chemistry it is often desirable to perform a chemical reaction under precise heat transfer and stirring conditions. conditions. Known laboratory stirrers suited for use with the present invention include the Opti CHEM Model CG-1993-01 hot plate stirrer from Chemglass of Vineland NJ; the Ikamag RET, RCT and RH Basic magnetic stirrers from IKA of Germany; and the Heidolph MR3000 series of magnetic stirrers. Typically such hotplates are round and have a diameter of 135 mm, although some hotplate stirrers, such as the Snijders Model 34532, from Snijders of the Netherlands, employ a top plate diameter of 194 mm. [0005] Magnetic stirrers that do not allow for heating are also known. Wanninger at al. (U.S. Pat. No. 5,547,280) illustrates a stirrer with a round, flat glass top. Other magnetic stirrers without a hotplate employ a 6 inch by 6 inch square top plate, such as the Model 1266 from Labline, or a square 7 inch by 7 inch square top plate, such as the Model S46720, from Thermolyne. [0006] The use of reaction blocks to hold reaction vessels upon a surface of a magnetic stirrer is known. Landsburger (U.S. Pat. No. 3,356,316) illustrates a vinyl block with a plurality of test tube holders. [0007] Where both stirring and heating are desired, prior art heat conduction blocks have been constructed of various configurations and materials. Kindmann (U.S. Pat. No. 5,529,391) illustrates thermoelectric elements and metal cooling fins attached to each of four sides of a square, aluminum heat conducting block, that then is positioned over a plurality of individual magnetic stirring devices. Ladlow et al. (U.S. Pat. No. 6,905,656) illustrates a solid adapter block with a plurality sockets to arrange test tubes outside of the periphery of a round hot plate stirrer, wherein the adapter block is said to be made of any chemically resistant material, such as PTFE, aluminum or stainless steel. Asynt, of the United Kingdom, sells a DrySyn aluminum adapter block for supporting a standard 1000 ml flask upon a round hot plate stirrer, with separate inserts available for accommodating 500 ml, 250 ml, 100 ml and 50 ml flasks, wherein two plastic handles are attached to opposing sides of a large aluminum block to allow lifting. [0008] Such apparatus can overheat a hot plate, due to a large mass of aluminum, are difficult to manipulate and include large exposed surfaces that invite burns from inadvertent contact. The present device is advantageous over such known devices in that it allows a conventional magnetic stirrer to be used with various sizes of common round bottom flasks and features a flask holder with thin walls and a small aluminum mass, except about the center where the excellent heat transfer is concentrated. A heat shield is cooled by natural convection through interconnected narrow air spaces, and is easy and safe to manipulate, even when quickly taking the reaction block off the hot plate. SUMMARY OF THE INVENTION [0009] A reaction block according to the invention provides a safe and cost effective solution for replacing existing oil baths and heating mantles. An innovative heat shield, preferably of solid Teflon (PTFE resin), substantially surrounds the exterior surfaces of an inner aluminum flask holder, to both provide a substantially continuous gripping surface region and keep the entire exterior surface area at a temperature safe to touch. For example, in the preferred embodiment discussed below, the PTFE shield remained at approximately 79° C. when heating a 100 mL round bottom flask to 179° C. Thereby, various common size flasks, holding a hot liquid and one or more magnetic stir bars, can be accommodated securely in this novel reaction block and the reaction block may be quickly and securely grabbed at any vertical side surface and placed upon, or removed from, a hot plate stirrer. [0010] The present invention provides an improved reaction block, wherein an inner flask holder is shielded both around the circumference of its vertical sides with an insulating material and also shielded at its outer upper surface by an annular surface of insulating material located between the sides and a central flask holding recess. The shielding preferably is a single piece of solid plastic or resin that is removably secured to the inner flask holder and spaced therefrom by spacers to provide a natural convection air space therebetween. [0011] The present invention preferably provides the bottom of the inner flask holder with a lip that acts to loosely engage the side surface of a hot plate. This ensures that the reaction block is in good heat transfer contact with the hotplate and also correctly locates the supported flask centrally within the magnetic flux being generated by the magnetic stirring mechanism. [0012] The inner flask holder preferably is cast, forged or machined from aluminum, but alternatively might be made of any non-ferrous metal, stainless steel, ceramic or other high heat transfer coefficient material that will not interfere with a magnetic flux. The preferred embodiment is an inner flask holder that has a lower surface and lip that are circular in shape, to accommodate the common, round hot plate stirrers, as discussed above, but rectangular, square or any other particular shape is contemplated. [0013] The preferred embodiment of the improved reaction block illustrated in the drawings comprises an inner flask holder with a central recess that will engage a 100 mL round bottom flask and will accept optional inserts for 10, 25 and 50 mL flasks. A second embodiment, not illustrated, comprises a reaction block with an inner flask holder with a central recess that will engage a 500 mL flask and will accept an optional insert for engaging a 250 mL round bottom flask. Preferably the flask inserts are color coded for easy identification by the lab technician. Each of the inserts preferably are shallow cups, made of aluminum and with a common lower convex surface configuration that will make a large area contact against the concave surface of the central recess in the inner flask holder. The upper concave surfaces of the insets are likewise shaped to make a large area contact with the bottom of a particular size of inserted flask. [0014] Hence, it is a first object of the present invention to provide a reaction block with an insulating heat shield that substantially surrounds an inner flask holder, to keep the exterior surface area at a temperature that is safe to touch. [0015] It is a second object of the present invention to provide a reaction block with a plastic or resin covering that substantially surrounds an inner flask holder, and provides gripping surface regions completely around its circumference. [0016] It is a third object of the present invention to provide a reaction block with an insulating heat shield, that substantially surrounds an inner flask holder which further comprises a concave, central recess that accepts a series of inserts sized to accommodate different round bottom flasks but with convex lower surfaces that will make good heat transfer contact with the central recess. [0017] It is a fourth object of the present invention to provide a reaction block essentially comprising a round, heat conducting inner flask holder with an air space between outer surfaces thereof and a surrounding layer of insulating material so as to cool, by natural convection, a continuous vertical gripping surface region around the circumference of the device. [0018] It is a fifth object of the present invention to provide a round reaction block essentially comprising a flask holder at its center and a surrounding layer of solid PTFE resin, wherein the inner flask further comprises a large vertically extending aluminum mass surrounding the central flask holder above a horizontal, thin wall aluminum circular element with a lower surface and vertical edge that will engage upon and around a common round hot plate stirrer. [0019] It is a sixth object of the present invention to provide a reaction block essentially comprising a round, aluminum inner flask holder with a surrounding layer of insulating material and a central recess that will make good heat transfer contact with a series of aluminum adapters for different size flasks, that also are color coded. BRIEF DESCRIPTION OF THE DRAWINGS [0020] A preferred embodiment of the invention is described in detail below, with reference to the accompanying drawings, wherein: [0021] FIG. 1 is a right front perspective, explosion view of a reaction block with an optional 50 ml. flask adapter insert according to a preferred embodiment of my invention, in an intended use upon a laboratory magnetic stirrer hot plate, that is shown in dotted line; [0022] FIG. 2 is a top plan view of the reaction block of FIG. 1 ; [0023] FIG. 3 is a is a bottom plan view of the reaction block of FIG. 1 ; [0024] FIG. 4 is a left side elevation view of the reaction block of FIG. 1 , the right side being a mirror image thereof; [0025] FIG. 5 is a vertical cross-section view of the reaction block of FIG. 1 , taken along the line 5 - 5 of FIG. 2 ; and also in an intended use upon a top surface of a laboratory magnetic stirrer and hotplate, that is shown in dotted line. [0026] FIG. 6 is a top plan view of a first insert for accommodating a 50 ml round bottom flask. [0027] FIG. 7 is a top plan view of a second insert for accommodating a 25 ml round bottom flask. [0028] FIG. 8 is a top plan view of a third insert for accommodating a 10 ml round bottom flask. [0029] FIG. 9 is a side elevation view of a first insert for accommodating a 50 ml round bottom flask. [0030] FIG. 10 is a side elevation view of a second insert for accommodating a 25 ml round bottom flask. [0031] FIG. 11 is a side elevation view of a third insert for accommodating a 10 ml round bottom flask. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0032] The preferred embodiment of the improved reaction block illustrated in FIG. 1 comprises an inner flask holder 2 of machined aluminum with an encircling heat shield 4 . The aluminum flask holder central element 12 has an upper support edge 50 , which surrounds a concave central recess 14 , and is supported above a thin wall, circular horizontal element 22 . The concave central recess 14 is sized to engage the bottom of a 100 mL round bottom flask. [0033] FIG. 1 illustrates a preferred reaction block with an insulating heat shield that is an annular solid block which substantially surrounds a central mass of an aluminum inner flask holder 2 , in a manner that keeps the exterior surface 32 at a temperature that is safe to touch. A block is preferably of cast or machined rigid Teflon (PTFE) resin 4 and shaped to shield substantially all exterior surfaces of the inner flask holder 2 . [0034] FIGS. 2 and 3 show top and bottom plan views of the reaction block when assembled. FIGS. 1 and 5 illustrate how the shield is removably mounted and separated from hot surfaces of the flask holder by three ceramic standoffs 6 , 8 , 10 that are ½ inch in diameter and ⅜ inches in length and are spaced equally upon the horizontal element 22 around the holder central element 12 . The shield is held in place by cap screws 16 , 18 , 20 that engage threaded holes 26 , 28 , 30 tapped into the top of the thin wall of horizontal element 22 and end at its lower surface 80 . As shown in FIG. 5 , the cap screw 18 also is countersunk in hole 28 well below the surface 38 in order to avoid a burn from contact with the head of the cap screw. [0035] Hence, interconnected horizontal and vertical spaces create a natural convection air path. As shown in FIGS. 2 and 5 , a top vertical air space 58 is defined between PTFE shield upper vertical wall 60 and flask holder top support surface 50 . Likewise, a horizontal air space 56 is defined between thin wall flask holder element 22 and the lower horizontal surface of the PTFE block 4 and a bottom vertical air space 54 is defined between outside of vertical element 24 and PTFE block lower vertical wall 72 . The PTFE block outer surface was found to remain at approximately 79° C. when heating a 100 mL round bottom flask to 179° C. The thin wall horizontal element 22 quickly conducts heat radially inward towards the mass of the central flask holder element 12 , so the aluminum flask holder overall has a minimized amount of mass and thermal capacity. Hence, the improved reaction block quickly responds to changes in temperature being required by the controller (not illustrated) which dictates the temperature at the hot plate surface 70 . [0036] FIGS. 1, 4 and 5 further illustrate the configuration of a solid PTFE shield that both substantially covers and surrounds all hot surfaces of the hot plate 70 as well as the inner flask holder 2 , and also provides gripping surface regions completely around the circumference 32 of the reaction block. The shield has a thick annular portion with an upper surface 38 that extends inward to a cylindrical inner surface 60 that is closely spaced outwardly from the outside of cylindrical holder element 12 . Hence, shield outer circumference 32 meets upper surface 38 at a chamfered corner and is backed by a thick annular ring of solid PTFE resin. That mass further acts to retard heat transfer away from the hot flask holder 2 or the hot plate 70 and towards the circumference 32 . That surrounding, thick annular layer of insulating material is quite rigid and allows a very stable and continuous gripping surface region to be defined by round grooves 34 , 36 which act as secure finger holding surfaces that are uniform and run completely around the circumference. [0037] FIG. 5 further illustrates an intended use of the assembled reaction block upon a top surface of a conventional laboratory magnetic stirrer and hotplate, 62 . The shape of a round hot plate upper surface 70 being about 135 mm in diameter is schematically represented by dotted line. The flat lower surface 80 of the thin wall, circular horizontal element 22 is about 138 mm in diameter and will engage over and around the flat area and edge of hot plate upper surface 70 . The reaction block will be located against sliding by the holder vertical element 34 , which in turn is covered by a PTFE shield. In this manner, the reaction block will remain fixed and centrally located within the magnetic field of the laboratory stirrer, but no hot surface will be exposed for an inadvertent contact with the hands of the lab technician. [0038] As shown in FIGS. 1, 6 and 9 , the concave central recess 14 , which is sized for engaging against a 100 ml flask bottom, also will engage against the rim 46 and lower convex surface 44 of an optional first adapter insert, that has an upper concave surface 48 sized to engage the bottom of a 50 mL flask. The upper surface 38 of the PTFE block has a notch 40 that registers radially with a notch 42 in the top support surface 50 of the inner flask holder 2 . That facilitates engaging a tool under the insert rim 46 in order to lift out the insert. [0039] FIGS. 7 and 10 show a second adapter insert, having an upper concave surface 68 that will engage the bottom of a 50 mL flask, an annular rim 66 and a lower convex surface 64 that likewise will engage central recess 14 . FIGS. 8 and 11 show a third adapter insert, having an upper concave surface 78 that will engage the bottom of a 10 mL flask, an annular rim 76 and a lower convex surface 74 that likewise will engage central recess 14 . [0040] The three inserts are machined from aluminum, and preferably are anodized in the different colors red, blue and yellow as a color code to facilitate proper selection in the lab. [0041] Each of the inserts are shallow cups are of the same overall diameter and with the same sized annular rims, but have different wall thicknesses, in order to present a common lower convex surface configuration that will assist in making a large area contact against the concave surface 14 of the central recess in the inner flask holder. The upper concave surfaces of the insets are likewise shaped to make a large area contact with the bottom of a particular size of inserted flask, and are shallow to permit the lab technician to visually inspect a reaction occurring within the liquid being synthesized without the need to employ a surrounding oil bath or a heating mantle. [0042] While preferred embodiments have been shown and described in order to satisfy the requirements of 35 USC § 112, the invention is to be defined solely by the scope of the appended claims
A reaction block for mounting various round bottom flasks upon a laboratory, magnetic hot plate stirrer. An aluminum inner flask holder effectively conducts heat and does not interfere with a magnetic flux. A solid heat insulating material substantially surrounds and is spaced from the flask holder, in order to keep the reaction block at a safe temperature and provide easy gripping surface regions that extend completely around its circumference.
1
FIELD OF THE INVENTION This invention relates to an intravascular stent to maintain vascular patency in humans and animals. Also, the invention relates to a means for reducing the risk of thrombosis due to the implanted stent. BACKGROUND OF THE INVENTION Intravascular stents have long been applied to maintain vascular patency. Intravascular stents are used in conjunction with balloon angioplasty wherein a balloon is inflated to expand a constricted vessel in order to restore proper blood flow. The intravascular stent is then positioned inside the now expanded vessel to ensure the vessel maintains the enlarged diameter. However, attempts to develop a prosthetic stent which would hold open a blood vessel and not develop transluminal thrombus have enjoyed limited long term success. There has been very little significant improvement with the exception of an effort to create a more expansible metallic stent. For a metallic stent to satisfy the limits for antithrombogenesis while simultaneously maintaining the lumen of a blood vessel in which the stent has been placed, the stent has to fulfill the electrochemical laws for thrombosis. That is, the stent has to maintain a potential difference more negative than plus 250 millivolts versus the normal hydrogen electrode. In addition, the stent must exhibit limited corrosion and limited tissue destruction over the duration of the stent life. It was found very early on that while some of the metals on the corrosive side of the electromotive series would maintain a very negative potential, many of these metals upon ionizing and going into solution produced cellular destruction due to tissue and cellular toxicity. For this reason, the number of materials which can be used to develop a metallic implantable intravascular stent is limited to four or five metals that are known to be antithrombogenic and anticorrosive. The most useful of these appears to be titanium or aluminum. Titanium and aluminum produce a non-soluble surface oxide on exposure to blood and tend not to go into solution. In addition, titanium and aluminum develop a very negative potential with reference to the normal hydrogen electrode. Titanium and aluminum deposit almost no coagulant materials, coagulant enzymes, or proteins. A number of patents have been found describing various stent designs as well as methods for delivery of the stent to the desired position in the vessel. These patents include: U.S. Pat. Nos. 3,868,956 and 4,503,569, each of which describes methods wherein a stent comprising a temperature responsive device is implanted in the damaged vessel and thereafter expanded by means of an external heat source. U.S. Pat. No. 4,553,545, which discloses a method whereby a complex mechanical rotating device and coaxial cables are employed to increase the diameter of the implanted stent. U.S. Pat. No. 4,580,568, which describes a stent wherein a single wire forming a closed loop is expanded in the damaged vessel to maintain vascular patency. The loop of wire is compressed to form a series of straight segments and bands, wherein said bends store energy in the compressed state. Upon removal of a compression means the stent expands and exhibits a circular configuration. U.S. Pat. No. 4,649,992, which describes a device in combination with a catheter which is a compression spring retained by a partially inflated balloon and an abutment immediately behind the balloon on the catheter shaft. The spring prosthesis is transported in this manner to the desired location and released by totally evacuating said balloon thereby allowing the spring prosthesis to expand linearly. U.S. Pat. No. 4,681,110, which describes a catheter for delivery of a stent comprising woven plastic strands forming a tube which can be compressed radially. The orientation of the plastic strands provide the resilience for tube to expand from the compressed state. U.S. Pat. No. 4,768,507, which discloses a catheter comprising an outer cylinder and inner core, wherein said inner core comprises spiral grooves for containing a coil spring stent. Pliers are used to facilitate the loading of the coil spring into said grooves whereupon completion of the loading of the outer cylinder is placed over the inner core thereby retaining the coil in the compressed state until the coil is released. U.S. Pat. Nos. 4,690,684, and 4,720,176, each of which discloses a stent for aligning the ends of the vessel during anatomosis by thermal bonding. The stent comprises an integral solid of biologically compatible material to align the vessel ends together during anatomosis. Upon completion of the anastomosis the stent fully melts into the fluid flowing through the vessel. U.S. Pat. No. 4,770,176 also discloses a method of anastomosing a vessel utilizing the stent described in U.S. Pat. No. 4,690,684. U.S. Pat. No. 4,878,906, which describes a prosthesis comprising a flexible thin-walled plastic sleeve for repairing damaged vessels. The sleeve having sufficient length to cover the damages area of the vessel forms a sealed interface on its outer peripheral ends with the inner peripheral surface of the vessel, thereby providing a bridge, bypassing the damaged area of the vessel. U.S. Pat. No. 4,830,003, which discloses a cylindrical shaped stent comprising angled wires of biocompatible metal. The angled wires are connected obliquely at alternate ends to form a compressible open ended tube. U.S. Pat. No. 4,866,062, which discloses a radially expandable coronary stent. The stent comprises a flat expandable wire band which is preformed in a zigzag pattern to provide expansion capability. The band which is wound into a cylindrical shape is inflated by means of a variable diameter device. The band expands radially exhibiting a cylindrical shape with increasing diameter. U.S. Pat. Nos. 4,800,882, 4,739,762 and 4,733,665, each of which discloses an expandable intraluminal graft. These grafts are made of wire or a thin balled tubular member and can be expanded by an angioplasty balloon associated with a catheter. U.S. Pat. No. 4,760,849, which discloses a planar blank which may be made into a helical coil spring stent. U.S. Pat. No. 4,665,918, which describes a system and method for implanting a generally tubular prothesis member having an unobstructed central passageway into the length of a blood vessel. The prosthesis member contracts to a smaller dimension for delivery through the unobstructed portion of the blood vessel, and is outwardly expansible in the blood vessel. The prosthesis member is positioned in a contracted condition between a delivery catheter and outer sheath, and expands outwardly in response to the removal of the sheath. None of the aforegoing patents, however, disclose an anti-thrombogenic stent which decreases turbulence and improves hydraulic flow of blood therethrough. Accordingly, there remains a need for such a device. SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved intravascular stent, whereby the intravascular stent decreases the turbulence and improves the hydraulic flow of the blood through the vessel, thus, reducing the possibility of transluminal or "out flow turbulence" thrombus developing in conjunction with the implanted stent. Another object of the present invention is to provide an intravascular stent that satisfies the electrochemical laws for thrombosis while exhibiting limited corrosion over the duration of stent life. The improvements of this invention over the prior art devices are the ability of the present invention to decrease the turbulence of blood flow and to improve the hydraulic flow of the blood through the vessel. These improvements are achieved in an antiturbulent, anti-thrombogenic intravascular stent comprising a helically shaped strip of predetermined thickness of a non-thrombogenic material capable of assuming a contracted position for insertion into a blood vessel and expansible to a normally expanded position having a first end, a second end, an outer surface in contact with the blood vessel for urging the blood vessel outwardly, and an internal surface in contact with blood passing therethrough from the first end to the second end. The stent internal surface includes an airfoil for increasing the velocity of blood flow through the stent without creating areas of stagnant or turbulent flow therein or adjacent thereto. A preferred material for the stent is titanium or aluminum and an airfoil may be formed on the strip of non-thrombogenic material by including a leading edge and a trailing edge connected by a smooth transition area therebetween across the width of the strip, with the height of the leading edge being greater than that of the trailing edge. Alternatively, the airfoil can be formed by providing the predetermined thickness of the strip at the first end to be greater than the predetermined thickness of the strip at the second end, with the predetermined thickness of the strip between the first and second ends gradually diminishing to form a relatively smooth transition therebetween. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side view of a stent in accordance with the present invention in position in a blood vessel; FIG. 2 is an exploded view of the stent of FIG. 1 to show the airfoil surface thereof; and FIG. 3 is an exploded view of another airfoil surface for a stent according to the invention. DETAILED DESCRIPTION OF THE INVENTION The stent of the present invention is preferably a titanium or aluminum air foil helix. FIG. 1 illustrates the stent 100 in position in a blood vessel 110. When implanted onto an obstruction 120 in the vessel 110, the outer surface of the stent 100 contacts the obstruction and inner surface of the vessel. The inner surface of the stent 100 allows blood to flow therethrough. Advantageously, the inner surface of the stent is shaped in the form of an airfoil. These shapes can be made by machining a flat strip of titanium or aluminum followed by configuring the machined strip in the form of a helix. The airfoil surface is achieved by configuring each stent segment to mimic the configuration of an airplane wing. Thus, each segment has a leading edge 130 of greater height than trailing edge 140, with a smooth transition 150 therebetween, as shown in FIG. 2. Thus, the thickness and cross sectional area of the stent is uniform throughout its length. FIG. 3 illustrates an alternate embodiment of an airfoil surface for the stent of the invention. In this embodiment, the thickness of the strip at the forward end 160 of the stent is made thicker than that of the rearward end 170 of the stent. The thickness of the strip between the forward and rearward ends gradually diminishes to form a relatively smooth transition area. Thus, the overall configuration of the internal surface of the stent is similar to that of an airplane wing. The spaces between the surface segments formed by the strip do not detract from its utility of increasing blood flow velocity without creating turbulence of stagnant areas. As the fluid in the vessel passes over the stent, the airfoil configuration increases the velocity of the blood flow therethrough in the same manner as air flows over the wing of an airplane. Blood flows in the direction of arrow A from the forward end to the rearward end of the stent. The increased velocity of the blood flow passing through said stent reduces the possibility of thrombosis because the blood flows more rapidly past the area which previously experienced the buildup or obstruction. When a blood vessel has an obstruction, blood also flows faster as it passes the obstruction, but it produces turbulence and stagnant pools of blood distal to the obstruction. This can cause thrombus and blood element growth of the obstruction due to material depositing from the turbulent and stagnant blood pools. The present invention avoids these problems by configuring the inner portion of the stent to have an airfoil or venturi, tube like surface. Thus, as blood flows by, its speed is increased and its pressure is decreased without creating turbulent or stagnant areas of blood. This higher speed, lower pressure blood flow moves rapidly past the stent, thus preventing the deposition of material therefrom. Also, the lower pressure of the blood flowing through the stent causes any material which would tend to deposit to be pulled away from the wall of the vessel where the stent is located. By use of the stent of the invention, the obstruction is removed and means are provided to prevent its regrowth. Advantageously, the stent is formed from a thrombosis resistant material, such as titanium or aluminum, as noted above. The titanium or aluminum stent upon exposure to blood maintains a potential difference more negative than 250 millivolts versus the normal hydrogen electrode, thereby fulfilling the electrochemical laws for prevention of thrombosis. Also, titanium and aluminum stents exposed to blood deposit almost no coagulant materials, coagulant enzymes or proteins, thereby further reducing the possibility of thrombosis. In addition, metals which tend to go into solution produce cellular destruction due to tissue and cellular toxicity thereby reducing stent life. Stents of titanium, and to a slightly lesser degree aluminum, produce a non-soluble oxide on exposure to blood and tend not to go into solution, thus preventing a shortened stent life. The stent of this invention can be inserted and be transported via a standard delivery system, such as that shown in U.S. Pat. No. 4,665,918, the content of which is expressly incorporated herein by reference thereto. Upon reaching the desired location in the damaged vessel, the outer sheath of the delivery system is removed and the stent expands radially contacting the inner walls of said vessel thereby preventing a decrease in the diameter of said vessel. While it is apparent that the invention herein disclosed is well calculated to fulfill the objects above stated, it will be appreciated that numerous modifications and embodiments may be devised by those skilled in the art. For example, the internal surface airfoil configuration may be obtained by bending or cold forming a strip, rather than by machining such surfaces on the strip. It is intended that the appended claims cover all such modifications and embodiments as fall within the true spirit and scope of the present invention.
An anti-turbulent, anti-thrombogenic intravascular stent of a helically shaped titanium or aluminum strip having an airfoil on internal surfaces thereof for increasing blood flow velocity through the stent without creating areas of stagnant or turbulent flow therein.
0
FIELD OF INVENTION The present invention relates to abrasive disks used in the conditioning of pads in chemical mechanical polishing of silicon wafers of the sort used in the production of integrated circuits. More specifically, the present invention relates to an apparatus and method for extending the service life of disks that are used to condition the polishing pads. BACKGROUND OF THE INVENTION Integrated circuits (ICs) are typically produced en mass upon single, circular semiconductor wafers having diameters of up to about 30 centimeters (cm). The semiconductor wafers from which the ICs are cut may have multiple layers of wiring devices on a single wafer. Each layer of circuitry consists of thousands of electrical circuits that will eventually be die cut from the wafer. The successive layers are separated from one another by intervening dielectric layers made of materials such as silicon dioxide. The dielectric and/or metal forming each layers has to be polished or ‘planarized’ before the next layer of circuitry can be deposited. The polishing (or planarization) process is called CMP, which stands for Chemical Mechanical Planarization. CMP is superior to previously used planarization technologies because it has proven capable of both local and global planarization of the materials used in the fabrication of multi-level ICs. During CMP, a slurry of fine abrasive particles suspended in liquid chemical solutions react with the surface being polished to achieve the necessary degree of flatness prior to the deposition of the next layer. A layer of insulating material, commonly silicon dioxide or variations thereof, is used to separate each successive layer of the fabricated circuitry so that each sequentially deposited IC layer will not, unintentionally, interconnect with subsequent layers of circuitry. In order to pack more devices into less space, the requirements for feature size within the ICs has shrunk dramatically. Features that protrude into or across circuitry layers and make contact where not intended, or do not make contact where intended, can cause short circuits or open circuits and other defects that make an otherwise valuable product unusable. One difficulty with CMP is a reduction in the rate at which the CMP pad, or CMP polishing pad, removes material from the wafer being polished and thus the speed of planarization decreases with use. Most conventional polishing pads are made of various kinds of filled or unfilled thermoplastics such as polyurethane. The polishing surface of the pads tends to become glazed and worn during the polishing of multiple wafers. The pad's surface characteristics change sufficiently to cause the polishing performance to deteriorate. Deterioration of polishing pad performance is typically reversed by the use of means to ‘condition’ the pad surface during use, or between polishing steps, as needed. The pad conditioning procedure uses a conditioning disk that has diamonds or other hard abrasive particles bonded to it. When this disk is applied to the polishing pad it mills away the top surface of the pad exposing fresh asperities and recreating the micro texture in the surface. Conditioning of the pad is also necessary because the surface of the polishing pads undergoes plastic deformation during use, due to pressure and heat. Pad conditioning provide a consistent pad polishing performance by periodically regenerating the surface of the pad. Some polishing operations use continuous pad conditioning, others intermittent, some between wafers. The conditioning apparatus generally consists of an arm to which is attached a rotating disk to which is attached the abrasive conditioning surface that rotates while it radially traverses the surface of the rotating polishing pad. The conditioning disk generally has fine diamond grit bonded to its active surface. Like the pad, the conditioning disk also undergoes wear of its abrasive surface, requiring that it be replaced periodically in a process that requires stopping of the CMP processing of wafer and a consequent reduction in productivity. Thus the conditioning of polishing pads places service-life constraints upon the conditioning disk. A way to increase the operational of the service life of the conditioning disk is thus a desirable goal. It is worth noting that the rotating conditioning disk also radially traverses the polishing pad while renewing the pad surface and restoring polishing pad performance. When the conditioning disks are new, the diamond particles are very sharp and quickly ‘roughen’ up the polishing pads. Over time, however, the conditioning effectiveness of the disks decreases until it has to be replaced. SUMMARY OF THE INVENTION According to the present invention, a circular abrasive conditioning disk having a rotational center comprises a plurality of abrasive portions that are independently movable in relation to an active abrasive conditioning surface of a CMP pad. The plurality of abrasive portions are independently movable in a direction that is approximately normal to the plane that defines said active abrasive conditioning surface. The plurality of congruent abrasive portions are arranged in relation to one another in such as way as to comprise a radially symmetrical pattern about the rotational center of the conditioning disk, and at least three of the plurality of independently movable abrasive portions are able to move more or less simultaneously into the plane that defines the active abrasive conditioning surface, and in such as way as to be radially symmetrical about the rotational center of the circular abrasive conditioning disk. Also according to the present invention, vertical movement means are provided for precise movement of at least three of the plurality of independently movable abrasive portions into or out of the plane that defines the active abrasive conditioning surface. Still further according to the present invention, each congruent abrasive portion of the plurality of congruent abrasive portions is wedge shaped and has a vertex that is oriented approximately toward the rotational center of circular abrasive conditioning disk, said congruency deriving from each of the plurality of wedge shaped abrasive portions having a similar shape and substantially equal characteristic dimensions to the other wedge shaped abrasive portions. Yet further according to the present invention, the abrasive segments can also be circular in shape and have diameters that are equal to that of the other circular abrasive portions. Still further according to the present invention, each abrasive portion of the plurality of abrasive portions can be other than wedge shaped or circular, so as to be noncircular in shape, but mutually similar in shape and having the same characteristic dimensions as each of the other of the plurality of abrasive portions. Each of the noncircular abrasive portions is disposed in relation to the other noncircular abrasive portions in such a way as to comprise a radially symmetrical pattern about the rotational center of the circular abrasive conditioning disk. At least three of the plurality of independently movable noncircular abrasive portions are able to move more or less simultaneously into the plane that defines the active abrasive conditioning surface, and they are able to move more or less simultaneously into the plane that defines the active abrasive conditioning surface and are disposed in relation to one another in such as way as to be radially symmetrical about the rotational center of the circular abrasive conditioning disk. Also, according to the invention, a circular abrasive conditioning disk has a rotational center and comprises a plurality of concentrically arranged and circular abrasive portions that are independently movable in relation to a plane that defines an active abrasive conditioning surface of a CMP pad. Each of the plurality of concentric and circular abrasive portions is independently movable in a direction that is more or less normal to the plane that defines said active abrasive conditioning surface of the CMP pad. Further according to the present invention, the means are provided for precise movement of at least one of the plurality of independently movable concentric abrasive portions into or out of the plane that defines the active abrasive conditioning surface of a CMP pad. According to the present invention, a method is disclosed by which to extend the operational service life of a circular abrasive conditioning disk. The method comprises the steps of arranging a plurality of independently movable congruent abrasive portions about a common center of rotation having an axis of rotation, and fixing the plurality of independently movable congruent portions having abrasive surfaces in a circular pattern such that the abrasive surfaces of the abrasive portions are in a plane that is perpendicular to the axis of rotation. Further according to the present invention, the method also consists of constraining each congruent abrasive portion from radial or tangential motion with respect to the common center of rotation and with respect to one another. Also, means are provided for precise movement of one or more of the independently movable congruent portions into or out of said same plane that is perpendicular to said axis of rotation. DEFINITION The word ‘circular’ refers hereinbelow to the overall shape of the proposed conditioning disk according to the present invention and is to be construed in such a way, as should be readily apparent to those who are skilled in the art, as to include regular polygonal shapes having n sides wherein n is some number greater than two. BRIEF SUMMARY OF THE DRAWINGS The structure, operation, and advantages of the present invention will become further apparent upon consideration of the following description taken in conjunction with the accompanying figures (Figs.). The figures are intended to be illustrative, not limiting. Certain elements in some of the figures may be omitted, or illustrated not-to-scale, for illustrative clarity. The cross-sectional views may be in the form of “slices”, or “near-sighted” cross-sectional views, omitting certain background lines which would otherwise be visible in a “true” cross-sectional view, for illustrative clarity. In the drawings accompanying the description that follows, often both reference numerals and legends (labels, text descriptions) may be used to identify elements. If legends are provided, they are intended merely as an aid to the reader, and should not in any way be interpreted as limiting. FIG. 1 is an oblique schematic view of the prior art CMP system. FIG. 2 is an edge-on schematic view of a wafer in contact with a polishing pad that is being conditioned. FIG. 3A is an edge-on schematic view of wafer in contact with a polishing pad that is being conditioned, prior to wear away of the asperities. FIG. 3B is an edge-on schematic view of wafer in contact with a polishing pad that is being conditioned, subsequent to wear away of the asperities. FIG. 4A is an orthogonal view of the abrasive surface a first embodiment of the present segmented conditioning disk. FIG. 4B is an edge-on schematic view of the abrasive surface the first embodiment of the present segmented conditioning disk. FIG. 5A is a generalized, polygonal embodiment of the present segmented conditioning disk invention. FIG. 5B is a four-sided embodiment of the present segmented conditioning disk invention. FIG. 6 is an embodiment of the present invention in which the segments are circular. FIG. 7 is an embodiment of the present invention wherein the independently movable portions are concentric with one another. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Prior Art and State of the Art System FIG. 1 is an oblique schematic, partially cut-away, view of a polishing system 10 for polishing/planarizing the surface of a semiconductor wafer 12 , showing a prior art conditioning disk 14 that is rotationally driven by shaft 14 ′ which can move radially, according to the double-headed arrow 15 , with respect to the center of the polishing pad 16 which is affixed to the rotating platen 18 that is driven by the shaft 18 ′ about the axis A-A′. More specifically, the wafer 12 is rotated against the rotating polishing pad 16 (which has a top-most surface 17 ) by means of the rotating head 18 , which is driven by shaft 18 ′. The head 18 can also move radially with respect to the rotating polishing pad, as indicated by the double-headed arrow 19 . Referring the FIG. 2 , which is an orthogonal, edge-on schematic edge view of the top-most portion 17 of the polishing pad 16 and the moving wafer 12 , said top-most portion 17 has numerous independent pores 20 that contain a continually refreshed slurry 30 (i.e., indicated by flow arrows 30 ) consisting of fine abrasive material carried in a liquid mixture that might or might not be chemically reactive with the wafer 12 being polished. The slurry 30 is fed to the polishing surface 16 by means of the supply pipe 21 , as shown in FIG. 1 . The pores 20 can be characterized as microscratches that are close enough together to form wall structures 22 , portions of which are micro asperities that protrude far enough upward to make intimate contact with the wafer 12 . Arrows 27 , as shown in FIGS. 3A and 3B , indicate relative motions of the pad surface 17 and the wafer 12 . The micro asperities 22 provide contact regions 24 , whereat the slurry 30 reacts with and polishes the surface of the wafer 12 . One can think of the slurry 30 as an abrasive lubricant that moves between wafer 12 and each asperity peak 24 so as to, in effect, pressurize the abrasive slurry against the wafer surface being polished or planarized. The asperity peaks 24 deform somewhat during abrasively lubricated contact with the wafer 12 . FIGS. 3A and 3B are schematic edge-on views of the wafer 12 in contact with the top-most surface 17 of the polishing pad 16 , illustrating the effects upon the surface 17 and the asperity peaks 24 and 24 ′ as the polishing process takes place. That is to say, the asperity peaks 24 become worn down to the condition 24 ′, with the deleterious effect upon the polishing process being accordingly degraded by the increased surface areas of the worn peaks 24 ′, which corresponds to reduced pressure between the asperity peaks 24 ′ and the wafer 12 . Deterioration occurs continuously during the polishing/planarizing process. The real contact area increases over time as the asperities make direct push the abrasive slurry 30 against the wafer 12 , the effect being a reduction in the real contact pressure, which causes the material removal rate (from the wafer) to decrease. To achieve constant removal rate and uniformity, it is required to maintain a more or less constant contact area and effective pressure of the slurry 30 against the surface of the wafer 12 being polished. Accordingly, the function of the diamond abrasive conditioning disk 14 ( FIG. 1 ) is to regenerate the sharp-pointed asperities 22 ( FIG. 2 ) on the top-most surface 17 of the polishing pad 16 . As material is being removed from the wafer 12 by means of the polishing pad 16 and slurry 30 (in FIG. 2 ), debris also gets deposited into the voids 30 of the top part 17 of the polishing pad 16 . In order to have a consistent pad surface each time a wafer is pressed on the pad, the diamond abrasive conditioner disk 14 ( FIG. 1 ) resurfaces, or conditions or reconditions, the pad 16 . The conditioner 14 is typically a plate with diamonds bonded to it creating an abrasive surface (not shown). However, with repeated use, even diamonds become dull and lose their cutting and conditioning effectiveness. Thus it is the case that the conditioning disk 14 has to be replaced periodically in a process that requires stopping the CMP process and a consequent reduction in manufacturing productivity. First Embodiment of the Invention Whereas the prior art conditioning disk 14 has a single contiguous abrasive surface, the present invention envisions a segmented condition disk 40 , as shown schematically in FIGS. 4A and 4B . The conditioning disk 40 is but one embodiment of the present invention. (Arrows 45 indicate rotary motion and relative motion respectively in FIGS. 4A and 4B .) FIG. 4A shows the conditioning disk 40 as comprising congruent pie-shaped segments 42 , of which the exemplary set of twelve segments shown comprise four subsets labeled A, B, C, and D, each of which comprises three segments. The segments 42 are arranged about a common center or axis of rotation 46 in a plane that is perpendicular to said axis of rotation. Each movable and congruent segment 42 is from radial or tangential motion with respect to said axis of rotation, or shared or common center of rotation, and with respect to one another. The inventors also envision more or fewer segments 42 , as will be discussed in more detail below. Each of the twelve segments 42 of FIG. 4A are independently movable in a vertical direction, as indicated in the schematic edge-on side view of FIG. 4B ; more specifically, they the inventors envision, in this example of 12 segments, that a radially symmetrical set of any three of them, such as, for example, all segments labeled ‘B’, might be lowered, as shown in FIG. 4B , to engage the surface 44 of pad 16 that is being abraded during the conditioning process. The remaining segments, i.e., A, C and D in FIG. 4B are disposed above the plane of 44 , in a kind of storage position in which they are held in anticipation of future use or when the three segments A have been expended or worn out subsequent to conditioning use. The inventors envision that the conditioning disk 40 of FIG. 4A might be mounted upon a swiveling drive shaft (not shown) that will automatically adjust the angle of contact of the segments 42 with the plain of abrasion 44 of surface 17 in such a way as to maintain uniform conditioning pressure and action upon the surface 17 , even if the set of segments 42 that are in abrading contact with the surface 17 are not necessarily radially disposed with respect to the rotational center 46 of the disk 40 . That is to say, the inventors envision that the segmented conditioning disk 40 , according to the present invention, can be used in such a way that, say, for example, two of segments 42 labeled ‘A’ might be used in conjunction with two or three segments ‘D’ and/or ‘B’. The inventors further envision a means 43 for the raising and lowering of individual segments or sets of segments 42 , said raising-and-lowering means consisting of such actuators as solenoids, pneumatic or hydraulic pistons, screw drives or the like. More generally, the conditioning disk 40 according to the present invention comprises multiple sections/zones 42 , such that specific zones can be activated independently, i.e., moved vertically into or out of contact with the plain of abrasion 44 , which is coincident with the top-most surface 17 of the polishing pad 16 . The schematic side view of FIG. 4B shows three segments 42 , each labeled ‘B’, making contact with the plain of abrasion 44 upon the top-most surface 17 of the CMP pad 16 . That is to say, the three segments 42 are independently movable in relation to an active abrasive conditioning surface 17 of a CMP pad 16 . As should be evident to those skilled in the art upon contemplation of FIG. 4A , the segmented conditioning disk 40 according to the present invention can comprise, in general, of n number of segments 42 , where n is greater than at least three. Moreover, those skilled in the art might reasonably surmise that the rounded portion 48 of each segment 42 could as well be a chord 49 , such that said disk 40 would more accurately be describable as having a regular polygonal shape, rather than an overall circular, shape. Hence, the specific definition given above for the adjective ‘circular’ as referring herein to regular polygonal shapes, even though irregular polygonal shapes might also be contemplated by those skilled in the art. Thus it is that the object of this invention is concerned with extending the service life and operational consistency of polishing-pad conditioner disks. In its simplest embodiment the individual controlled multiple segment disk 40 ( FIG. 4A ) allows users to move one or more fresh conditioner surfaces into action by activating fresh segments and deactivating spent segments without having to stop the CMP process. An embodiment that offers further control would continue to use the segments as they wear but activate just enough fresh material from unused segments to compensate for the worn segments. In its most refined form, the present invention allows modulation not only of the number of segments in use at any given time but also the pressure applied to each in order to maintain a far more consistent cut rate of the polishing pad then the prior art conditioner disk can generate. As describe hereinabove, the raising-and-lowering means allows various segments or abrasive zones of the invention to be selectively brought into contact with the polishing pad 16 when needed to improve consistency of conditioning operation and consistency of the CMP process. As some of the abrasive segments/zones on the conditioner wear, others can be brought into or removed from action, thus maintaining the cut rate of the disk 40 and extending the time between tool downs for servicing of this part 40 . This invention would allow better use of conditioning disks by providing more stable conditioning rate. It is worth mentioning that another alternative is to use several zones or segments 42 to start and then slowly ramp the pressure on one or more other zones to maintain the optimal conditioning rate and desired result. Additional Embodiments of the Invention Those skilled in the art might easily imagine additional ways to provide a conditioning disk having the properties described hereinabove. For example, a conditioning disk 50 , shown in the schematic view of FIG. 5A , is shown comprising a plurality of independently moveable abrasive segments/zones/portions 52 having a collective shape equivalent to a regular polygon of n portions. FIG. 5B is an example of a disk 54 comprising only four portions 56 which add up to a ‘circular’ disk in accordance with the specific definition of ‘circular’ given hereinabove. FIG. 6 is an embodiment 60 of a conditioning disk comprised of multiple circular portions or segments 62 , each of which, either independently or in groups, can be raised or lowered to provide conditioning action of a polishing pad. As should be apparent to those skilled in the art, the segments 62 of the embodiment 60 and which are shown in FIG. 6 as having circular shapes need not be constrained only to circular shapes or to other regular shapes such as triangles or polygons. FIG. 7 is yet another embodiment of the present invention, wherein a segmented conditioning disk 70 comprises 3 or more or fewer concentric portions/zones 72 , 74 , 76 which can be moved into our out of operation independently or in groups. The circular abrasive conditioning disk 70 has vertical movement means (not shown in FIG. 7 ) that provide for precise movement of at least one of the plurality of independently movable concentric abrasive portions into or out of the plane that defines the active abrasive conditioning surface of a CMP pad. Although the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character—it being understood that only preferred embodiments have been shown and described, and that all changes and modifications that come within the spirit of the invention are desired to be protected. Undoubtedly, many other “variations” on the “themes” set forth hereinabove will occur to one having ordinary skill in the art to which the present invention most nearly pertains, and such variations are intended to be within the scope of the invention, as disclosed herein.
The present invention is an apparatus and method for extending the life of abrasive disks used in the conditioning of polishing pads used in chemical mechanical planarization (CMP) of polishing pads used to polish and/or planarize the surfaces of semiconductor wafers during the production of integrated circuits. The invention consists of the a disk comprising a plurality of abrasive segments, each of which is fixed in tangential and radial relationship to one another about the common axis of rotation of the conditioning disk. Means are provided for movement of the abrasive segments, individually or in sets, into or out of the plane of the active abrasive surface of the conditioning disk according to the present invention.
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CROSS-REFERENCE TO RELATED APPLICATION [0001] This application claims the benefit of U.S. Provisional Application Ser. No. 61/503,748, filed Jul. 1, 2011, which is incorporated herein by reference in its entirety. BACKGROUND [0002] The present disclosure relates to spray hood assemblies adapted to be moved over undesired foliage so as to temporarily enclose them when liquids (e.g., agricultural chemicals such as herbicide) are sprayed. The spray hood assemblies may assist in ensuring that a high percentage of the sprayed liquids are deposited where they are intended to be sprayed rather than being blown away or onto adjacent desired plants. [0003] Known are several spray hood, or shield, assemblies adapted to be moved over plants being grown in rows in a field so as to temporarily enclose them when liquids or agricultural chemicals are sprayed thereby helping to ensure that a high percentage of the sprayed liquids are deposited on or around undesired foliage intended to be sprayed rather than being blown away or onto adjacent plants. Such spray hoods have been sold by Ryan Manufacturing, Box 239, Newark, Ill. 60551 and Hiniker Company, P.O. Box 3407, Mankato, Minn. 56001, and are described in U.S. Pat. No. 4,947,581 and U.S. Pat. No. 5,155,933. Further, additional spray hoods, or shields, have been described in U.S. Pat. No. 5,155,933, U.S. Pat. No. 5,371,969, and U.S. Pat. No. 5,526,605. SUMMARY [0004] The exemplary spray hood, or shield, assemblies described herein may be adapted to be connected to a support frame moved over desired foliage, or plants, being grown in spaced rows from a ground surface (e.g., earthen surface) and to be moved along the ground surface between the rows of desired foliage while liquids such as herbicides (e.g., the herbicide commercially available as “Roundup” from Monsanto) not intended for contact with desired foliage in the rows may be sprayed between the rows onto undesired foliage (e.g., weeds) located between the rows of desired foliage over which the spray hood assembly passes. [0005] One exemplary spray hood assembly may be operable to spray liquid onto undesired foliage between rows of desired foliage using at least one spray nozzle. The at least one spray nozzle may extend along an axis and may include an upper flange and a lower flange. Each flange may extend perpendicularly from the axis around the at least one spray nozzle. The exemplary spray hood assembly may include a spray hood and at least one spray nozzle assembly. [0006] The spray hood may extend from a front end to a rear end and may define an outer surface and an inner surface. The inner surface may define a channel from the front end to the rear end. The spray hood may further define at least one spray nozzle aperture configured to receive the at least one spray nozzle. In at least one embodiment, the least one spray nozzle aperture defines an opening larger than each of the upper and lower flanges of the at least one spray nozzle. [0007] The at least one spray nozzle assembly may be configured to retain the at least one spray nozzle within the at least one spray nozzle aperture of the spray hood. The at least one spray nozzle assembly may include a first retention plate and a second retention plate. The first retention plate may be coupled to the spray hood and may define a receiving opening configured to receive a spray nozzle therein (e.g., a slot extending from an edge surface into an interior portion). The first retention plate may further define a top side and a bottom side. The second retention plate may be coupled to the spray hood and may define a receiving opening configured to receive a spray nozzle therein (e.g., a slot extending from an edge surface into an interior portion). The second retention plate may further define a top side and a bottom side. [0008] The at least one spray nozzle may be retained within the receiving opening of each of the first retention plate and the second retention plate such the top side of the first retention plate is adjacent the upper flange of the at least one spray nozzle and the bottom side of the first retention plate is adjacent the top side of the second retention plate and such that the bottom side of the second retention plate is adjacent the lower flange of the at least one spray nozzle. In at least one embodiment, the receiving opening of the first retention plate and the receiving opening of the second retention plate may be located opposite one another when the at least one spray nozzle is retained within the receiving opening of each of the first retention plate and the second retention plate. [0009] In one or more exemplary spray hood assemblies described herein, the spray hood may define a first fastener aperture and a second fastener aperture. Each of the first and the second fastener aperture may be located proximate the at least one spray nozzle aperture, and the at least one spray nozzle assembly may further include a first fastener configured to couple the first retention plate to the spray hood using the first fastener aperture, and second fastener configured to couple the second retention plate to the spray hood using the second fastener aperture. Further, the spray hood may further include a threaded nut molded into the spray hood for each of the first and the second fastener apertures—the threaded nut being configured to receive a threaded fastener. [0010] In one or more exemplary spray hood assemblies described herein, the spray hood may further include a raised area proximate the at least one spray nozzle aperture configured to contact the bottom side of the first retention plate. Further, the second retention plate may define an edge perpendicular to each of the top and the bottom sides and proximate the receiving opening, and the edge of the second retention plate may contact a side surface of the raised area of the spray hood. [0011] In one or more exemplary spray hood assemblies described herein, the receiving opening of each of the first and the second retention plates may define a first retaining surface, a second retaining surface, and a third retaining surface. The first, second, and third retaining surfaces may be configured to receive three of four sides of a square portion of the at least one spray nozzle located between the first flange and the second flange to restrict rotational movement of the at least one spray nozzle about the axis. [0012] Another exemplary spray hood assembly may be operable to traverse a ground surface and to spray liquid using spray nozzles onto undesired foliage between rows of desired foliage located on the ground surface. The spray hood assembly may include a spray hood and a closure sheet. [0013] The spray hood of the exemplary spray hood assembly may extend from a front end to a rear end along an axis and may define an outer surface and an inner surface. The inner surface may define a channel extending from the front end to the rear end. The channel may define an open end located at the front end of the spray hood. [0014] The spray hood may include a tapered front portion and a rear portion. The tapered front portion may extend from the front end to a transition region (e.g., the transition region may be a transition plane perpendicular to the axis) and may define a tapered front portion length parallel to the axis. In at least one embodiment, the spray hood may converge from the transition region to the front end such that the channel proximate the front end is smaller than the channel proximate the transition region. The rear portion may extend from the rear end to the transition region and may define a rear portion length parallel to the axis. In at least one embodiment, the tapered front portion length may be greater than 30% of the rear portion length. In at least one embodiment, the tapered front portion length may be greater than 40% of the rear portion length. [0015] The closure sheet may be coupled to the spray hood proximate the open end of the channel. The closure sheet may be configured to retain liquid when sprayed by spray nozzles within the channel and to allow the passage of undesired foliage into the channel of the spray hood when operating. Further, the channel of the spray hood may further define a rear open end located at the rear end of the spray hood. The spray hood assembly may further include a rear closure sheet coupled to the spray hood proximate the rear open end of the channel, and the rear closure sheet may be configured to retain liquid sprayed by spray nozzles within the channel and to allow the passage of undesired foliage out of the channel of the spray hood. [0016] In one or more exemplary spray hood assemblies described herein, the spray hood assembly may further include at least one gathering rod extending from the spray hood proximate the transition region to the front end. The at least one gathering rod may be configured to direct undesired foliage into the channel. Further, the at least one gathering rod may define a proximal portion and a distal portion. The proximal portion may be coupled to the spray hood proximate the transition region and may extend beyond the front end parallel to the axis. The distal portion may be coupled to the spray hood proximate the front end and coupled to the proximal portion. [0017] In one or more exemplary spray hood assemblies described herein, the spray hood assembly may further include at least one knock-down bar located within the channel extending perpendicular to the axis. The at least one knock-down bar may be configured to deflect undesired foliage located within the channel downwardly towards the ground surface. [0018] The above summary is not intended to describe each embodiment or every implementation of the present disclosure. A more complete understanding will become apparent and appreciated by referring to the following detailed description and claims taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0019] FIG. 1 is a perspective view of an exemplary spray hood assembly. [0020] FIG. 2 is a front view of the spray hood assembly of FIG. 1 . [0021] FIG. 3 is a rear view of the spray hood assembly of FIG. 1 . [0022] FIG. 4 is a left side view of the spray hood assembly of FIG. 1 . [0023] FIG. 5 is a right side view of the spray hood assembly of FIG. 1 . [0024] FIG. 6 is a top view of the spray hood assembly of FIG. 1 . [0025] FIG. 7 is a bottom view of the spray hood assembly of FIG. 1 . [0026] FIG. 8 is a perspective view of an exemplary spray nozzle assembly of the spray hood assembly of FIG. 1 . [0027] FIG. 9 is an exploded perspective view of the spray nozzle assembly of FIG. 8 . [0028] FIG. 10 is a cross-sectional view of the spray nozzle assembly of FIG. 8 . [0029] FIG. 11 is another cross-sectional view of the spray nozzle assembly of FIG. 8 . [0030] FIGS. 12A-B are right side views of prior art spray hoods. [0031] FIGS. 12C is a right side view of an exemplary spray hood of the spray hood assembly of FIG. 1 . [0032] FIG. 13 is a perspective view of a plurality of spray hood assemblies attached to a frame mounted to a tractor. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS [0033] In the following detailed description of illustrative embodiments, reference is made to the accompanying figures of the drawing which form a part hereof, and in which are shown, by way of illustration, specific embodiments which may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from (e.g., still falling within) the scope of the disclosure presented hereby. [0034] Exemplary apparatus and systems shall be described with reference to FIGS. 1 - 1 - 11 & 12 C. It will be apparent to one skilled in the art that elements from one embodiment may be used in combination with elements of the other embodiments, and that the possible embodiments of such apparatus and systems using combinations of features set forth herein is not limited to the specific embodiments shown in the Figures and/or described herein. Further, it will be recognized that the embodiments described herein may include many elements that are not necessarily shown to scale. Still further, it will be recognized that the size and shape of various elements herein may be modified but still fall within the scope of the present disclosure, although certain one or more shapes and/or sizes, or types of elements, may be advantageous over others. [0035] Multiple views of an exemplary spray hood assembly 10 are depicted in FIGS. 1-11 & 12 C. Generally, the exemplary spray hood assembly 10 is operable to traverse a ground surface and to spray liquid, such as herbicide, using spray nozzles onto undesired foliage (e.g., weeds) between rows of desired foliage (e.g., crops such as cotton) located on the ground surface. To traverse the ground surface, the spray hood assembly 10 , or multiple spray hood assemblies 10 , may be attached to a frame mounted on a tractor. [0036] For example, a tractor 200 towing a frame 202 attached to a plurality of spray hood assemblies 204 is shown in FIG. 13 . The spray hood assemblies 204 are positioned along the frame 202 in parallel positions such that the spray hood assemblies 204 may be moved by the tractor 200 between rows of desired foliage (e.g., crops such as cotton, plants, etc.) being raised in field to temporarily enclose weeds between the rows of desired foliage while liquids such as herbicides are sprayed onto the weeds through the spray hood assemblies 204 by a pumping system carried by the tractor 200 . [0037] The exemplary spray hood assembly 10 includes a spray hood 12 . The spray hood 12 extends from a front end 14 to a rear end 16 along an axis 18 . Further, the spray hood 12 may further define an outer surface 20 and an inner surface 22 (see FIG. 7 ) opposite the outer surface 20 . The spray hood 12 may have a generally U-shaped cross section (i.e., a cross section taken perpendicular to the axis 18 ) and may be made of uniformly thick, resiliently flexible polymeric material (e.g., made of about 0.21 inch thick polypropylene). The spray hood 12 may be made, or formed, by spin or rotary molding to form two of the spray hoods 10 together as a generally cylindrical part, and by then cutting the spray hoods 12 from each other, but could also be made by injection molding. [0038] The inner surface 22 defines a channel 24 within which the undesired foliage (e.g., weeds) may be temporarily located as the spray hood assembly 10 is moved over a ground surface. The channel 24 defines at least a portion of a chamber that encloses the undesired foliage such that any liquid sprayed within the channel 24 only contacts the undesired foliage and not the desired foliage located outside of the channel 24 . The channel 24 extends from the front end 14 to the rear end 16 . The channel 24 may define an open front end 15 located at the front end 14 of the spray hood 12 and an open rear end 17 located at the rear end 16 of the spray hood 12 . As described previously, the spray hood defines an axis 18 . The channel 24 of the spray hood 12 may be described as extending along the axis 18 . [0039] The spray hood 12 includes a tapered front portion 30 and a rear portion 40 . The tapered front portion 30 extends from the front end 14 to a transition region 50 . As shown in FIG. 12C , the tapered front portion 30 defines a tapered front portion length 32 that is parallel to the axis 18 . The rear portion 40 extends from the rear end 16 to the transition region 50 and, as also shown in FIG. 12C defines a rear portion length 42 that is parallel to the axis 18 . [0040] The tapered front portion 30 may be described as the portion of the spray hood 12 where the spray hood 12 converges from the transition region 50 to the front end 14 such that the channel 24 proximate the front end 14 is smaller than the channel proximate the transition region 50 . Conversely, the tapered front portion 30 may be described as including divergent surfaces extending from the front end 14 toward the transition region 50 (e.g., at an angle a greater than or equal to about 10 degrees, about 15 degrees, about 20 degrees, about 25 degrees, about 30 degrees, 35 degrees, and/or less than or equal to about 25 degrees, about 30 degrees, 35 degrees, about 40 degrees, about 45 degrees with respect to the axis 18 ) so that its outer surface 20 may assist in lifting and directing portions of desired foliage along adjacent rows away from the channel 24 of the spray hood 12 . [0041] The exemplary spray hood 12 is a substantial improvement over prior art spray hoods. Right side views of prior art spray hoods 300 , 400 are depicted in FIGS. 12A-B , respectively, and a right side view of the exemplary spray hood 12 is depicted in FIG. 12C . The drawings shown in FIGS. 12A-C are shown to scale. Two measurements are shown for each of the spray hoods 300 , 400 , 12 depicted in FIGS. 12A-C : a tapered front portion length 302 , 402 , 32 , respectively, extending from the front ends of the spray hoods 300 , 400 , 12 to a transition region and a rear portion length 304 , 404 , 42 , respectively, extending from the rear ends of the spray hoods 300 , 400 , 12 to the transition region. The transition region is the region of the spray hood where the shape of the spray hood changes either to or from a taper. More specifically, a transition plane may extend through the transition region perpendicular to an axis that extends through the channel of each spray hood. The transition plane 306 , 406 , 51 may be used for the end points within the transition region for the tapered front portion lengths 302 , 402 , 32 and for the rear portion lengths 304 , 404 , 42 . [0042] The tapered front portion length 302 of the prior art spray hood 300 is about 5.5 inches and the rear portion length 304 of the prior art spray hood 300 is about 22.25 inches. In other words, the tapered front portion length 302 is about 25% of the rear portion length 304 in the prior art spray hood 300 . [0043] The tapered front portion length 402 of the prior art spray hood 400 is about 17.75 inches and the rear portion length 404 of the prior art spray hood 400 is about 22 inches. In other words, the tapered front portion length 402 is about 80% of the rear portion length 404 in the prior art spray hood 400 . Further, this spray hood 400 does not include an opening located proximate the front end. [0044] The tapered front portion length 32 of the exemplary spray hood 12 is about 12.75 inches and the rear portion length 42 of the exemplary spray hood 12 is about 26.25 inches. In other words, the tapered front portion length 32 is about 50% of the rear portion length 42 in the exemplary spray hood 12 . Such dimensions provided by the exemplary spray hood 12 provide improvements and advantages over the prior art spray hood 300 , 400 . For example, the prior art spray hood 300 has been often used to spray between rows of young cotton but has been found to not be as effective between rows of more mature cotton (e.g., due to entanglement with the more mature cotton, etc.). To spray the more mature cotton, the prior art spray hood 400 has often been used. The dimensions of the exemplary spray hood 12 allow to be used with young and more mature cotton with greater success than the prior art spray hoods 300 , 400 . [0045] Although as depicted the tapered front portion length 32 is about 50% of the rear portion length 42 , the tapered front portion length 32 may be greater than or equal to about 30%, about 35%, about 40%, about 45%, about 50%, and about 60% of the rear portion length 42 in the exemplary spray hood 12 . Further, the tapered front portion length 32 may be less than or equal to about 80%, about 70%, about 60%, about 55%, about 50%, and about 45% of the rear portion length 42 in the exemplary spray hood 12 . [0046] The spray hood 12 may further include axially spaced circumferentially extending rib-like reinforcing portions 13 spaced along its length. The rib-like reinforcing portions 13 may have V-shaped cross sections, with their leading outer surfaces being inclined at an angle so that they may assist in the lifting and directing of portions of desired foliage along adjacent rows away from liquid distribution and spraying apparatus described herein. [0047] A top portion 21 of the spray hood 12 may be adapted, e.g., by having two recessed areas between side bosses, to have lifting apparatus 60 attached thereto for suspending and raising/lowering the spray hood assembly 10 from a support frame. [0048] As shown in FIG. 7 , the spray hood 12 may further define one or more spray nozzle apertures 70 (e.g., at least one spray nozzle aperture, a plurality of spray nozzle apertures, etc.). Each spray nozzle aperture 70 may be configured to receive a spray nozzle 80 . The spray nozzle apertures 70 may be located about the spray hood 12 so as to allow spray nozzles 80 located therein to spray liquid within the channel 24 so as to contact any undesired foliage located in the channel 24 . In at least one embodiment, wherein the nozzle apertures 70 define an opening larger than the upper and lower flanges of the spray nozzles 80 , e.g., such that the nozzles 80 are not in direct contact with the spray hood 12 . [0049] The exemplary spray hood assembly 10 may include a liquid distribution apparatus 90 . The liquid distribution apparatus 90 may include anything that may be used to distribute sprayable liquid to the spray nozzles 80 . As shown, the liquid distribution apparatus 90 includes three hoses 92 extending to spray nozzles 80 . [0050] The spray nozzle 80 (e.g., as shown in FIGS. 8-12 ) may extend along an axis 82 and may include an upper flange 84 and a lower flange 86 . Each of the upper flange 84 and the lower flange 86 may extend perpendicularly from the axis 82 around the spray nozzle 80 . An exemplary spray nozzle 80 may be a nozzle of the type provided under the trademark “TeeJet” by Spraying Systems Co., Wheaton, Ill. The spray nozzles 80 may direct spray at desired orientations and locations within the channel 24 of the spray hood 12 . The spray pattern from each nozzle 80 can further be adapted as desired to the type of plant or location on the plant at which the spray is to be directed by selecting nozzles that provide different spray angles or spray patterns such as a circular or fan like pattern, nozzles with such types of patterns being well known in the art and available from Spraying Systems Co., Wheaton, Ill. [0051] The spray nozzles 80 may be located within the spray nozzle openings 70 and may be coupled to the spray hood 12 through the use of a spray nozzle assembly 100 . The spray nozzle assembly 100 may include a first retention plate 110 and a second retention plate 120 . [0052] Each of the retention plates 110 , 120 may be coupled to the spray hood and may define a receiving opening 112 , 122 , respectively, as shown in FIG. 9 . The receiving openings 112 , 122 are configured to receive the spray nozzle 80 therein. Further, each of the retention plates 110 , 120 further defines a top side 114 , 124 , respectively, and a bottom side, 116 , 126 , respectively (e.g., the bottom sides opposite from the top sides). [0053] A spray nozzle 80 may be retained within the receiving openings 112 , 122 of each of the retention plates 110 , 120 such that the top side 114 of the first retention plate 110 is adjacent (e.g., in contact with) the upper flange 84 of the spray nozzle 80 and the bottom side 116 of the first retention plate 110 is adjacent (e.g., in contact with) the top side 124 of the second retention plate 120 , and further such that the bottom side 126 of the second retention plate 120 is adjacent (e.g., in contact with) the lower flange 86 of the spray nozzle 80 . In effect, it may be described that the flanges 84 , 86 of the spray nozzle 80 “sandwich” both of the retention plates 110 , 120 . [0054] Further, an intermediate portion 88 of the spray nozzle 80 , which is the portion of the spray nozzle between the upper flange 84 and the lower flange 86 , is located in each of the receiving openings 112 , 122 of the retention plates 110 , 120 , respectively. As shown, the retention plates 110 , 120 are positioned about the spray nozzle 80 such that the receiving openings 112 , 122 are located opposite one another. In effect, it may again be described that the retention plates 110 , 120 are “sandwiching” the spray nozzle 80 between each other and within each of the receiving openings 112 , 122 . [0055] Although the receiving openings 112 , 122 may be defined by any shape operable to retain a spray nozzle, as shown, the receiving openings 112 , 122 define a slot extending from an edge surface 113 , 123 into an interior portion of the retention plates 110 , 120 , respectively. More specifically, the receiving openings 112 , 122 are defined by a first retaining surface 127 , a second retaining surface 128 , and a third retaining surface 129 (only labeled with respect to the second retention plate 120 in FIG. 9 ). The first, second, and third retaining surfaces 127 , 128 , 129 may be configured to receive three of four sides of a square portion (e.g., intermediate portion 88 ) of the spray nozzle 80 . Locating a square portion of the spray nozzle 80 within such retaining surfaces may assist in the restriction of rotational movement of the spray nozzle 80 about the axis 82 , which may, e.g., result in less adjustment to the spray nozzles 80 and better spray coverage inside the channel 24 . [0056] Although the retention plates 110 , 120 may be coupled to the spray hood 12 using various techniques, as depicted, the retention plates 110 , 120 are connected to the spray hood 12 using fasteners 102 . For example, the retention plates 110 , 120 may define apertures 104 and the spray hood 12 may define apertures 106 for receiving the fasteners 102 . Further, the spray hood 12 may further include threaded nuts molded into the spray hood 12 (although not shown) corresponding to apertures 104 and configured to receive a threaded fastener 102 (e.g., the thread fasteners 102 may include a serrated flange). [0057] As shown, the spray hood 12 includes a raised area 143 proximate the spray nozzle aperture 70 . The raised area 143 may be configured to be adjacent (e.g., to be in contact with) the bottom side 116 of the first retention plate 110 when the first retention plate is coupled to the spray hood 12 . Further, a portion of the edge 123 proximate the receiving opening 122 of the second retention plate 120 may be configured to be located adjacent, or in contact with, a side surface of the raised area 143 of the spray hood 12 (e.g., as shown in FIG. 11 ). [0058] The spray hood assembly 10 may further include a pair of closure sheets 150 , 152 coupled to the spray hood 12 at opposite ends of the channel 24 that are configured to retain liquid when sprayed by the spray nozzles 80 within the channel 24 . The front closure sheet 150 may be coupled to the spray hood 12 proximate the open end 15 of the channel 24 and may be further configured to allow the passage of undesired foliage into the channel 24 when the spray hood assembly 10 is being used (e.g., moved over a ground surface upon which undesired foliage is growing). Further, the rear closure sheet 152 may be coupled to the spray hood 12 proximate the open end 17 of the channel 24 and may be further configured to allow the passage of undesired foliage out of the channel 24 when the spray hood assembly 10 is being used (e.g., moved over a ground surface upon which undesired foliage is growing). For example, while the spray hood assembly 12 is being moved over undesired foliage, the undesired foliage may pass through the closure sheet 150 into the channel 24 , be sprayed by the spray nozzles 80 while the undesired foliage is in the channel 24 , and may exit the channel 24 through the closure sheet 152 . [0059] The closures sheets 150 , 152 may be formed of stiff polymeric material (e.g., 0.6 inch thick polyethylene). Further, the closure sheets 150 , 152 may each include continuous or un-slotted upper portions proximate their attachment or coupling to the spray hood 12 and may each include longitudinal side by side flap portions (e.g., each about 3 inches wide) extending from the upper portion toward the ground surface defining parallel slots or slits. [0060] The spray hood assembly 10 may further include one or more elongate knock-down bars 160 extending between opposite side wall portions of the spray hood 12 (as shown in FIG. 7 ) (e.g., perpendicular to the axis 18 ) and proximate the front end 14 of the spray hood 12 and front open end 15 of the channel 24 . The knock-down bars 160 may be configure to deflect undesired foliage located within the channel 24 downwardly towards the ground surface to, e.g., allow more of the undesired foliage to be sprayed with liquid when in the channel 24 . [0061] The spray hood assembly 10 may further include a pair of gathering rods 170 that are configured to direct undesired foliage into the channel 24 . The gathering rods 170 may extend from the spray hood 12 proximate the transition region 50 to the front end 14 . More specifically, the gathering rods may define a proximal portion 172 and a distal portion 174 . The proximal portion 172 may be coupled to the spray hood 12 proximate the transition region 50 and may extend beyond the front end 14 parallel to the axis 18 . The distal portion 174 may be coupled to the spray hood 12 proximate the front end 14 and may be coupled to the proximal portion 172 . [0062] Suspension apparatus 60 may also be included as part of the spray hood assembly 10 . The suspension apparatus 60 may be configured to suspend, or support, the spray hood 12 from a frame to be used in conjunction with a tractor (as shown in FIG. 13 ). The suspension apparatus 60 may include two rigid bars pivotally coupled to the spray hood 12 proximate the top portion 21 of the spray hood 12 . The two rigid bars may also be pivotally coupled to a frame member, which may be part of a frame or may be coupled to a frame. Such pivotal couplings may allow the spray hood 12 to be raised and lowered with respect to the ground surface. The suspension apparatus 60 may further include actuation apparatus (e.g., a hydraulic piston, etc.) to raise and lower the spray hood 12 . [0063] As an example, the spray hood 12 may be adapted for use between crop rows separated by about 36 to 40 inches (e.g., cotton) and may a have a length (parallel the axis 18 ) of about 39 inches and a channel width (perpendicular the axis 18 ) between the outer surfaces within the rear portion 40 of about 30 inches (e.g., in a range of about 15 inches to about 40 inches depending on use). Further, the spray hood 10 may define a channel width (perpendicular the axis 18 ) between the outer surfaces proximate the front end 14 of about 18 inches. Still further, the spray hood 10 may define a channel height (perpendicular the axis 18 ) between a lowermost portion of the spray hood 10 and the uppermost portion of the channel 24 . For example, the front open end 15 of the spray hood 10 may have a channel height of about 11.5 inches (e.g., in a range of about 6 inches to about 30 inches depending on use). [0064] All patents, patent documents, and references cited herein are incorporated in their entirety as if each were incorporated separately. This disclosure has been provided with reference to illustrative embodiments and is not meant to be construed in a limiting sense. As described previously, one skilled in the art will recognize that other various illustrative applications may use the techniques as described herein to take advantage of the beneficial characteristics of the apparatus and methods described herein. Various modifications of the illustrative embodiments, as well as additional embodiments of the disclosure, will be apparent upon reference to this description.
Spray hood assemblies may be adapted to be moved over undesired foliage so as to temporarily enclose them when liquids (e.g., agricultural chemicals such as herbicide) are sprayed. The spray hood assemblies may assist in ensuring that a high percentage of the sprayed liquids are deposited where they are intended to be sprayed rather than being blown away or onto adjacent desired plants.
1
CROSS-REFERENCE TO RELATED APPLICATION [0001] This application is a continuation-in-part of International Applications No. PCT/KR2014/002746 filed on Mar. 31, 2014 and No. PCT/KR2014/002748 filed on Mar. 31, 2014 which claims priority from Korean Patent Applications No. 10-2013-0034929 filed with Korean Intellectual Property Office on Mar. 30, 2013, No. 10-2013-0034930 filed with Korean Intellectual Property Office on Mar. 30, 2013, No. 10-2013-0150316 filed with Korean Intellectual Property Office on Dec. 5, 2013 and No. 10-2013-0150314 filed with Korean Intellectual Property Office on Dec. 5, 2013, the entire contents of which are incorporated herein by reference. FIELD OF THE INVENTION [0002] The inventive concepts relate to a precursor manufacturing a lithium rich cathode active material and a Lithium rich cathode active material manufactured using the same, and more specifically relates to a novel precursor for manufacturing a lithium rich cathode active material of which capacity properties and cycle life characteristics are considerably improved by solving problems of conventional lithium rich cathode active material and a Lithium rich cathode active material manufactured using the same. BACKGROUND [0003] Lithium batteries are widely utilized in electric home appliances because of relatively high energy density. Rechargeable batteries are generally referred to secondary batteries, and lithium secondary batteries usually include anode material introducing Lithium. [0004] Presently, lithium containing cobalt oxide such as LiCoO 2 of layered structure, lithium containing nickel oxide such as LiNiO 2 of layered structure or lithium containing manganese oxide such as LiMnO 2 of spinel structure is used for cathode activate material of the lithium ion secondary battery, and graphite material is mostly used for anode active material. [0005] LiCoO 2 is being widely employed at present because various properties such as cycle life characteristic are excellent, but there is limit to use in large quantity for a power source in such a field of electric vehicle because its stability is low and cobalt is short in resources and expensive. Therefore, it is difficult to introduce LiNiO 2 in a practical mass product process at a rational cost because of characteristics in manufacturing method. [0006] In contrast, the lithium manganese oxides such as LiMnO 2 , LiMn 2 O 4 are rich in resources, have advantage of using manganese with environment affinity and then becoming the center of interest as cathode active materials capable of replacing LiCoO 2 . However, these lithium manganese oxides also have disadvantage that cycle life characteristics is inferior. LiMnO 2 has disadvantages of small initial capacity and needs dozens of charge/discharge cycles to reach specific capacity. [0007] Further, the capacity of LiMn 2 O 4 is more seriously declined as repeating the cycles, and more specifically cycle characteristic is rapidly declined by manganese eruption and electrolyte dissolution at a temperature over 50° C. [0008] Recently, it has been suggested that Li 2 MnO 3 is introduced to elevate stability of layered base cathode active material and to increase theoretical available capacity. This cathode active material has properties in which a plane section appears at a high voltage section between 4.3V to 4.6V. This plane section is found where lithium and oxygen are desorbed from a crystal structure of Li 2 MnO 3 and lithium is inserted into an anode. Li 2 MnO 3 may not be used as an insertion electrode of the lithium battery because an insertion site of tetrahedral structure facing octahedral structure is inefficient to receive additional lithium. It is impossible to extract Lithium because a manganese ion is 4-valent and not oxidized easily in real potential. But, according to Materials Research Bulletin (Volume 26, page 463 (1991)), Rossouw et al., Li 2 O is removed from Li 2 MnO 3 structure by a chemical treatment producing Li 2-x MnO 3−x/2 thereby activating Li 2 MnO 3 electrochemically, and this process is accompanied by a little H + —Li + ion exchanges. According to Journal of Power Sources (Volume 80, page 103 (1999)), Kalyani et al. and Chemistry of Materials (Volume 15, page 1984, (2003)), Robertson et al., Li 2 MnO 3 is also activated electrochemically by removing Li 2 O from a lithium battery. However, this activated electrode is not preferable to performance of lithium battery. [0009] As described above, the lithium battery tends to lose in capacity when a Li 2−x MnO 3−x/2 electrode is solely used. However, U.S. Pat. Nos. 6,677,082 and 6,680,143 disclose that a composite electrode, for example, two components electrode system such as xLi 2 MnO 3 .(1−x)LiMO 2 (M=Mn, Ni, Co) in which Li 2 MnO 3 and LiMO 2 components are layered structure, is used thereby improving electrochemical properties and having high efficiency. [0010] There is electrochemical activation caused by lithium and oxygen desorption at the high voltage section of 4.3V through 4.6V and capacity may be increased by existing of the plane section, even if the cathode active material of the composite electrode structure is used, however, oxygen gas is generated in the battery to raise possibility of electrolyte dissolution and gas generation under high voltage and crystal structure is physically and chemically deformed by frequent charging/discharging such that rate capability is declined. As a result, there is a problem that the performance of battery is declined [0011] Further, a tail section of discharge voltage becomes lower such that it cannot contribute to capacity for mobile phones, or it is impossible for practical battery to achieve high output because the power for vehicles is insufficient to be at an invalid SOC (State Of Charge) region. [0012] Therefore, there is a growing necessity of technology to solve these problems basically. SUMMARY [0013] The present invention is objected to remedy the problems of the prior lithium rich cathode active material, and to provide a novel precursor for manufacturing lithium rich cathode active material of which capacity properties and cycle life characteristics are improved remarkably and lithium rich cathode active material using the same. [0014] In order to solve the above-described problems, the present invention provides a precursor for manufacturing lithium rich cathode active material expressed by following chemical formula 1 or 2: [0000] Ni α1 Mn β1 Co γ1−δ1 A δ1 CO 3   [Chemical formula 1] [0015] (In the chemical formula 1, A is at least 1 or 2 selected from the group consisting B, Al, Ga, Ti and In; α1 is 0.05 to 0.4; β1 is 0.5 to 0.8; γ1 is 0 to 0.4; and M is 0.001 to 0.1), and [0000] Ni α2 Mn β2−y2 Co γ2−δ2 Al δ2 A y2 CO 3   [Chemical formula 2] [0016] (In the chemical formula 2, A is at least 1 or 2 selected from the group consisting Mg, Ti and Zr; α2 is 0.05 to 0.4; β2 is 0.5 to 0.8; γ2 is 0 to 0.4; δ1 is 0.001 to 0.1; and y2 is 0.001 to 0.1). [0017] The particle diameter of the precursor for manufacturing lithium rich cathode active material is 5 to 25 μm. [0018] In the precursor for manufacturing lithium rich cathode active material according to the present invention, A of the chemical formula 1 is Al. [0019] The present invention also provides lithium rich cathode active material expressed by following chemical formula 3, which is manufactured from the precursor for manufacturing lithium rich cathode active material, [0000] Li 1+x Ni α1 Mn β1 Co γ1−δ1 A δ1 O 2   [Chemical formula 3] [0020] (In the chemical formula 3, x is 0.4 to 0.7; A is at least one or two selected from the group consisting B, Al, Ga, Ti and In; α is 0.05 to 0.4; β1 is 0.5 to 0.8; γ1 is 0 to 0.4; and δ1 is 0.001 to 0.1). [0021] The lithium rich cathode active material according to the present invention is expressed by xLiNi α1 Mn β1 Co γ1−δ1 A δ1 O 2 .(1−x)Li 2 MO 3 (0<x<1, M is a compound of Ni, Co, and Mn; and A is at least one or two selected from the group consisting B, Al, Ga, Ti and In). In the lithium rich cathode active material according to the present invention, A is Al. [0022] Namely, lithium rich cathode active material according to the present invention consists of layered bases expressed by LiNi α Mn β Co γ−δ A δ O 2 and Li 2 MO 3 , and different metal A displaces Co in the layered base expressed by LiNi α Mn β Co γ−δ A δ O 2 to improve high voltage life properties of the layered base expressed by LiNi α Mn β Co γ−δ A δ O 2 . During charging/discharging, metal ions such as A moves and disperses between layers to stabilize hexagonal structure, and to prevent Ni +2 ions from oxidizing into +3-valent or +4-valent ions. However, if the different metal A displaces Co excessively, output and capacity may be declined by decreasing Co content. Therefore, displacement amount of the different metal is preferable to 0.001 to 0.1. [0023] The lithium rich cathode active material according to the present invention is a layered structural composite or a solid solution. [0024] In the lithium rich cathode active material according to the present invention, A content: δ1, Li content: x1, Mn content: β1, Ni content: α1 and Co content: γ1-δ1 satisfy following relative formula, [0000] X 1≧δ1 and [0000] B 1≧3( x 1+α1+γ1−δ1) [0025] The present invention further provides lithium rich cathode active material which is expressed by following chemical formula and manufactured by the precursor for manufacturing lithium rich cathode active material, [0000] Li 1+x2 Ni α2 Mn β2−y2 Co γ2−δ2 Al δ2 A y2 O 2   [Chemical formula 4] [0026] (In the chemical formula 4, x2 is 0.2 to 0.7; A is selected from the group consisting Mg, Ti, and Zr; α2 is 0.05 to 0.4; β2 is 0.5 to 0.8; γ2 is 0 to 0.4; δ2 is 0.001 to 0.1; and y2 is 0.001 to 0.1). [0027] The lithium rich cathode active material according to the present invention is expressed by xLiMAl δ2 O 2 .(1−x)Li 2 Mn 1−y2 A y2 O 3 (0<x<1, M is a compound of Ni, Co, and Mn; A is selected from the group consisting Mg, Ti, and Zr; δ2 is 0.001 to 0.1; and y2 is 0.001 to 0.1). Namely, the lithium rich cathode active material according to the present invention consists of layered bases expressed by LiMAl δ2 O 2 and Li 2 Mn 1−y2 A y2 O 3 , and different metal Al displaces M in the layered base expressed by LiMAl δ2 O 2 and different metal A displaces Mn in the layered base expressed by Li 2 MnO 3 . Therefore, the different metal A participate electro-chemical activation of the Li 2 MnyO 3 to improve high voltage life properties and prevent Mn eruption, simultaneously. [0028] In the chemical formula 4, when M is Co, it is preferred that the replacement amount of Al is 0.001 to 0.1 because output and capacity are declined by decreasing Co content if the different metal A displaces Co position excessively. [0029] It is preferred that the displacement amount of the different metal A is 0.001 to 0.1 because capacity is declined if A displaces Mn excessively. It is more preferred that the displacement amount of the different metal A is 0.02 to 0.05. [0030] In the lithium rich cathode active material according to the present invention, in the chemical formula 4, Al content: δ2, Li content: x2 and different metal A content: y2 satisfy following relative formula, [0000] X 2≧δ2 and [0000] Y 2≧δ2 [0031] The lithium rich cathode active material according to the present invention is layered structural composite or solid solution state. [0032] The lithium rich cathode active material according to the present invention has particle intensity of at least 115 Mpa. BRIEF DESCRIPTION OF THE DRAWINGS [0033] The inventive concepts will become more apparent in view of the attached drawings and accompanying detailed description. [0034] FIG. 1 shows SEM images of precursor particles for manufacturing lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0035] FIG. 2 shows EDS analyses about sections of precursor particles for manufacturing lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0036] FIG. 3 shows SEM images of precursor particles for manufacturing lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0037] FIG. 4 shows EDS analyses about sections of precursor particles for manufacturing lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0038] FIG. 5 shows a XRD analysis about particles of lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0039] FIG. 6 shows a particle size analysis about particles of lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0040] FIGS. 7 through 9 show SEM images about particles of lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0041] FIGS. 10 through 12 show EDS analyses about particle sections of lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0042] FIGS. 13 through 15 show charging/discharging characteristics of batteries including lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0043] FIG. 16 shows cycle life characteristics of a battery including lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0044] FIG. 17 shows a XRD analysis about particles of lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0045] FIG. 18 shows a particle size analysis about particles of lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0046] FIGS. 19 through 21 show charging/discharging characteristics of batteries including lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0047] FIG. 22 shows cycle life characteristics of a battery including lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0048] FIGS. 23 and 24 show SEM images and EDS analyses of precursor for manufacturing lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0049] FIGS. 25 and 26 show SEM images and EDS analyses of precursor for manufacturing lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0050] FIGS. 27 and 28 show SEM images and EDS analyses of lithium rich cathode active material which is fabricated by an embodiment of the present invention; [0051] FIGS. 29 and 30 show SEM images and EDS analyses of lithium rich cathode active material which is fabricated by an embodiment of the present invention; and [0052] FIGS. 31 and 32 shows charging/discharging characteristics of a coin-half cell using lithium rich cathode active material which is fabricated by an embodiment of the present invention. [0053] FIGS. 33 and 34 show cycle life characteristics of the coin-half cells using the lithium rich cathode active materials which are manufactured by an embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS [0054] The inventive concepts will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the inventive concepts are shown. The advantages and features of the inventive concepts and methods of achieving them will be apparent from the following exemplary embodiments that will be described in more detail with reference to the accompanying drawings. It should be noted, however, that the inventive concepts are not limited to the following exemplary embodiments, and may be implemented in various forms. Accordingly, the exemplary embodiments are provided only to disclose the inventive concepts and let those skilled in the art know the category of the inventive concepts. In the drawings, embodiments of the inventive concepts are not limited to the specific examples provided herein and are exaggerated for clarity. [0055] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the singular terms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be understood that when an element is referred to as being “connected” or “coupled” to another element, it may be directly connected or coupled to the other element or intervening elements may be present. [0056] Similarly, it will be understood that when an element such as a layer, region or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present. In contrast, the term “directly” means that there are no intervening elements. It will be further understood that the terms “comprises”, “comprising,”, “includes” and/or “including”, when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. [0057] The present inventions will be described below in more detail with reference to exemplary embodiments. However, the inventive concept should not be construed as limited to the embodiments set forth herein. Example 1 Synthesis of a Precursor for Manufacturing Lithium Rich Cathode Active Material [0058] Nickel sulfate hexahydrate (NiSO 4 .6H 2 O), cobalt sulfate heptahydrate (CoSO 4 .7H 2 O), manganese sulfate hydrate (MnSO 4 .7H 2 O), and metal compound solution containing aluminum sulfate as aluminum compound was poured into a coprecipitation reactor and continuously supplied to perform coprecipitation reaction for 50 hours while 28% ammonia solution as a complexing agent and Na 2 CO 3 as a carbonate compound was continuously supplied to adjust pH as 8 to 10, and a slurry solution in the reactor was filtrated and washed by ultrapure distilled water followed by drying in a 110° C. vacuum oven for 12 hours, thereby nickel cobalt aluminum metal complex carbonate compound was obtained. This nickel cobalt aluminum metal complex carbonate compound was Ni 0.2 Co 0.07 Mn 0.7 Al 0.03 CO 3 . [0000] TABLE 1 Ni Co Mn Al Example 1-1 20 7 70 3 Example 1-2 20 4 70 6 Comparative Example 1 20 10 70 0 Comparative Example 2 20 2 70 8 [0059] Precursor of the example 1-2 and the comparative examples 1, 2 were synthesized using the same condition except for manufacturing metal compound solution using compound rate in Table 1. Test Example 1-1 SEM Imaging for Precursor [0060] SEM images for precursor particles containing Al 3 mol %, which was manufactured in the example 1-1 were taken in accordance with synthesis time, and then the results were shown in FIG. 1 . The precursor particles in FIG. 1 were spherical shape of 5 to 25 μm and had dense surfaces. Test Example 1-2 EDS Analysis for Precursor [0061] EDS analysis for a section of precursor containing Al 3 mol %, which was manufactured in the example 1-1 were performed in accordance with synthesis time, and then the results were shown in FIG. 2 . Saturation amount of Al was maintained at 3 mol % during synthesis time. Test Example 1-3 SEM Imaging for Precursor [0062] SEM images for precursor particles containing Al 6 mol %, which was manufactured in the example 1-2 were taken in accordance with synthesis time, and then the results were shown in FIG. 3 . The precursor particles in FIG. 1 were spherical shape of 5 to 25 μm and had dense surfaces. Test Example 1-4 EDS Analysis for Precursor [0063] EDS analysis for a section of precursor containing Al 6 mol %, which was manufactured in the example 1-2 were performed in accordance with synthesis time, and then the results were shown in FIG. 4 . Saturation amount of Al was maintained at 6 mol % during synthesis time. Example 2 Synthesis of Lithium Rich Cathode Active Material Containing Al 3 mol % [0064] The carbonate precursor containing Al 3 mol % manufactured in the example 1-1 and Li 2 CO 3 as a lithium compound were mixed at equivalent ratio, wherein transition metal ratio was in Table 2 followed by thermal treatment at 900° C. and pulverizing, thereby lithium rich cathode active material was synthesized. [0000] TABLE 2 Li/(NiCoMnAl) Example 2-1 1.40 Example 2-2 1.45 Example 2-3 1.50 Test Example 2-1 XRD Analysis for Active Material [0065] XRD analysis for particles of lithium rich cathode active material which were manufactured in the examples 2-1 through 2-3 were performed, and then the results were shown in FIG. 5 . As shown in FIG. 5 , the lithium rich cathode active material had a peak at 2θ=21°. Test Example 2-2 Particle Size Analysis [0066] Particle size analysis for particles of lithium rich cathode active material which were manufactured in the examples 2-1 through 2-3 were performed, and then the results were shown in FIG. 6 . As shown in FIG. 6 , the lithium rich cathode active material manufactured by the example of the present invention had D50 of 17 to 22 μm. Test Example 2-3 SEM Imaging for Active Material [0067] SEM images for particles of lithium rich cathode active material which were manufactured in the examples 2-1 through 2-3 were taken, and then the results were shown in FIGS. 7 to 9 . As shown in FIGS. 7 to 9 , the particles of the lithium rich cathode active material were secondary particles formed by cohered first particles and had spherical shape. Test Example 2-4 EDS Analysis for Active Material [0068] EDS analysis for sections of particles of lithium rich cathode active material which were manufactured in the examples 2-1 through 2-3 were performed, and then the results were shown in FIGS. 10 to 12 . As shown in FIGS. 10 to 12 , the lithium rich cathode active material was coated by Al. Test Example 2-5 Measuring Charging/Discharging Characteristic [0069] The lithium rich cathode active material manufactured in the examples 2-1 through example 2-3, carbon black and PVDF[Poly(vinylidene fluoride)] as a binder were mixed with organic solution NMP at weight ratio of 94:3:3 to form a slurry. The slurry was coated on an Al foil of 20 um followed by drying, thereby a cathode was manufactured. A CR2016 coin-half cell was assembled using the cathode, an anode of metal lithium and a membrane of a porous poly ethylene film (CellGard 2502). Solution of 1.1M LiPF 6 EC/EMC/DEC was used for electrolyte. [0070] FIGS. 13 to 15 show discharging capacity and cycle life characteristic. Example 2-6 Measuring Cycle Life Characteristic [0071] FIG. 16 shows 50 cycle life characteristic of a battery which was manufactured using the lithium rich cathode active material manufactured by the Examples 2-1 through 2-3. It is shown in FIG. 16 that at least 90% of life was sustained when ratio of Li/M is 1.45 and 1.5. Example 3 Synthesizing Lithium Rich Cathode Active Material Containing Al 6 mol % [0072] The carbonate precursor containing Al 6 mol % manufactured in the example 1-2 and Li 2 CO 3 as a lithium compound were mixed at equivalent ratio, wherein transition metal ratio was in Table 2 followed by thermal treatment at 900° C. and pulverizing, thereby lithium rich cathode active material was synthesized. [0000] TABLE 3 Li/(NiCoMnAl) Example 3-1 1.40 Example 3-2 1.45 Example 3-3 1.50 Test Example 3-1 XRD Analysis for Active Material [0073] XRD analysis for particles of lithium rich cathode active material which was manufactured in the examples 3-1 through 3-3 was performed, and then the results were shown in FIG. 17 . As shown in FIG. 17 , the lithium rich cathode active material shows a peak at 2θ=21°. Test Example 3-2 Particle Size Analysis [0074] Particle size analysis for particles of lithium rich cathode active material which was manufactured in the example 2-1 through 2-3 was performed, and then the results were shown in FIG. 18 . As shown in FIG. 18 , the lithium rich cathode active material containing Al 6 mol % manufactured by the examples 3-1 through 3-3 of the present invention had D50 of 23 to 25 μm. Test Example 3-3 Measuring Charging/Discharging Characteristic [0075] The lithium rich cathode active material manufactured in the examples 3-1 through example 3-3, carbon black and PVDF[Poly(vinylidene fluoride)] as a binder were mixed with organic solution NMP at weight ratio of 94:3:3 to form a slurry. The slurry was coated on an Al foil of 20 μm followed by drying, thereby a cathode was manufactured. A CR2016 coin-half cell was assembled using the cathode, an anode of metal lithium and a membrane of a porous poly ethylene film (CellGard 2502). Solution of 1.1M LiPF 6 EC/EMC/DEC was used for electrolyte. [0076] FIGS. 19 to 21 show discharging capacity and cycle life characteristic. Test Example 3-4 Measuring Cycle Life Characteristic [0077] FIG. 22 shows 50 cycle life characteristic of a battery which was manufactured using the lithium rich cathode active material manufactured by the examples 3-1 through 3-3. It is shown in FIG. 16 that at least 90% of life was sustained when ratio of Li/M is 1.45 and 1.5. Example 4 Synthesizing a Precursor for Manufacturing Lithium Rich Cathode Active Material [0078] Nickel sulfate hexahydrate (NiSO 4 .6H 2 O), cobalt sulfate heptahydrate (CoSO 4 .7H 2 O), manganese sulfate hyemppledrate (MnSO 4 .7H 2 O), aluminum sulfate as aluminum compound and metal compound solution containing TiO 2 as a different metal was poured into a coprecipitation reactor and continuously supplied to perform coprecipitation reaction for 50 hours while 28% ammonia solution as a complexing agent and Na 2 CO 3 as a carbonate compound was continuously supplied to adjust pH as 8 to 10, and then a slurry solution in the reactor was filtrated and washed by ultrapure distilled water followed by drying in a 110° C. vacuum oven for 12 hours, thereby nickel cobalt manganese aluminum titanium metal complex carbonate compound was obtained. This transition metal complex carbonate compound was Ni 0.2 Co 0.07 Mn 0.67 Al 0.03 Ti 0.03 CO 3 . [0000] TABLE 4 Ni Co Mn Al Ti Zr Mg Example 4-1 20 7 67 3 3 0 0 Example 4-2 20 7 67 3 0 3 3 Example 4-3 20 7 67 3 0 0 1 Example 4-4 20 7 67 3 0 0 2 Comparative Example 4-1 20 10 70 0 0 0 0 Comparative Example 4-2 20 7 70 3 0 0 0 Comparative Example 4-3 20 7 67 0 3 0 0 Comparative Example 4-4 20 7 67 0 0 3 3 Comparative Example 4-5 20 7 64 3 6 0 0 Comparative Example 4-6 20 7 64 3 0 6 6 [0079] Precursor of the examples 4-2 through 4-4 and the comparative examples 4-1 through 4-6 were synthesized using the same condition except for manufacturing metal compound solution using compound rate in Table 4. Test Example SEM Imaging and EDS Analysis [0080] Results of SEM images and EDS analysis of precursor manufactured by the example 4-3 was shown in FIGS. 23 and 24 , and results of SEM images and EDS analysis of precursor for manufacturing lithium rich cathode active material which was manufactured at constituent of the example 4-4 was shown in FIGS. 25 and 26 . [0081] The SEM images in FIGS. 23 and 25 shows that Al 2 O 3 coated on a surface was cohered, and the result of the EDS measurement shows indicates that doped Al and Mg are coated on particles uniformly. Example 5 Synthesis of Lithium Rich Cathode Active Material [0082] The carbonate precursor manufactured in the examples 4-1 through 4-4 and the comparative example and Li 2 CO 3 as a lithium compound were mixed at equivalent ratio followed by thermal treatment at 900° C. and pulverizing, thereby lithium rich cathode active material was synthesized. Test Example SEM Imaging and EDS Analysis [0083] Results of SEM images and EDS analysis of the example 5-3 which is lithium rich cathode active material manufactured at the precursor constituent of the example 4-3 was shown in FIGS. 27 and 28 , and results of SEM images and EDS analysis of the example 5-4 which is lithium rich cathode active material manufactured at the constituent of the example 4-4 was shown in FIGS. 29 and 30 . Test Example Measuring Battery Properties [0084] The lithium rich cathode active materials of the examples 5-1 through 5-4 and the examples comparative examples 5-1 through 5-6 manufactured by the example 4-1 through 4-4 and the comparative examples 4-1 through 4-6, carbon black and PVDF[Poly(vinylidene fluoride)] as a binder were mixed with organic solution NMP at weight ratio of 94:3:3 to form a slurry. [0085] The slurry was coated on an Al foil of 20 μm followed by drying, thereby a cathode was manufactured. A CR2016 coin-half cell was assembled using the cathode, an anode of metal lithium and a membrane of a porous poly ethylene film (CellGard 2502). Solution of 1.1M LiPF 6 EC/EMC/DEC was used for electrolyte. [0086] Following Table 5 shows discharging capacity and cycle life characteristic. [0000] TABLE 5 Discharge Room Temperature life Capacity/mAhg−1 after 50 cycles/% Example 5-1 249 95 Example 5-2 250 96 Comparative Example 5-1 261 87 Comparative Example 5-2 259 93 Comparative Example 5-3 254 92 Comparative Example 5-4 253 93 Comparative Example 5-5 240 92 Comparative Example 5-6 239 93 [0087] As shown in Table 5, the lithium rich cathode active material according to examples of the present invention is more improved than the comparative examples in discharging capacity and cycle life characteristic. [0088] FIGS. 31 and 32 show results of charging/discharging characteristics of CR2016 coin-half cells using the lithium rich cathode active materials at the constituents of the examples 5-3 and 5-4. Test Example Measuring Cycle Life Characteristic [0089] FIGS. 33 and 34 show cycle life characteristics of the CR2016 coin-half cells using the lithium rich cathode active materials of the examples 5-3 and 5-4 which are manufactured at constituents of the examples 4-3 and 4-4. [0090] As shown in FIGS. 33 and 34 , the CR2016 coin-half cells using the lithium rich cathode active materials of the examples 5-3 and 5-4 which are manufactured at constituents of the examples 4-3 and 4-4 maintain capacities until 40 cycles. Test Example Measuring Particle Intensity [0091] Following Table 6 shows particle intensities of the lithium rich cathode active materials of the examples 5-3 and 5-4 which are manufactured at constituents of the comparative examples 4-3 and 4-4, and particle intensities of the lithium rich cathode active materials of the comparative examples 5-3 and 5-4 which are manufactured at constituents of the examples 4-3 and 4-4. [0000] TABLE 6 ID Particle hardness Comparative Example 5-1 bare 101 Comparative Example 5-2 Al 0.3 111 Example 5-3 Al 0.3 Mg1 116 Example 5-4 Al 0.3 Mg2 116 [0092] According to the present invention, a battery, of which high voltage capacity is improved and cycle life characteristics are improved, can be fabricated by adjusting species and a composition of substituted metal and by adjusting species and an amount of substituting metal, in the precursor for manufacturing lithium rich cathode active material and the lithium rich cathode active material using the same. [0093] According to the precursor for manufacturing lithium rich cathode active material and the lithium rich cathode active material using the same, species and content of substituted metal from the precursor are adjust and species and addition amount of substituting metal are adjust to manufacture a battery of which high voltage properties and cycle life characteristics are improved.
The disclosure relates to a precursor manufacturing a lithium rich cathode active material and a Lithium rich cathode active material using the same, more specifically relates to a novel precursor for manufacturing a lithium rich cathode active material of which capacity properties and cycle life characteristics are considerably improved by solving a problem of conventional lithium rich cathode active material, and a Lithium rich cathode active material using the same.
2
RELATED APPLICATIONS The present application claims priority under 35 U.S.C. §119(e) to Provisional Application No. 61/784,010, filed on Mar. 14, 2013. FIELD OF THE INVENTION The present invention relates generally to cardiac implants and particularly to flexible annuloplasty rings having stranded core members heat set into desired shapes. BACKGROUND OF THE INVENTION In vertebrate animals, the heart is a hollow muscular organ having four pumping chambers: the left and right atria and the left and right ventricles, each provided with its own one-way valve. The natural heart valves are identified as the aortic, mitral (or bicuspid), tricuspid and pulmonary, and are each mounted in an annulus comprising dense fibrous rings attached either directly or indirectly to the atrial and ventricular muscle fibers. Each annulus defines a flow orifice. Prosthetic annuloplasty rings are used to repair or reconstruct damaged or diseased heart valve annuluses. An annuloplasty ring is designed to support the functional changes that occur during the cardiac cycle: maintaining leaflet coaptation and valve integrity to prevent reverse flow while permitting good hemodynamics during forward flow. The annuloplasty techniques may be used in conjunction with other repair techniques. The rings either partially or completely encircle the valve, and may be rigid, flexible, or selectively flexible. Although mitral valve repair and replacement can successfully treat many patients with mitral valve insufficiency, techniques currently in use are attended by significant morbidity and mortality. Most valve repair and replacement procedures require a thoracotomy, to gain access to the patient's thoracic cavity. Surgical intervention within the heart frequently requires isolation of the heart and coronary blood vessels from the remainder of the arterial system and arrest of cardiac function, using a cardiopulmonary bypass machine. Open chest techniques with large sternum openings are used. Those patients undergoing such techniques often have scarring retraction, tears or fusion of valve leaflets, as well as disorders of the subvalvular apparatus. Naturally, surgical patients desire operations that are performed with the least amount of intrusion into the body. Recently, a great amount of research has been done to reduce the trauma and risk associated with conventional open heart valve replacement surgery. In particular, the fields of minimally invasive surgery (MIS) and percutaneous surgery have exploded since the early to mid-1990s, with devices now being proposed to enable valve repair without opening the chest cavity, and some without even requiring bypass. Proposed MIS heart valve repair procedures are accomplished via elongated tubes or cannulas introduced through one or more small access incisions in the thorax, with the help of endoscopes and other such visualization techniques. For example, see U.S. Pat. No. 6,602,288 to Cosgrove. Such minimally invasive procedures usually provide speedier recovery for the patient with less pain and bodily trauma, thereby reducing the medical costs and the overall disruption to the life of the patient. A minimally invasive approach also usually results in a smaller incision and, therefore, less scarring, which is an aesthetic advantage attractive to most patients. What is needed are devices and methods for carrying out heart valve repair that reduce the trauma, risks, recovery time and pain that accompany current techniques. SUMMARY OF THE INVENTION The present application provides an annuloplasty ring comprising a flexible braided cable extending around the entire periphery of the ring in either a closed or open shape. The annuloplasty rings disclosed herein may have a flexible core member comprises a multi-stranded braided cable. Desirably, the multi-stranded braided cable has at least seven braided cables in cross-section, and may comprise strands of at least two different metals braided together. In one embodiment a multi-stranded cable replaces solid core wire for both the tricuspid and mitral valves. Cable allows for greater deployment flexibility for minimally-invasive surgical (MIS) implant, while still maintaining the required strength and similar tensile properties of solid-core wire. Cable results in a MIS annuloplasty ring with sufficient flexibility in the x-y plane to allow a surgeon to squeeze the ring into a 1 cm×1 cm incision, while maintaining structural rigidity under forces exerted on the implanted ring by the cardiac cycle and allowing for asymmetrical deflection to be designed into the product. A majority of the length of the inner core member has a first elastic modulus sufficiently flexible to enable the core member to be compressed from its relaxed ring shape into a narrow shape suitable for passage through a tubular access device. In one embodiment of the invention there is contemplated a method for forming an annuloplasty ring, comprising providing a flexible core member formed from a braided metal cable. The core member is held in a desired peripheral shape of the annuloplasty ring, and then heated above its austenitic final temperature. That temperature is maintained for a period of time, and then the core member is rapidly cooled. A suture-permeable outer covering is added around the flexible core member to form the annuloplasty ring. The metal core member is preferably formed from a multi-stranded braided cable formed of multiple wire strands wound into multi-strand braids with the multi-strand braids being braided into the multi-stranded braided cable. In some embodiments, the multi-stranded braided cable has at least seven multi-strand braids in cross-section and has sufficient flexibility to enable it to be manipulated into an elongated shape to fit within a small tubular access device. The peripheral shape of the core member can be closed or open with two free ends, and if open, the method can include capping or welding the two free ends to cover individual strand ends. The braided metal cable can be made of MP35N LT or Nitinol. A holding fixture can be provided, the fixture having a base member and at least one clamping member. The base member and clamping member have complementary channels that together provide a three-dimensional mold for the desired peripheral shape of the annuloplasty ring. The step of holding the core member comprises placing the core member between the base member and the at least one clamping member. In some instances, the desired peripheral shape of the annuloplasty ring is open with two free ends. In such case, the holding fixture preferably has three clamping members: a first one for a closed side of the core member and two other for the two free ends. The clamping members are placed sequentially over the core member with the first clamping member first and the two others second and third. The desired peripheral shape of the annuloplasty ring can be three-dimensional, and the base member and three clamping members have raised areas such that the channel defines the three-dimensional peripheral shape. In some cases, the clamping members bolt to the base member to hold the core member firmly in the channel. In another embodiment, there is provided an annuloplasty ring comprising a flexible core member comprising a braided metal cable. The cable is formed of a metal that has been heat set by exposure to a temperature above its austenitic final temperature for a period of time to cause a crystalline structure alteration from martensitic to austenitic, and a change in the lowering of the austenite-martensite transition temperature such that the molecules are in the austenitic phase at room temperature. The core member is preferably shaped for mitral or tricuspid implantation, and includes a suture-permeable outer covering around the flexible core member. In one embodiment, the core member of the annuloplasty ring defines a saddle shape with both a posterior portion and an anterior portion defined by two free ends rising upward from left and right sides. The core member can include a cap or weld on the two free ends to cover individual strand ends. In some embodiments, the core member is made from a multi-stranded braided cable formed of multiple wire strands wound into multi-strand braids with the multi-strand braids being braided into the multi-stranded braided cable. The multi-stranded braided cable has at least seven multi-strand braids in cross-section, and has sufficient flexibility to enable it to be manipulated into an elongated shape to fit within a small tubular access device. The metal core is preferably made of MP35N LT or Nitinol. A further understanding of the nature and advantages of the invention will become apparent by reference to the remaining portions of the specification and drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of an exemplary open annuloplasty ring implanted at a mitral annulus and having free ends that extend significantly past commissure markings; FIGS. 2A and 2B are plan and elevational views, respectively, of the exemplary annuloplasty ring shown in FIG. 1 ; FIGS. 3A-3C are posterior, anterior and side elevational views, respectively, of an exemplary inner core member of the annuloplasty ring of FIG. 1 formed of a heat set braided cable; FIG. 4 is a sectional view through the exemplary annuloplasty ring taken along line 4 - 4 of FIG. 2B ; FIG. 5 is a sectional view through the annuloplasty ring inner core member taken along line 5 - 5 of FIG. 3B ; FIGS. 6A and 6B are plan and posterior elevational views, respectively, of an exemplary inner core member having a braided cable for a closed mitral annuloplasty ring; FIGS. 7A and 7B are plan and posterior elevational views, respectively, of an exemplary inner core member having a braided cable for a closed asymmetric mitral annuloplasty ring; FIGS. 8A and 8B are plan and septal elevational views, respectively, of an exemplary inner core member having a braided cable for an open tricuspid annuloplasty ring; FIG. 9A is a perspective view of the core member from FIGS. 3A-3C seen exploded with an exemplary fixture for holding the core in a desired shape during a heat setting procedure; FIG. 9B is a perspective view of the assembled fixture for holding the core in a desired shape during a heat setting procedure; FIGS. 10A-10G show a number of different possible braided cable configurations that may be used; FIG. 11A is a schematic view of a core member of a closed ring squeezed into an elongated shape and passed through a delivery tube; and FIGS. 12A and 12B are schematic views of a core member of an open ring extended into an elongated shape and passed through a delivery tube. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a number of different annuloplasty rings or repair segments. It should be understood that the term annuloplasty ring or repair segments refers to any generally elongated structure attachable to the native valve annulus and used in annulus repair, whether straight or curved. For example, an annuloplasty ring is conventionally understood to provide either a complete or substantially complete loop sized to correct a misshapen and or dilated native annulus and which is sutured or otherwise attached to the fibrous annulus from which the valve leaflets extend. In many instances, a partial ring or even a straight repair segment may be used around just a portion of the annulus, such as around the posterior edge. A first embodiment of the present invention is illustrated in FIGS. 1 and 2A-2B in which a mitral annuloplasty ring 20 defines a posterior portion 22 and an anterior portion 24 which has free ends 24 a , 24 b separated across a gap. Per convention, the annuloplasty ring 20 somewhat resembles an open D-shape with the outwardly convex posterior portion 22 and the free ends 24 a , 24 b together defining a substantially straight anterior portion extending generally between commissures, or possibly the trigones, of the annulus. The annuloplasty ring 20 typically includes a suture-permeable outer covering 26 , described in more detail below, for attaching the ring to the annulus with sutures. A word about the mitral valve anatomy is necessary. The mitral valve includes a posterior leaflet PL that surrounds approximately two thirds of the circumference of the mitral valve and an anterior leaflet AL that occupies approximately one third of the annular circumference, both of which attach at their outer peripheries at the mitral annulus MA. The conventional representation of these two leaflets shows the posterior leaflet below the anterior leaflet, with their line of coaptation, or contact in the flow stream, as a smile-shaped curve. The mitral valve commissures define distinct areas where the anterior and posterior leaflets come together at their insertion into the annulus—which can be imagined as the corners of the smile-shaped coaptation line. Indeed, the mitral annuloplasty ring 20 includes commissure markings 28 that help the surgeon register or position the ring at the appropriate location around the mitral annulus MA. The markings 28 may be lines of colored thread, whereas the outer covering 26 is typically a white fabric. Ink, toner from a laser printing system or even a yarn knit into the cloth can also be used for marker. A third marking 30 can be provided at the midpoint of the posterior portion 22 of the ring. The anterior portion of the mitral annulus attaches to the fibrous trigones and is generally more resistant to tearing and less likely to stretch or elongate than the posterior annulus. The right fibrous trigone RT is a dense junctional area between the mitral, tricuspid, non-coronary cusp of the aortic annuli and the membranous septum. The left fibrous trigone LT is situated at the junction of both left fibrous borders of the aortic and the mitral valve. Although the trigones and commissures are proximate to each other, they are not at the exact same location. Indeed, because of the tough, fibrous nature of the trigones, the free ends 24 a , 24 b of the exemplary annuloplasty ring 20 extend substantially beyond the commissure markings 28 , into the area of the trigones RT, LT. In a preferred embodiment, each of the free ends 24 a , 24 b extends beyond its respective commissure markings 28 (and thus beyond the native commissures) by a length L indicated in FIG. 2B of between about 7-9 mm. With reference to the posterior elevational view of FIG. 2B , and also the elevational views shown in FIGS. 3A-3C , the three-dimensional contours of the annuloplasty ring 20 , and in particular an inner core member 40 will be described. The core member 40 provides a skeleton for the ring 20 , and is merely covered with flexible silicone and/or fabric which conforms to its shape. Therefore, the shape of the annuloplasty ring 20 will be described with reference to the shape of the core member 40 . The core member 40 has an overall saddle shape, with the posterior portion 22 and anterior portion defined by the free ends 24 a , 24 b rising upward from left and right sides 42 in between. Although there is a gap between the free ends 24 a and 24 b , they generally define upward slopes which extend toward one another. The upward rise of the free ends 24 a , 24 b corresponds to the anterior annulus adjacent to the aortic valve and avoids having a structure that projects into the left ventricular outflow track where it could impede flow out of the aortic valve. This shape also preserves the natural saddle shape of the anterior leaflet of the mitral valve, reducing the stress on the mitral leaflets during systole. Moreover, an imaginary extension can be drawn between the free ends 24 a , 24 b which is generally smooth and continuous, and defines an upward arc that rises higher than the upward arc of the posterior portion 22 , such as shown in dashed lines in FIGS. 2A-2B . The relative height of the anterior portion and the posterior portion 22 of the core member 40 is most evident in the side elevational view of FIG. 3C . At this point, it is instructive to define coordinate axes for the various directions used to define the ring shape. These definitions are included to aid one of ordinary skill in the art in understanding the geometry of the ring both in and out of the body. The term “axis” or “central axis” 44 in reference to the illustrated ring, and other non-circular or non-planar rings, refers to a line generally perpendicular to the ring that passes through the area centroid of the ring when viewed in plan view (i.e., FIG. 2A ). “Axial” or the direction of the “axis” can also be viewed as being parallel to the general direction of blood flow within the valve orifice and thus within the ring when implanted therein; as is known to those of ordinary skill in the art, blood flows normally in a forward direction from the right atrium through the tricuspid valve and into the right ventricle; blood flows normally in a forward direction from the left atrium through the mitral valve and into the left ventricle. Thus, stated another way, the implanted annuloplasty ring orients about a central flow axis aligned along an average direction of normal blood flow through the valve annulus. Although the rings of the present invention are generally 3-dimensional, and saddle-shaped, portions thereof may be planar and lie perpendicular to the flow axis. Accordingly, with reference to FIGS. 2A-2B and 3A-3C , left and right sides 42 of the core member 40 are located at low points axially, while the midpoint of the posterior portion 22 rises to a high point axially on that side, and the two free ends 24 a , 24 b rise up to axial high points on the anterior portion. In between the low points and the high points, the core member 40 has gradual curves. The core member 40 when in its relaxed, unstressed state is shaped similar to a Carpentier-Edwards® Physio II™ Annuloplasty Ring available from Edwards Lifesciences of Irvine, Calif. As will be clear below, the open nature of the core member 40 , and annuloplasty ring 20 formed thereby, permits a surgeon to open the structure up into an elongated strand for delivery through a small tube such as a catheter or cannula, as will be described below. FIGS. 3A and 3B illustrate caps or welds 46 formed on the free ends of the core member 40 . This is necessary to help prevent fraying of the gradients, and also to minimize abrasion of the surrounding suture-permeable cover at the ends. Depending on the material, laser or plasma welding can be used to melt and form a bead at the ends 46 . Alternatively, the ends can be first welded and then a swage die (e.g., Fenn swaging machine) used to round or otherwise even out the weld. Alternatively, a smooth or rounded cap may be welded or adhered to the ends. FIGS. 4 and 5 shows cross-sections of the ring 20 and exemplary core member 40 , respectively. The ring 20 includes the aforementioned core member 40 surrounded by a suture-permeable interface 50 , such as a silicone rubber tube. The interface 50 closely surrounds the core member 40 , and surrounding that is a fabric cover 52 . As seen in FIG. 5 , the illustrated core member 40 desirably comprises a braided cable with multiple cables 54 of braided strands 56 braided amongst themselves. This construction is also known in the art as a multi-stranded braided cable. In the illustrated embodiment, the braid pattern includes 19 separate braided cables 54 of seven strands 56 each, or a 19×7 pattern. Other multi-stranded braids are possible having 7×7, 7×19, 19×7 or even 7×7×7 braided cables. Indeed, even simple cable constructions may be used, such as 1×3, 1×7, or 1×19. Each of these possible braid constructions are seen in FIGS. 10A-10G , and will be described in greater detail below. One example of materials is a cable from Fort Wayne Metals (FWM), 1058 Elgiloy, 19×7 strand arrangement having an overall diameter of 0.062″ (1.57 mm). Another is a 7×7 0.069″ (0.175 mm) diameter strand arrangement of MP35N LT (again, from FWM) having an overall diameter of 0.062″ (1.57 mm). A second embodiment of an annuloplasty ring core member is illustrated in FIGS. 6A and 6B in which the core member 60 for a flexible mitral annuloplasty ring defines a posterior portion 62 and an anterior portion 64 . As before, the core member 60 resembles a D-shape with the outwardly convex posterior portion 62 and a substantially straight anterior portion 64 . However, in contrast to FIGS. 3A-3C the core member 60 has a closed peripheral shape. An annuloplasty ring that includes the core member 60 may also have a suture-permeable outer covering (not shown), such as a silicone tube surrounding the core member 60 which is then surrounded by a fabric tube, such as seen in FIG. 4 . The core member 60 when in its relaxed, unstressed state desirably has the same shape as the Carpentier-Edwards® Physio® Annuloplasty Ring available from Edwards Lifesciences. A still further embodiment of the present invention is shown in FIGS. 7A and 7B . A core member 70 for a flexible mitral annuloplasty ring defines a posterior portion 72 and an anterior portion 74 . The core member 70 has a modified D-shape with the outwardly convex posterior portion 72 being pulled in on the right side so as to be asymmetric. FIG. 7B shows the right side of the posterior portion dipping downward at 76 . As with FIGS. 6A-6B the core member 70 has a closed peripheral shape, but in this embodiment in its unstressed state mimics the shape of the Carpentier-McCarthy-Adams IMR ETlogix™ Annuloplasty Ring, also available from Edwards Lifesciences. FIGS. 8A and 8B show a still further core member 80 in the shape of a tricuspid annuloplasty ring. As in the earlier embodiments, exterior components such as a silicone interface and fabric cover are not shown to better illustrate the flexible core member 80 . The core member 80 includes a flexible braided cable 82 having two free ends 84 a , 84 b . The core member 80 has the classic tricuspid shape in plan view, starting at the first free end 84 a and extending in a clockwise direction around a first segment that ends at a point 86 in the aortic part of the anterior leaflet. Adjacent to the first segment is a second segment corresponding to the remaining part of the anterior leaflet that ends at the postero septal commissure 88 . Finally, a third segment 90 extends from the postero septal commissure 88 to the second free end 84 b , which is mid-way along the septal leaflet. As seen in FIG. 8B , the third segment 90 angles downward relative to a flow axis (not shown). The nomenclature for these segments is taken from the standard anatomical nomenclature around the tricuspid annulus. The core member 80 when in its relaxed, unstressed configuration is the same shape as an Edwards MC 3 Annuloplasty System available from Edwards Lifesciences. Alternatively, although not shown, the unstressed configuration may have the same shape as a Carpentier-Edwards Physio Tricuspid Annuloplasty Ring, such as described in U.S. Patent Publication No. 2012/0071970, filed Aug. 30, 2011, the contents of which are expressly incorporated herein by reference. The various braided cables that may be used for core members for the annuloplasty rings described herein have a great degree of elasticity and flexibility, and prior to any special processing are unable to form the three-dimensional ring-shapes described above. That is, they tend to spring back to their original braided shape, which is typically linear. Consequently, the present application contemplates heat setting the core members to fix particular desirable shapes therein. Heat setting or more generally heat treatment involves elevating the temperature of the metal core member while maintaining it in a ring-shaped neutral position using a fixture, which shape remains after quenching and removal from the fixture. More specifically, applied heating can instigate a “heat memory effect,” which is essentially when the material is heat treated to retain a specific form, different from its original geometry. After the material has been heated, cooled, and brought back to room temperature, it will naturally remain in the constrained shape. Some terms of the art are presented below, with Nitinol referenced as a potential candidate material: As (Austenite Start Temperature): Temperature where material begins to transform into austenite. Internal crystalline structure begins to change. For Nitinol, this change normally occurs around 500° C. Af (Austenite Final Temperature): Temperature where material has completed transforming to austenite. The aim of the processing is to cause the core member material to remain in its austenitic form after being heated to a particular temperature range, such as from 500° C. to 600° C., for a period of time. The core member will be rigidly constrained in its desired shape and heat treated. The metal is exposed to a temperature above its austenitic final temperature for a period of time to cause its crystalline structure to be altered from martensitic to austenitic, and its austenite-martensite transition temperature is lowered such that the molecules are in the austenitic phase at room temperature. The heat treating essentially “relaxes” the stress initially within the material so that it does not spring back to its unformed shape. Cooling should be rapid to avoid aging effects; for instance a water quench or air cooling may be required. The duration of heating should be sufficient such that the core member reaches the desired temperature throughout its cross-section, which depends on the mass of the holding fixture, the material, as well the heating method. Various studies have been done with metals that are good candidates for use in cardiac implants. Table I, below, indicates performance parameters for two NiTi cable samples which were heated in a ring fixture at temperatures ranging from 500° C.-600° C. The resulting shape retention and other relevant notes were recorded for the stress relieved (STR), and the non-stress relieved (Non STR) NiTi samples in Table I. The NiTi tested was comprised of approximately 56% Nickel and 44% Titanium. The ring samples were stretched from their new neutral positions after heat treatment and released to see if they returned to its constrained shape during heat treating. These tests revealed that a treatment temperature of 550° C. for either material resulted in good shape retention. TABLE I Results of Heat Treating Nitinol (NiTi) Temperature 500° C. 550° C. 600° C. STR Did not fully Fully returned to Fully returned to return to original jig position. original jig position. original jig More spring back More spring back (constrained) force than at force than at 550° C. position 500° C. More cracking than No cracking Minimal cracking 550° Non STR Did not fully Fully returned to Fully returned to return to original jig position. original jig position. original jig More springback More spring back (constrained) force than at force than at 550° C. position 500° C. More cracking than No cracking Minimal cracking 550° In addition to the characterization of the NiTi samples, heat shaping characterization was also conducted using samples of a new alloy developed by Fort Wayne Metals (FWM) denoted MP35N LT. MP35N LT is a composition which is mainly Nickel, Chromium and Molybdenum. The samples were treated at 500° C., 600° C., and 700° C. The 700° C. showed the greatest shape retention and proved MP35N LT can be heat shaped as well. From these tests both NiTi and MP35N LT cables showed promise. However, while highly resistant to permanent deformation, NiTi cables are likely to lose their passivation layer during heat shaping, which makes it a less ideal cable choice than the MP35N LT cable type. One possibility is to form the core member from strands of at least two different metals braided together for a particular performance outcome. NiTi is a highly flexible material that may not require the braided construction to get a 3-D shape that can be flexed to go through a 1 cm catheter. On the other hand, for CoCr alloys (e.g., MP35N LT) the braided structure is necessary. Nevertheless, MP35N LT has superior fatigue resistance compared to NiTi, which is a significant factor in a system that must flex 40K times per year for most of a patient's remaining lifetime (average of 10-20 years). Consequently, CoCr alloys are preferred, with MP35N LT being especially desirable. In a preferred embodiment of an annuloplasty ring, a core member 40 such as shown in FIGS. 3A-3C was heat set to have the following characteristics: The percent ratio of the minor axis to the major axis is 75%±10%. The percent ratio of the height of the posterior portion 22 relative to the major axis dimension is 5±2%. The distance apart on the free ends 24 a , 24 b , or the gap there between, relative to the major axis dimension is 52±5%. The material used is MP MP35N LT 7×7 stranded cable available from Fort Wayne Metals. Finally, the proportional shapes of the rings change over a set of rings having nominal sizes of 24-44 mm. First of all, the percent ratio of the height of the free ends 24 a , 24 b relative to the major axis dimension is 5±3% for ring sizes of 24-28 mm, and 15±3% for larger ring sizes of 30-44 mm. Also, the plan view shape changes over the set of rings, with the ratio of the minor axis to the major axis preferably increasing for ring sizes 30 mm and above to go from generally D-shaped to becoming more circular. The exemplary process for heat setting the core member 40 is to place it in a fixture in a vacuum furnace at 775° centigrade for 20 minutes. Argon then flooded the chamber for a minimum of one minute. The core member was left in the holding fixture and quenched with water, then removed and allowed to dry. At this point, the free ends of the core member 40 are welded and/or capped, and the entire core member is electropolished. A suitable cleaning process is then done to ensure removal of any metal particles from the fabrication. Subsequently, the suture-permeable cover is added, as indicated in FIG. 4 . FIGS. 9A and 9B illustrate exploded and assembled views of an exemplary holding fixture 100 for the core member 40 . The fixture comprises a base member 102 having a generally rectangular periphery and defined therein a channel 104 shape to hold the core member 40 . Of course, a core member 40 initially starts out as a straight or slightly curved cable, and is positioned within the channel 104 beginning on a front side (toward the reader). Above the base member 102 , three clamp members 106 and 108 a , 108 b are shown. The clamp members 106 , 108 fasten to the base member 102 using bolts 110 , or the like. After the proximal side of the core member 40 is seated within the channel 104 , the larger of the clamp members 106 is placed thereover and secured to the base member 102 . The clamp member 106 covers approximately half of the area of the base member 102 . At this point, the free ends of the core member 40 project out from between the base member 102 and the front clamp member 106 . The smaller clamp members 108 a , 108 b are symmetric and shaped to each hold down one of the free ends of the core member 40 . Each free end is thus pushed down one at a time into the corresponding portion of the channel 104 and one of the clamp members 108 a , 108 b is secured to the base member 102 . In this way, the process for loading the core member 40 into the holding fixture 100 is easily accomplished in sections. It should be noted that the base member 102 has a three-dimensional contour that provides a mold for the final shape of the core member 40 . For example, a front end 110 of the base member 102 shows a slight upward bow such that the same curve can be imparted to the posterior portion of the core member 40 . Likewise, a rear end 112 features a raised contour that imparts the upward curvatures to the free ends of the core member 40 . The precise mold shape for the core member 40 is defined by the channel 104 which generally follows the contours of the base member 102 . Although not shown, an opposite half of the channel is provided in the underside of the clamp members 106 , 108 such that the core member 40 is surrounded by a generally cylindrical channel around its entire periphery. This prevents any movement and imparts a precise shape to the core member 40 in the heat setting process. The heat setting of the core members thus fixes defined bends where desired in the final shape. FIGS. 10A-10G show a number of different braided wire configurations that may be used. These include: a simple 1×3 cable in FIG. 10A , a simple 1×7 cable in FIG. 10B , and a simple 1×19 cable in FIG. 10C . Multi-stranded cables include multiple braided cables braided with one another, and include: a 7×7 cable in FIG. 10D , a 7×19 cable in FIG. 10E , a 19×7 cable in FIG. 10F , and a 7×7×7 cable in FIG. 10G . Each of these cables comprises many individual strands that are twisted around each other whereas solid-core wire is composed of a single strand. Even though wide ranges of materials and alloys can be used for both, cable is much more versatile than solid-core wire since different alloys can be used for different strands, different strand counts and geometric placements can be used, and different amounts of coiling can be used. This contrasts the basic nature of solid-core wire where only a single alloy can be used. Because of this unique geometry, cables typically provide a better balance of strength and flexibility. When pulled in tension from both ends, cable acts similarly to wire since the different strands are all being pulled in the same direction. However, when a cable is bent, the stress on the outermost surface of each strand in the cable is proportional to the diameter of the strand. Since each strand in a cable is much smaller than a solid core wire with the same total diameter, the bending stress and resistance to bending force is greatly reduced. This difference provides the increased flexibility as well as improved fatigue properties for a multi-strand cable compared to a solid core wire of the same total diameter. It is this unique property of cable that makes it an attractive alternative to solid-core wire with respect to annuloplasty rings for minimally invasive surgery. More information on medical grade cables is available from Fort Wayne Metals headquartered in Fort Wayne, Ind. In particular, some cables may be coated with inert polymers for greater biocompatibility. It should be understood that the stranded cable core members described herein are sufficiently elastic so as to be elongated and stressed from their relaxed shapes as shown into a more linear configuration for delivery through an access tube. The rings described herein thus have a relaxed or unstressed shape and a stressed delivery shape. The unstressed shape as shown in the drawings generally describes the shape after implant, though external forces from the surrounding annulus may deflect the unstressed shape a little. Desirably there is a balance between permitting the ring to elongate for delivery while at the same time being able to remodel to a certain extent the particular annulus consistent with the relaxed shape. Conventional remodeling rings include a more rigid core, such as solid titanium, while wholly flexible rings are typically formed of silicone/cloth combinations or just PET or PTFE cloth, neither of which would be suitable for the present purpose. The solid core rings cannot be deformed to go through a very small incision (e.g. 1 cm), while the entirely flexible rings cannot impart a shape that corrects the anatomy in a pathological valve that is often flattened by the disease process. Consequently, the present rings restore the three dimensional normal anatomical shape to the annulus which can reduce the stress seen in the native leaflets. FIG. 11A schematically illustrates a core member of a closed annuloplasty ring 114 of the present application squeezed into an elongated shape to fit within a tubular access device 116 . The flexible cable 118 facilitates the conversion from D-shaped to linear so that the ring 114 may be introduced to an implant site through the access device 116 . The access device 114 may be a cannula or introducer tube, or other similar expedient. FIGS. 12A and 12B schematically illustrate a technique for delivering an annuloplasty ring having a core member 120 in a minimally-invasive manner. Because of the open nature of the core member 120 , with the two free ends, the ring may be opened up or stretched out relatively straight in a stressed state as seen in FIG. 12A and inserted within a tubular access device 122 . The access device 122 may be inserted through an access port in the patient's chest, for example, so that its distal end is positioned at the tricuspid annulus. The core member 120 is seen being expelled from one end of the access device 122 in FIG. 12B and immediately starts assuming its relaxed unstressed state. In practice, the ring will be expelled from the distal end of the access device 122 so as to assume the unstressed ring shape in approximately the proper implant location, at which time sutures or staples may be used to attach the ring to the annulus. These delivery methods are enabled by the multi-stranded cables described herein which have the flexibility to accommodate large amounts of bending without permanent deformation. Desirably, the stranded cable rings described herein may be passed through less-invasive access catheters or the like having a size of 18 Fr, 16 Fr, 14 Fr or even smaller. However, the disadvantage of cable is that it is not as easy to permanently shape into a ring. This issue is addressed by heat setting the core members to fix defined bends where desired. Although the present application contemplates using both simple (i.e., single braided) and multi-stranded (i.e., multiple braids intertwined) cables, multi-stranded cables are believed better suited for the MIS delivery approach. For open rings, simple cables may be easily stretched linearly for passage through an access tube, but once permitted to relax and resume the annuloplasty ring shape, these simple cables may not have the requisite stiffness for annulus remodeling. As such, a greater number of bends would have to be used, which may place undesirable limitations on overall ring performance. Furthermore, simple cables formed into closed rings may not be able to be squeezed into a linear shape without kinking into permanent bends. On the other hand, multi-stranded cables are more flexible in bending due to their generally smaller individual strands and the ability of those strands to slide with respect to one another. Moreover, in open rings multi-stranded cables retain larger stiffness in the plane of the ring to provide good remodeling. This is not to say that simple cables are excluded from the present application, an annuloplasty ring that is not delivered through a small access port may be made of simple cable that is heat set to a particular shape and performs suitably. Preliminary Evaluation of Fort Wayne Metals Cable Samples A. Semi-Quantitative Analysis of Cable Samples A series of cable samples, representing typical standard products for biomedical applications, was provided by Fort Wayne Metals (FWM). Table II summarizes physical properties of the samples. It should be noted that these are not the only materials contemplated, and the list of suitable materials includes alloys of stainless steel, Titanium, Titanium Alloys, Cobalt Chromium, Nitinol (NiTi) and Nickel Alloys. Further, blends or combinations of these various materials could be utilized to obtain particular performance characteristics. The number of permutations is essentially limitless. TABLE II Cable samples provided by FWM Diameter Strand Sample Material (in) Count 1 Ti 6Al 4V ELI 0.0375 19 × 7  2 Ti 6Al 4V ELI 0.0423 7 × 7 3 L-605 0.0625 19 × 7  4 L-605 0.080 7 × 7 5 FWM-1058 0.062  7 × 19 6 316 LVM 0.078 7 × 7 7 316 LVM 0.0475  1 × 19 8 316 LVM 0.0425 1 × 7 9 MP35N 0.063 7 × 7 10 FWM-1058 0.125  7 × 19 A preliminary, semi-quantitative analysis was performed on these samples to determine issues with cable material, diameter, and strand count. A minimum bending diameter was determined visually, by bending the cable sample back upon itself until either permanent deformation occurred or cable strands began to separate. At this orientation, measurements were taken by a caliper. The force required to hold this minimum bending diameter was estimated by manually applying the necessary load while the cable was resting on a laboratory scale. Additionally, the cable samples were evaluated for minimum bending diameter with moderate deformation (defined as a ˜10 degree bend remaining in the cable after removing load), as well as “robustness”, which was based on qualitative observation of how much bending/deformation cables could withstand without suffering permanent damage (kinking, strand separation, or permanent deformation). The results of this preliminary analysis are presented in Table 3. TABLE III Results of semi-quantitative analysis on cable samples provided by FWM. Sample Min Dia (mm) Force (g) Robustness Def. Dia (mm) 1 6.9 48 F 4.8 2 9.5 130 G 6.5 3 14.9 228 G 9.4 4 25.4 460 G 13.7 5 12.1 185 G 8 6 20.4 560 G 12 7 16.2 480 F 10.7 8 22.8 580 P 20 9 17.6 385 G 9.9 10 16.5 410 G 10.5 Results in Table III may be sorted to identify good (G), acceptable or fair (F), and poor (P) values with respect to the features necessary for use in MIS Annuloplasty Rings. As discussed previously, the ideal characteristic is for a cable to be sufficiently flexible to compress for delivery through a catheter, yet maintain rigidity in the deployed state. Given this, samples that had a minimum bending diameter of <10 mm were considered good, while those with a minimum bending diameter of >20 mm were considered poor. While force to maintain this bending diameter is not a direct measure of cable bending modulus, it is a reasonable indirect measure; for this reason, an arbitrary value of >400 g was considered good, while <200 g was considered poor. One noticeable result was that low-strand-count cables (#7 & #8), were considerably less robust compared to the higher strand count cables. Among these cable samples, samples 2, 3, 9, & 10 had the best overall relative combination of stiffness, compressibility, and robustness. While it is premature to form specific cable selection recommendations, qualitative observations and this data suggest that a cable diameter of less than 0.08 in, combined with a strand count of 7×7, 7×19, or 19×7, is best suited for annuloplasty ring applications. B. Cable Selection Considerations Preliminary evaluation of FWM samples are consistent with the results of computer simulations, with both indicating that a wide variety of cable materials could be used for annuloplasty ring applications. Since the eventual core shape will dictate the effective modulus of a given cable type, material selection is not constrained by the inherent stiffness of the cable material. A likely cable selection strategy is to: Select material based on availability/familiarity. Select cable diameter to be similar in diameter to current “solid-core” rings. Select a standard, off-the-shelf cable, with moderate strand count and low bending modulus, to achieve maximum compression for delivery through catheter. Iterate with greater strand count if local maximum displacements are too great. Thus a flexible cable provides the ring with sufficient flexibility to compress for delivery through a catheter, while maintaining rigidity in the deployed state. Prototypes have been constructed employing this strategy. It is also possible to combine multiple cable types to achieve the combination of high bending for deployment as well as high post-deployed stiffness. While the foregoing is a complete description of the preferred embodiments of the invention, various alternatives, modifications, and equivalents may be used. Moreover, it will be obvious that certain other modifications may be practiced within the scope of the appended claims.
An annuloplasty repair segment for heart valve annulus repair. In one embodiment a multi-stranded cable replaces solid core wire for both the tricuspid and mitral valves. Cable allows for greater deployment flexibility for minimally-invasive surgical (MIS) implant, while still maintaining the required strength and similar tensile properties of solid-core wire. Stranded cable provides a MIS annuloplasty ring with sufficient flexibility in the x-y plane to allow a surgeon to squeeze the ring into a small incision, such as being able to pass through an 18 Fr or smaller catheter, while maintaining structural rigidity under forces exerted on the implanted ring by the cardiac cycle. The particular shape of the annuloplasty ring is fixed using a heat setting process.
0
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention pertains to methods and apparatus for re-heating and stretch-blow molding plastic parisons into containers having, in horizontal cross-section, at least in part a rotationally non-symmetric conformation, e.g., a generally oval, triangular or rectangular conformation. The present invention particularly pertains to methods and apparatus for the formation of such containers of substantially uniform wall thickness from physically symmetric parisons in which thermal variations are achieved which facilitate the rotationally non-symmetric conformation. 2. Description of the Prior Art Earlier attempts to reheat and stretch blow mold plastic parisons into rotationally non-symmetric containers utilized parisons that were uniformly heated throughout. The resulting containers had sidewalls of non-uniform thickness, due to differential stretching of the parisons. Unfortunately, containers having sidewalls of varying thickness are generally unacceptable due to increased incidence of structural degradation and failure. SUMMARY OF THE INVENTION In order to aid in the understanding of the present invention, it can be stated in essentially summary form that it is directed to methods and apparatus for asymmetrically heating symmetric parisons and placing the parisons in a desired angular orientation in an asymmetric stretch blow mold, for molding into containers having a uniform sidewall thickness. More specifically, the present invention includes a blow molding apparatus configured to receive a plurality of rotationally symmetric plastic parisons and output a plurality of non-round blow molded containers having a substantially uniform side wall thickness. The blow molding apparatus includes a transportation system extending through first and second heating stations and a blow molding station, capable of transporting parisons through the first and second heating stations and into the blow molding station in a step-wise fashion. The transportation system has coupling elements including a parison conveyor attached to a support frame for coupling a plurality of parison holders together in an endless loop, and a stepping servomotor for driving the parison holders in a generally oval-shaped circuit. Each parison holder is capable of supporting one parison on one parison retainer. The parison conveyor moves in response to the stepping servomotor in the generally oval-shaped circuit which includes a first linear segment, a first curved segment, a second linear segment, and a second curved segment. The conveyor stepping servomotor is coupled to the conveyor and is adapted for transporting the plurality of parison holders in step-wise fashion, with each step advancing all parison holders by a spacing corresponding to a pair of parison holders. A parison loader is disposed proximate to first linear segment, and includes a loader tray and a pair of pick arms. The loader tray defines a pair of generally parallel delivery tracks disposed adjacent to a parison hopper assembly, whereby parisons may be delivered from the parison hopper assembly along the delivery tracks to the pick arms. Each pick arm is adapted to engage a parison delivered along a delivery track, rotate towards parison holders, whereby parisons are delivered to and supported upon one of the parison holders. Preferably, the pick arm jaws may simultaneously engage and grab a pair of parisons, rotatably move the parisons to the parison holders, and release the parisons for support upon the parison holders in coordination with each step-wise movement of the parison holders. As the parison holders advance step-wise relative to the parison loader, each advancing parison holder receives one parison. The parison conveyor includes a guide assembly mounted to the support frame and defining a drive chain guide. A drive chain is provided for sliding movement through the drive chain guide, and rides upon a drive chain guide insert. The first and second heating stations are attached to the support frame proximate to the first and second linear segments, respectively, and are capable of heating parisons supported upon parison holders prior to blow molding using a source of heat such as heating lamps. Each of a plurality of mandrel assemblies includes a rotatable member that is rotatably disposed through and carried by a mandrel pallet of each parison holder. Each rotatable member includes a parison engaging mandrel and a sprocket. A first chain extends through the first heating station and engages a sprocket on each parison holder while the parison holders are in the first heating station. A first servomotor engages and drives the first chain as the parisons are step-wise transported through the first heating station by the conveyor, to effect a predetermined constant rate of rotation of the parisons relative to the heating lamps by rotation of the rotatable members, and consequently of the sprockets and the mandrels engaging the parisons. By rotating the parisons uniformly during movement through the first heating station, the parisons are heated in a rotationally symmetric fashion. For thicker parisons, or for other circumstances, it may be appropriate to rotate the parisons in the first heating station at a non-uniform rate as described below with respect to the second heating station. A second chain extends through the second heating station and engages the sprocket on each parison holder while the parison holders move step-wise through the second heating station along with the conveyor. A second servomotor engages the second chain to drive the second chain at a prescribed cyclic non-uniform rate as the parisons are transported through the second heating station, to effect a predetermined non-uniform rotation of each parison. By rotating the rotatable members and the parisons mounted thereto at a non-uniform rate during movement through the second heating station, each parison is heated in a rotationally asymmetric fashion. The resulting controlled thermal variations as a function of angular orientation of each parison facilitates stretch blow molding of such heated parisons into rotationally non-symmetric containers having substantially uniform side wall thickness. To determine the thermal variations as a function of angular orientation of each parison produced in the second heating station, at least one sensor is provided to identify an angular orientation of each parison at a selected position in the second heating station. The sensor includes at least one marker fixed to each rotatable member. In the case where a blow molded container having 180 degree symmetry is to be formed, a pair of markers may be fixed to each rotatable member by defining a pair of apertures through each sprocket and separated by 180 degrees with respect to the rotation axis of the rotatable member. Where blow molded containers having other than 180 degree symmetry are to be formed by the present invention, appropriate numbers and locations of the markers may be fixed to each rotatable member by defining appropriate apertures through each sprocket. The sensor includes a pair of detectors is fixed at a selected position in the second heating station to detect the markers on each of a pair of parison holders during the non-uniform rate of rotation, for independently detecting the angular position of the markers so as to define an angular orientation relation between the markers of each of the pair of parison holders and a selected point in the cycle of the non-uniform rate of rotation. Where the markers include apertures, detectors may be adapted to detect aperture edges as the sprockets rotate. Each detector is coupled to an optic cable, and is mounted to a detector mount defining a detector hole disposed to permit light to enter the detector. The blow molding station or stations may be disposed proximate to second linear segment, and an idle station or stations may be disposed after the second heating station, where the second chain disengages from the sprockets. At the idle station, the rotatable members and parisons engaged thereon may rotate freely, whereby information concerning the angular orientation of the parisons is lost. To regain such angular orientation information and reorient the parisons, a repositioning apparatus is disposed between the idle station and blow molding station, for independently angularly reorienting each parison immediately prior to introduction into the blow molding station. By such angular orientation, thermal variations in the parisons are employed to facilitate formation of non-round containers having a substantially uniform side wall thickness within blow molding station. The repositioning apparatus includes a pair of spindles positioned to engage conical ends of the mandrels of the rotatable members. A separately controllable spindle servomotor is coupled to each spindle. A pickup is situated adjacent to each spindle for detecting the rotational position of the markers fixed to the rotatable member on each parison holder, and is coupled to an optic cable. Where the markers include apertures, the pickups may be adapted to detect the aperture edges as the sprocket rotates. Each spindle is movable into and out of engagement with a mandrel by sliding action of powered slide coupled to spindle and operated pneumatically. An electrical circuit is provided for independently operating each spindle servomotor for a time sufficient to reconstruct the angular orientation relation between each marker and the selected point in the cycle of the non-uniform rate of rotation for each rotatable member. The spindle servomotors are adapted to independently reposition each parison holder and hence each parison to a desired, optimum orientation immediately prior to introduction of the parisons into the blow molding station. As a result, thermal variations in the parisons caused by non-uniform heating in the second heating station are employed to facilitate formation of non-round containers having a substantially uniform side wall thickness within the blow molding station. The blow molding station includes a pair of blow mold units having non-round interior surfaces and defining an axis that corresponds with a symmetry axis defined by parisons positioned in the blow mold units prior to blowing. Additionally, each non-round interior surface has rotational periodicity corresponding with the number and location of the markers fixed to the rotatable members. The blow molding station is adapted to simultaneously blow a pair of parisons to form non-round blow molded containers having a substantially uniform side wall thickness from rotationally symmetric parisons in coordination with each step-wise movement, where the repositioning apparatus has oriented those portions of each parison having relatively higher temperature to be blown into contact with regions of the interior surfaces disposed relatively closer to the axis of the blow mold unit, and has oriented those portions of each parison having relatively lower temperatures to be blown into contact with regions of the interior surfaces disposed relatively more distant from the axis of the blow mold unit. By orienting the parisons in this manner prior to blow molding, lower temperature portions of each parison are blown to relatively larger radial distances from the axis of the blow mold unit, while higher temperature portions of each parison are blown to relatively smaller radial distances from the axis of the blow mold unit, resulting in formation of non-round containers having a substantially uniform side wall thickness. After the blow molding station has blown a pair of parisons into blow molded containers with each step-wise movement of parison holders, conveyor moves the blow molded containers from the blow molding station to a parison unloader disposed proximate to the second curved segment and capable of disgorging the blow molded containers. It is preferred that the unloader disgorge the blow molded containers in coordination with each step-wise movement of the parison holders. The present invention further includes a programmable unit for coupling and coordinating movements of the stepping servomotor, the parison loaders, the blow molding station, the first and second servomotors, the spindle servomotors, and the parison unloader. The programmable unit includes an apparatus controller coupled to a protocol converter, which is in turn coupled to a servomotor controller. The apparatus controller may also receive a variety of information from other components of the apparatus of the present invention, and provide outputs to control such components. An operator interface is also coupled to the apparatus controller. The programmable unit acts so that during each step-wise movement of parison conveyor, the parison holders step-wise advance around the parison conveyor. The servomotor controller is coupled through a first servo drive amplifier to the first servomotor for prescribing rotation of the parisons being transported through the first heating station, and to the second servomotor through a second servo drive amplifier for prescribing the non-uniform rate of rotation of the parisons as the parisons are transported through the second heating station. The programmable unit electronically "gears" the first and second servomotors to the stepping servomotor. The programmable unit is also coupled to each detector through the optic cables for correlating the angular orientation of each parison at a selected position in the second heating station with a cycle of the non-uniform rate of rotation, and is coupled to each pickup for independently detecting the rotational position of the markers fixed to the rotatable member on each parison holder. In addition, the servomotor controller is coupled to the spindle servomotors through third and fourth servo drive amplifiers for independently angularly reorienting each parison holder, so that each parison is disposed at a chosen angular orientation prior to introduction into the blow molding station. The programmable unit also acts so that during each step-wise movement of the parison conveyor, a pair of parisons moves from the second heating station to the idle station, another pair of parisons moves from the idle station to the repositioning apparatus, yet another a pair of parisons moves from the repositioning apparatus to the blow molding station, and a pair of blow molded containers moves from the blow molding station to the parison unloader. Further, after each step-wise movement of parison conveyor, a pair of parisons is loaded onto the parison holders at the first linear segment, another pair of parisons is blow molded to form containers at the blow molding station, and a pair of blow molded containers is disgorged from the parison unloader. Although the number of pick arms, parison delivery tracks, detectors, spindles, spindle servomotors, blow mold units, and unloader arms is selected to be two, and each step-wise movement of the conveyor advances parison holders by a spacing corresponding to two parison holders within the scope of the present invention, the number of pick arms, parison delivery tracks, detectors, spindles, spindle servomotors, blow mold units, and unloader arms may be chosen to be greater or less than two. The method of the present invention for blow molding a non-round container having a substantially uniform sidewall thickness from a rotationally symmetric parison includes transporting the parison through the second heating station, and cyclically rotating the parison a prescribed non-uniform rate as the parison is transported through the second heating station to induce thermal variations in the parison. The step of cyclically rotating the parison may also include engaging the second chain with the sprocket on the rotatable member of the parison holder while the parison holder is in the second heating station, and coupling the second servomotor to drive the second chain at the prescribed non-uniform rate as the parison is transported through the second heating station. The method further includes sensing an angular orientation of the parison at a selected position in the second heating station, and may also include detecting a rotational position of at least one marker fixed to the rotatable member of the parison holder during a cycle of the prescribed non-uniform rate of rotation and defining a relation between the rotational position of the at least one marker and the cycle of the non-uniform rate of rotation. In addition, the method includes angularly reorienting the parison after heating and immediately prior to introduction into the blow molding station so that the thermal variations can be employed to facilitate formation within the blow molding station of a non-round container having a substantially uniform side wall thickness. The step of angularly reorienting the parison may also include positioning the spindle to engage the rotatable member and operating the spindle servomotor for a time sufficient to angularly reorient the parison to reconstruct the relation between a marker and a selected point in the cycle of the non-uniform rate of rotation. The method of the present invention may further include coupling the programmable unit to the sensor for correlating the angular orientation of the parison at the selected position in the second heating station with a cycle of the non-uniform rate of rotation, coupling the programmable unit to the pickup for detecting the rotational position of the at least one marker, and coupling the programmable unit to the spindle servomotor for angularly reorienting parison holder, whereby the parison is disposed at a chosen angular orientation prior to introduction into the blow molding station. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a plan view of a non-round container blow molding apparatus representing the present invention. FIG. 2 is an enlarged detail partial section view taken along line 2--2 of FIG. 1. FIG. 3 is block diagram representing operation of the present invention. FIG. 4 is an enlarged detail bottom plan view of the mandrel assembly of a non-round container blow molding apparatus representing the present invention. FIG. 5 is an enlarged detail bottom plan view of the mandrel assembly of a non-round container blow molding apparatus representing a second embodiment of the present invention. FIG. 6 is an enlarged detail partial section view taken along line 6--6 of FIG. 1. DESCRIPTION OF THE PREFERRED EMBODIMENTS The following portion of the specification, taken in conjunction with the drawings, sets forth the preferred embodiments of the present invention. The embodiments of the invention disclosed herein are the best mode contemplated for carrying out this invention in a commercial environment, although it should be recognized and understood that various modifications can be accomplished within the parameters of the present invention. Turning now to the drawings for a detailed description of the present invention, reference is first made to FIGS. 1-4, generally depicting blow molding apparatus 100 configured to receive a plurality of rotationally symmetric plastic parisons and output a plurality of non-round blow molded containers having a substantially uniform side wall thickness. Blow molding apparatus 100 includes transportation system 101 extending through first and second heating stations 102 and 103, respectively, and blow molding station 104, for transporting parisons through first and second heating stations 102 and 103 and into blow molding station 104 in a step-wise fashion. Transportation system 101 has coupling elements 105 including parison conveyor 106 attached to support frame 107 for coupling a plurality of parison holders 108 together in an endless loop, and stepping servomotor 109 for driving parison holders 108 in a generally oval-shaped circuit. Each parison holder 108 is capable of supporting one parison on one parison retainer 110. Parison conveyor 106 moves in response to stepping servomotor 109 in the generally oval-shaped circuit which includes first linear segment 112, first curved segment 113, second linear segment 114, and second curved segment 115. As depicted in FIG. 1, parison conveyor 106 moves in an anti-clockwise motion. Conveyor stepping servomotor 109 is coupled to conveyor 106 and is adapted for transporting the plurality of parison holders 108 in step-wise fashion, with each step advancing all parison holders 108 by a spacing corresponding to a pair of parison holders 108. As shown in FIG. 1, parison loader 117 is disposed proximate to first linear segment 112. Parison loader 117 includes loader tray 118 and a pair of pick arms 119. Loader tray 118 defines a pair of generally parallel delivery tracks 120 disposed adjacent to parison hopper assembly 121, whereby parisons may be delivered from parison hopper assembly 121 along delivery tracks 120 to pick arms 119. Each pick arm 119 has a pair of opposing, movable pick arm jaws 122 and is mounted along one side of rotatable loader axle 123. Each pick arm 119 is adapted to engage or grab a parison delivered along a delivery track 120 by pinching movement of pick arm jaws 122 actuated by air pressure supplied to pick arm jaw pneumatic actuators 125 by air tubing 127. After pick arm jaws 122 pinch together to grip parisons, pick arms 119 rotate towards parison holders 108 due to rotation of loader axle 123 resulting from actuation of a pick arm rotation driver, not shown. In this way, pick arms 119 move parisons from loader tray 118 to parison holders 108. Thereafter, pick arm jaw pneumatic actuators 125 cause pick arm jaws 122 to separate, releasing parisons, whereby parisons are delivered to and supported upon one of parison holders 108. Preferably, pick arm jaws 122 may simultaneously engage and grab a pair of parisons, rotatably move the parisons to parison holders 108, and release the parisons for support upon parison holders 108 in coordination with each step-wise movement of parison holders 108. As parison holders 108 advance step-wise relative to parison loader 117, each advancing parison holder 108 receives one parison. Parison conveyor 106 includes guide assembly 130 mounted to support frame 107 and defining drive chain guide 132. Drive chain 134 is capable of sliding movement through drive chain guide 132, riding upon drive chain guide insert 136. First and second heating stations 102 and 103 are attached to support frame 107 proximate to first and second linear segments 112 and 114, respectively. First and second heating stations 102 and 103 are capable of heating parisons supported upon parison holders 108 prior to blow molding, using a source of heat, such as heating lamps, not shown. Mandrel assembly 149 includes rotatable member 150 rotatably disposed through and carried by mandrel pallet 151 of parison holder 108. Rotatable member 150 includes parison engaging mandrel 152 and sprocket 154, as shown in FIG. 2. Each sprocket 154 is mounted to a mandrel 152 using a pair of snap rings 153 and dowel 155. First chain 156 extends through first heating station 102 and engages sprocket 154 on each parison holder 108 while parison holders 108 are in first heating station 102. First servomotor 158 engages and drives first chain 156 as the parisons are step-wise transported through first heating station 116 by conveyor 106, to effect a constant predetermined rate of rotation of the parisons relative to the heating lamps by rotation of rotatable members 150, and hence of sprockets 150 and mandrels 152 engaging the parisons. By rotating the parisons during movement through first heating station 102, the parisons are heated in a rotationally symmetric fashion. Second chain 160 extends through second heating station 103 and engages sprocket 154 on each parison holder 108 while parison holders 108 move step-wise through second heating station 103 with conveyor 106. Second servomotor 162 engages second chain 160 to drive second chain 160 at a prescribed cyclic non-uniform rate as the parisons are transported through second heating station 103, to effect a predetermined non-uniform rotation of each parison. By rotating rotatable members 150 and hence the parisons at a non-uniform rate during movement through second heating station 103, each parison is heated in a rotationally asymmetric fashion. The resulting controlled thermal variations as a function of angular orientation of each parison facilitates stretch blow molding of such heated parisons into rotationally non-symmetric containers having substantially uniform side wall thickness, as will be described. In order to determine the thermal variations as a function of angular orientation of each parison produced in second heating station 103, at least one sensor 164 is provided to identify an angular orientation of each parison at a selected position in second heating station 103. Sensor 164 includes at least one marker 166 fixed to each rotatable member 150. As depicted in FIGS. 2 and 4, in the case where a blow molded container having 180 degree symmetry is to be formed by the present invention, a pair of markers 166 may be fixed to each rotatable member 150 by defining a pair of apertures 168 through each sprocket 154 and separated by 180 degrees with respect to the rotation axis of rotatable member 150. Where blow molded containers having other than 180 degree symmetry are to be formed by the present invention, appropriate numbers and locations of markers 166 may be fixed to each rotatable member 150, for instance by defining appropriate apertures 168 through each sprocket 154. By way of example, as depicted in FIG. 5, where blow molded containers having 120 degree symmetry are to be formed, three markers 166 in the form of three apertures 168 defined through sprocket 154 at 120 degree separation may be provided. As a further example, not illustrated, where asymmetric blow molded containers such as a teardrop shape are to be formed, a single marker 166 may be fixed to each rotatable member 150. Referring to FIGS. 1-3, sensor 164 includes a pair of detectors 170 fixed at end 171 of second heating station 103 to detect markers 166 on each of a pair of parison holders 108 during the non-uniform rotation. Detectors 170 independently operate to detect the angular position of markers 166 so as to define an angular orientation relation between markers 166 of each parison holder 108 and a selected point in the cycle of the non-uniform rotation. Where, as illustrated in FIGS. 4 and 5, markers 166 include apertures 168, detectors 170 may be selected to be any of a wide variety of available photoelectric sensors, such as Cutler-Hammer Diffuse Reflective Photoelectric Sensor, Comet Series, No. 13106A6517 available from Eaton, Milwaukee, Wis., and adapted to detect aperture edges 172 as sprockets 154 rotate. Each detector 170 is coupled to optic cable 173, such as Cutler Hammer No. E51KF563. As shown in FIG. 1, blow molding station 104 is disposed proximate to second linear segment 114. The operation of blow molding station 104 will not be described in detail for the reason that the characteristics of such blow molding stations are well known in the art, such as described in U.S. Pat. No. 5,516,274. Also as shown in FIG. 1, the present invention includes idle station 177 disposed after second heating station 103, where second chain 160 disengages from sprockets 154. At idle station 177, rotatable members 150 and parisons engaged thereon may rotate freely, whereby information concerning the angular orientation of the parisons is lost. To regain such angular orientation information and reorient the parisons, repositioning apparatus 178 is disposed between idle station 177 and blow molding station 104, for independently angularly reorienting each parison immediately prior to introduction into blow molding station 104. By such angular orientation, thermal variations in the parisons can be employed to facilitate formation of non-round containers having a substantially uniform side wall thickness within blow molding station 104. With reference to FIG. 6, repositioning apparatus 178 includes a pair of spindles 180 positioned to engage conical ends 181 of mandrels 152 of rotatable members 150. A separately controllable spindle servomotor 182 is coupled to each spindle 180. A pickup 184 is situated adjacent to each spindle 180 for detecting the rotational position of the at least one marker 166 fixed to rotatable member 150 on each parison holder 108. Where markers 166 include apertures 168 as illustrated in FIGS. 4, 5, and 6 pickups 184 may be selected to be photoelectric sensors, such as Cutler-Hammer Diffuse Reflective Photoelectric Sensor, Comet Series, already described, coupled to optic cables 173 and adapted to detect aperture edges 172 as sprockets 154 rotate. Air pressure is provided for moving each spindle 180 into and out of engagement with a mandrel 152 by sliding action of powered slide 186. In a preferred embodiment, powered slide 186 may be selected to be any of a variety of powered slides, such as Powered Slide SEB25X.75-PBDBU7EJ6-AE available from PHD, Fort Wayne, Ind. An electrical circuit, not shown, is provided for independently operating each spindle servomotor 182 for a time sufficient to reconstruct the angular orientation relation between each marker 166 and the selected point in the cycle of the non-uniform rate of rotation for each rotatable member 150. In this way, spindle servomotors 182 are adapted to independently reposition each parison holder 108 and hence each parison to a desired, optimum orientation immediately prior to introduction of the parisons into blow molding station 104. As a result, thermal variations in the parisons caused by non-uniform heating in second heating station 103 can be employed to facilitate formation of non-round containers having a substantially uniform side wall thickness within blow molding station 104, as next described. As illustrated in FIG. 1, blow molding station 104 includes a pair of blow mold units 248 having non-round interior surfaces, not shown, with each blow mold unit 248 capable of blowing a parison to form a blow molded container. Each blow mold unit 248 defines an axis that corresponds with a symmetry axis defined by parisons positioned in the blow mold units 248 prior to blowing. Additionally, each non-round interior surface has rotational periodicity about the axis corresponding with the number and location of markers 166 fixed to rotatable members 150. For example, as depicted in FIG. 4, where blow molded containers having 180 degree symmetry are to be formed, two markers 166 in the form of two apertures 168 defined through sprocket 154 at 180 degree separation are provided, and the non-round interior surface of each blow mold unit 248 has rotational periodicity of 180 degrees. As a second example, as illustrated in FIG. 5, in a second embodiment of the present invention, where blow molded containers with 120 degree symmetry are to be formed, three markers 166 in the form of three apertures 168 defined through sprocket 154 at 120 degree separation are utilized, and the non-round interior surface of each blow mold unit 248 has rotational periodicity of 120 degrees. Blow molding station 104 is adapted to simultaneously blow a pair of parisons to form non-round blow molded containers having a substantially uniform side wall thickness from rotationally symmetric parisons in coordination with each step-wise movement, where repositioning apparatus 178 has oriented those portions of each parison having relatively higher temperature to be blown into contact with regions of the interior surfaces disposed relatively closer to the axis of blow mold unit 248, and has oriented those portions of each parison having relatively lower temperatures to be blown into contact with regions of the interior surfaces disposed relatively more distant from the axis of blow mold unit 248. By orienting the parisons in this manner prior to blow molding, lower temperature portions of each parison are blown to relatively larger radial distances from the axis of blow mold unit 248, while higher temperature portions of each parison are blown to relatively smaller radial distances from the axis of blow mold unit 248, resulting in formation of non-round containers having a substantially uniform side wall thickness. After blow molding station 104 has blown a pair of parisons into blow molded containers with each step-wise movement of parison holders 108, conveyor 106 moves the blow molded containers from blow molding station 104 to parison unloader 250. Parison unloader 250 is disposed proximate to second curved segment 115 and is capable of disgorging blow molded containers from the present invention. Parison unloader 250 includes a pair of unloader arms 252. Each unloader arm 252 is adapted to engage or grab a blow molded container by pinching movement of unloader arm jaws 254 actuated by air pressure delivered to unloader arm jaw pneumatic actuators 258 by tubing 260. After unloader arm jaws 254 pinch together to grip the blow molded containers, each unloader arm 252 rotates away from the proximate second curved segment 115 with rotation of unloader axle 262 resulting from actuation of unloader arm rotation driver 264. As a result, unloader arms 252 act to move blow molded containers away from the present invention. Thereafter, unloader arm jaw pneumatic actuators 258 cause unloader arm jaws 254 to separate, releasing blow molded containers and consequently disgorging the blow molded containers from the present invention. It is preferred that unloader arm jaws 254 simultaneously grip blow molded containers, rotate about the axis of unloader axle 262 to move the blow molded containers away from the second curved segment 115, and release blow molded containers in coordination with each step-wise movement of parison holders 108. The present invention further includes programmable unit 270 for coupling and coordinating movements of stepping servomotor 109, parison loaders 117, blow molding station 104, first and second servomotors 158 and 162, spindle servomotors 182, and parison unloader 250. Referring to FIG. 3, programmable unit 270 includes apparatus controller 272 coupled to protocol converter 274, which is in turn coupled to servomotor controller 276. Apparatus controller 272 may also receive a variety of information from other components of the apparatus of the present invention, and provide outputs to control such components. Operator interface 278 is also coupled to apparatus controller 272. Programmable unit 270 acts so that during each step-wise movement of parison conveyor 106, parison holders 108 step-wise advance around parison conveyor 106. Servomotor controller 276 is coupled through servo drive amplifier 280a to first servomotor 158 for prescribing rotation of the parisons being transported through first heating station 102, and to second servomotor 162 through servo drive amplifier 280b for prescribing the non-uniform rate of rotation of the parisons as the parisons are transported through second heating station 103. As used herein, electronic "gearing" refers to continuously sensing the instantaneous velocity of stepping servomotor 109 during step-wise movement, and continually adding such variable instantaneous velocity to the rate of rotation of first and second servomotors 158 and 162. Programmable unit 270 thus electronically "gears" the first servomotor 158 and the second servomotor 162 to the stepping servomotor 109. Programmable unit 270 is also coupled to each detector 170 through optic cables 173 for correlating the angular orientation of each parison at a selected position in second heating station 103 with a cycle of the non-uniform rate of rotation, and is coupled to each pickup 184 for independently detecting the rotational position of markers 166 fixed to rotatable member 150 on each parison holder 108. In addition, servomotor controller 276 is coupled to spindle servomotors 182 through servo drive amplifiers 280c, 280d for independently angularly reorienting each parison holder 108, whereby each parison is disposed at a chosen angular orientation prior to introduction into blow molding station 104. Programmable unit 270 further acts so that during each step-wise movement of parison conveyor 106, a pair of parisons moves from second heating station 103 to idle station 177, another pair of parisons moves from idle station 177 to repositioning apparatus 178, yet another a pair of parisons moves from repositioning apparatus 178 to blow as molding station 104, and a pair of blow molded containers moves from blow molding station 104 to parison unloader 250. Further, after each step-wise movement of parison conveyor 106, a pair of parisons is loaded onto parison holders 108 at first linear segment 112, another pair of parisons is blow molded to form containers at blow molding station 104, and a pair of blow molded containers is disgorged from parison unloader 250. Although as represented in FIGS. 1 and 2, in a preferred embodiment of the apparatus of the present invention, the number of pick arms 119, parison delivery tracks 120, detectors 170, spindles 180, spindle servomotors 182, blow mold units 248, and unloader arms 252 is selected to be two, and each step-wise movement of conveyor 106 advances parison holders 108 by a spacing corresponding to two parison holders 108, it will, of course, be understood that within the scope of the present invention, the number of pick arms 119, parison delivery tracks 120, detectors 170, spindles 180, spindle servomotors 182, blow mold units 248, and unloader arms 252 may be chosen to be greater or less than two. The method of the present invention for blow molding a non-round container having a substantially uniform sidewall thickness from a rotationally symmetric parison includes transporting the parison through second heating station 103, and cyclically rotating the parison a prescribed non-uniform rate as the parison is transported through second heating station 103 to induce thermal variations in the parison. The step of cyclically rotating the parison may also include engaging second chain 160 extending through second heating station 103 with sprocket 154 on rotatable member 150 of parison holder 108 while parison holder 108 is in second heating station 103, and coupling second servomotor 162 to drive second chain 160 at the prescribed non-uniform rate as the parison is transported through second heating station 103. The method further includes sensing an angular orientation of the parison at a selected position in second heating station 103, and may also include detecting a rotational position of at least one marker 166 fixed to rotatable member 150 of parison holder 108 during a cycle of the prescribed non-uniform rate of rotation and defining a relation between the rotational position of the at least one marker 166 and the cycle of the non-uniform rate of rotation. In addition, the method includes angularly reorienting the parison after heating and immediately prior to introduction into blow molding station 104 so that the thermal variations can be employed to facilitate formation within blow molding station 104 of a non-round container having a substantially uniform side wall thickness. The step of angularly reorienting the parison may also include positioning spindle 180 to engage rotatable member 150 and operating spindle servomotor 182 coupled to spindle 180 for a time sufficient to angularly reorient the parison to reconstruct the relation between a marker 166 and a selected point in the cycle of the non-uniform rate of rotation. The method of the present invention may further include coupling programmable unit 270 to sensor 164 for correlating the angular orientation of the parison at the selected position in second heating station 103 with a cycle of the non-uniform rate of rotation, coupling programmable unit 270 to pickup 184 for detecting the rotational position of the at least one marker 166, and coupling programmable unit 270 to spindle servomotor 182 for angularly reorienting parison holder 108, whereby the parison is disposed at a chosen angular orientation prior to introduction into blow molding station 104. The present invention having been described in its preferred embodiments, it is clear that the present invention is susceptible to numerous modifications and embodiments within the ability of those skilled in the art and without the exercise of the inventive faculty. Accordingly, the scope of the present invention is defined as set forth by the scope of the following claims.
Method and apparatus for forming stretch blow molded containers having uniform sidewall thickness from physical symmetric parisons. Parisons are heated non-uniformly by rotating at a non-uniform rate in a heating station. A sensor determines the angular orientation of the parisons emerging from the heating station. Each parison is angularly reoriented at a repositioning station prior to introduction into a stretch blow molding station having non-round interior surfaces, so that the temperature profile of each parison corresponds with differential expansion required to form the desired non-round container.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to an insertion apparatus for inserting various continuously supplied products into containers with ejection means arranged to move parallel to the products over an endless belt. According to the invention, the ejection movement of a piston of the ejection means is provided by a directrix which is inclined relative to the direction of movement of the products. The ejection means can be made to bypass the directrix by a switching mechanism. 2. Description of Prior Art Apparatus of the above types are generally known and are used in connection with continuous packaging apparatus which, for example, comprise a product chain with product compartments positioned thereon in which products such as vials, bottles, soap bars, etc., are positioned. Containers such as folded containers in which the products are to be inserted are provided and moved parallel to the product chain. Insertion occurs by means of ejection pistons which are moved along a principal movement direction by means of chain conveyors which are also moved parallel to the product chain. Insertion occurs by providing the ejection piston with a component of movement along a direction perpendicular to the principal direction of movement. To accomplish this, in one apparatus known in the art, a directrix is provided which is inclined with respect to the principal movement direction and is mounted on the product chain. In certain cases it becomes necessary that the product not be inserted within the container. This is because there is no container positioned opposite the product to receive it, or because such a container is positioned in a faulty manner. In this case the piston must not be guided and caused to move by the directrix. In the known apparatus a pivotable lever is provided, which, as desired, is either mounted on the directrix or can be so aligned, such that the pistons do not move along the directrix but rather are moved past the directrix without any component of force being impressed on the piston in the direction of ejection. Such a lever is disadvantageous insofar as the pistons which are initially moved only along the principal direction of movement meet the lever with a given pressure and then are suddenly reversed away from the lever and receive an ejection component of force. This involves a damaging impact, which can result in increased wear on the apparatus, which in turn reduces the reliability of the apparatus. In order to increase the operational reliability of the apparatus, and in particular, to reduce the risk of damage resulting from vibrations and the like which occur during the insertion of products into containers, the directrix is spring supported, such that with an insertion disturbance which occurs when the products jam either during insertion or when in the container, which exert an excessive force on the directrix, the ejector undergoes a slight relative movement to contact the ejector with the container and the machine is disconnected. A disadvantage of such an apparatus is that the apparatus tends to continue somewhat even after disconnection has occurred, such that the ejector continues its movement somewhat due to its contact with the directrix to immediately cause damage to occur. Furthermore, the directrix undergoes a pivoting movement such that the force necessary to remove the apparatus from the insertion location varies in accordance with the position of the insertion location with respect to the length of the directrix. SUMMARY OF THE INVENTION It is, therefore, an object of the invention to overcome each of the above disadvantages and to provide a surer, more reliable and dependable apparatus. According to the invention, a stationary guide curve is provided to guide the ejection means. By virtue of the inventive arrangement, the direction of movement of the ejection means is reversed in a soft and vibration-free manner, without impulse, in front of the directrix. The apparatus is reliably controlled over the entire reversal process such that impulses to the ejection means and/or impulses to the guide curve drive rollers are reliably prevented. According to the inventive apparatus, a further disadvantage associated with prior art apparatus is avoided in that according to a preferred embodiment, the guide curve is positioned on the direction reversing axle of the advancement means of the ejection means; the means may include a chain mounted on a chain wheel axle. With prior apparatus, a pivotable lever had to be mounted stationary in the housing of the apparatus. As a result, the chains are further tensioned such that the movement conditions vary, which can lead to poorer operation of the apparatus. According to the inventive arrangement, the movement conditions do not chage during subsequent tensioning of the chains between the ejection apparatus and/or the guide portions, such as guide rollers, and the guide curves. Yet a further advantage according to the invention is that the guide curve is formed as an outer curve on the exterior or outer portion of the cylinder of a guide cylinder. In this case the cam rollers of the apparatus are already being directed during direction reversal, which leads to a smoother run. Besides this, flatter insertion curves result for products of the same outside dimensions, since the insertion movement of the insertion ejection apparatus through the guide curve can already have occurred in the reversal zone of the transport means for the ejection means. The lever present in apparatus made according to the state of the art require a costly switching mechanism. In comparison, by virtue of the inventive arrangement, one achieves a reduction in the number of parts as well as a simpler arrangement from a constructional point of view. According to a preferred embodiment, the movement of the insertion ejection apparatus is vibration-free with respect to the cam roller positioned within the guide curve, which is particularly true when the guide has a configuration defined by a fifth order polynomial. A particularly smooth and clean as well as stable guide which guarantees a good guidance is achieved when the guide is not formed out of flat bent material nor cast, but rather when it is milled in one piece. While in principle it can be provided that the guide curve may be linearly adjustable relative to the guide roller at the zone of the oncoming movement of the injection ejection apparatus, it is notable that according to a most preferred embodiment, the guide cylinder is arranged such that its axle is perpendicular to the direction of forward movement, and the guide curve is reversed in the direction of the directrix, beginning at a spaced initial zone running parallel to the direction of movement of the edges of the guide cylinder and wherein the cylinder is mounted to be adjustable on its axle. The movement of the cylinder, i.e., the pivoting or the linear movement can be made to occur with either a hydraulic or pneumatic fluid cylinder-piston apparatus or can be achieved electromagnetically. Naturally, pivoting may be achieved by other drive means as well. The reliability and dependability sought according to the invention are further achieved according to the inventive apparatus, in that upon application of a force to the ejection means exceeding a preset limit value, the directrix releases and can be easily pivotable. To achieve this, in contrast with systems provided by the prior art, in which the directrix is always spring mounted, according to the invention, the directrix is mounted so as to be freely movable when subjected to an excess pressure. This may, for example, be achieved by pivoting the directrix out of its normal guide position to a rest position. However, it can further be provided that the directrix is actively moved away from the ejection means after encountering an excess resistance pressure as a result of a small relative movement switch which initially affects the entire forward movement, such as by a fluid cylinder arrangement or an electromagnet. In both cases there is no further pressure exerted on the ejection means nor on the product being inserted during subsequent movement of the apparatus, so that no damage can occur. According to yet another preferred aspect of the invention, the directrix is moved back to a rest or free position which is essentially parallel to its normal engagement position. As a result, the release pressure is essentially equal along all points along the directrix. After removal of the disturbance or interference, the directrix may then be manually returned to its normal position. To accomplish this simply, it is preferable to provide a apparatus having a release assembly having a release notch and a release cam, for example in the form of a roller mounted on ball-bearings, such that a lifter provided with a movable contact associated with a fixed contact functions to disconnect the apparatus when the lever has been lifted by virtue of a disturbance along the directrix. BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be described with reference to the annexed drawings, given by way of example only, in which: FIG. 1 illustrates one embodiment of the inventive apparatus for insertion of products in containers; FIG. 2 is a view illustrating the guide curve on the cylinder at the reversal location of the apparatus; FIG. 3 illustrates the same cylinder as previously but when the injection ejector is in the free-running position; FIG. 4 is a detailed view of another embodiment of the apparatus which illustrates the reversal location in dashed-lines in the free-running position of the ejection means; FIG. 5 is a view along line V--V of FIG. 1; FIG. 6 is a partical view of FIG. 1 with some elements particularly broken away to show cooperation of axis 84 with axis 80 via toothed wheels 81, 83 in order to journal arm 72 and consequently to move directrix 62 in portion 62'; and FIG. 7 shows merely for information deflecting means of prior art, namely lever 51 as described on pages 1 and 2 of this specification. DESCRIPTION OF PREFERRED EMBODIMENTS The inventive apparatus, according to one embodiment shown in FIG. 1, is housed in a casing 12. Chain wheel axles 14 and 16 are journalled at the ends into casing 12. Chain wheel axle 16 is driven by drive means and a motor (not shown). Spaced wheels 18, 20 and 22, 24 are each fixedly mounted on axles 14 and 16, respectively. Chains 26 and 28 are mounted on corresponding wheels 18, 22 and 20, 24, respectively. The chains are shown in chain lines in FIGS. 1, 4 and 5. Chain wheel axle 14 moves chain 28 in direction 30 (which delineates clockwise rotation of reel 20). in frame 12 and is securable such that by movement of chain wheel axle 14 in direction 30 the chains can be tensioned. Spaced insertion ejection carriers are mounted on the chains in a preselected, adjustable, spaced manner. Ejector carriers 32 comprise two stabilizers 34 and 36 which are secured directly to the chains. The ejector carriers further comprise two parallel guide shafts 38 and 40. An axially movable carrier block 42 is mounted to slide along each of shafts 38 and 40. Ejection or push rod 44 is mounted on carrier block 42 and moves together therewith. The pushing rod slidably extends through an opening in stabilizer 36, the opening being positioned between both of shafts 38 and 40 (see FIG. 1). A cam roller 46 is mounted at the lower end of carrier block 42 and extends radially with respect to axles 14 and 16 at each chain reversal zone. The apparatus of the invention is used in conjunction with a packaging apparatus in which products such as vials, bottles, etc. are packaged in containers. The products are conveyed by means of a product chain positioned parallel to and in front of chain 28. The product chain is not illustrated, and reference is herein made to U.S. Pat. No. 3,333,396, which illustrates such an apparatus, this document being incorporated herein by reference thereto. Cam roller 46 moves along a slide 48 as will be explained in greater detail below. After reversal along chain wheels 22 and 24, carriers 32 move back towards wheels 18 and 20 behind the plane shown in FIG. 1. Guide cylinder 50 is journalled onto chain wheel axle 14 and has an outer casing 52 comprising a guide curve 54 adapted to seat and guide cam rollers 46 (see also FIG. 5), the cam surface being milled out of the surface of the casing. In the embodiment of guide cylinder 50 shown in FIGS. 1 and 2, guide curve 54 opens into a guide 56 which guides cam rollers 46 whereby guide 56 is formed in a portion of casing wall 58 and extends essentially along a straight inclined line portion 60. The guide is formed between straight line portion 60 and a directrix 62 arranged parallel to line portion 60 in a movable manner. Line portion 60 turns into a curved portion near chain wheel 24 and then from the beginning of wheel 24 the curvature of the line portion changes into a cut-away portion 64 configured as well as guide curve 54 in the form of a higher order polynomial, particularly a fifth order polynomial, which can be easily represented and which has found to ensure a smooth deflection of cam roller 46 without pushing with a slowly increasing acceleration of movement component parallel to e.g. shaft 40. This is because such a movement law provides small forces, momenta, especially small impetus due to small static burden and inertia forces. An ideal range function of such a polynomial could be f(z)=10z 3 -15z 4 +6z 5 with 0≦z≦1. Casing wall portion 66 is secured to cut-away portion 64 so as to provide a guide surface 68 which is arranged essentially radially to chain wheel axle 16. Beneath drive axles 14 and 16 and under the plane of FIG. 1 (and therefore not visible in FIG. 1) slide 48 again initially comprises a curved guide surface for cam rollers 46 which return the moving insertion ejection apparatus along a movement path which is parallel to guide 56, before reaching the vicinity of guide cylinder 50, at which point it again curves such that cam roller 46 is moved along a direction perpendicular to the radius of axle 14. When guide cylinder 50 is rotated by about 45° by means of an eccentrically mounted fluid cylinder or electromagnetic or other drive means (not shown in detail in FIG. 1, but illustrated by a block schematically therein) guide cylinder 50 presents a surface, as shown in the embodiment of FIG. 3, in which the guide surface appears straight while the curved cut-out 70 is moved aside as a result of the rotation of the cylinder. Directrix 62 is mounted on two pivotable arms 72 and 74, pivotable along two pivot axes 76 and 78, respectively. Pivot arms 72 and 74 are themselves journalled along journal axes 80 and 82. Pivot arms 72 and 74 are adapted such that the directrix is moved to an essentially parallel position 62' as a result of the movement of the pivot arms. In the embodiment shown, journal axis 80 is located at the lower end of pivot arm 72 and comprises a toothed bevel wheel 81 which mates with another toothed bevel wheel 83 (FIG. 6) mounted on an axle 84 which is vertically aligned with respect to axis 80. Arm 74 is freely journalled both upon axis 82 and on axis 78. A disk 88 is mounted on axle 84 in the vicinity of front cover 86 of casing 12, which is provided at its outer periphery with a notch 90 (see FIG. 5), Projection or bearing 96 is biased into notch 90 by means of spring 92 though a lever 94 and locks into a preselected position on disk 88. As a result, directrix 62 in the embodiments of FIGS. 1 and 4 is held over axle 84, both toothed wheels, axle 80 and pivot arm 72. A movable contact 98 is mounted on lever 94 which operates in conjunction with fixed contact 100 (see FIG. 5). The embodiment described in FIGS. 1, 2, 3 and 5 operates as follows: Insertion ejection carrier 32 is moved by means of chains 26 and 28 on chain wheel 16, beneath the plane of FIG. 1 and in the direction of the return plane on axle 14 such that cam roller 46 enters a cam surface guide curve 54 of guide cylinder 50 at location 102 (see FIG. 5) and is guided during the further movement of ejector carrier around guide cylinder 50. In the embodiment of the guide cylinder and guide curve of FIGS. 1 and 2, cam roller 46 is moved over cut-out 70 of guide curve 54 and continues along guide 56 between directrix 62 and line portion 60. Carrier block 42, together with push rod 44, is moved along shafts 38 and 40 such that a product to be packaged into containers which is being moved along a product chain (not shown) at the same velocity as the insertion injection apparatus can be inserted into containers such as boxes by movement of the piston. Push rod 44 is forced into the box or container and, as it passes over section 64 is retracted from the container. As insertion ejection apparatus 32 is moved around chain wheel axle 16, cam roller 46 is moved along guide surface 68. Finally, cam roller 46 is returned along the rear plane, described above, along guide means, which are not illustrated in detail, to the exit point shown on the left side of FIG. 1, while at the same time push or piston rod 44 is retracted to the position shown. In the event of of a disruption or disturbance to the packaging machine, to that at a given location no product is advanced, or that no compartment is available, or that there is no container present, guide cylinder 50 is moved by a hydraulic cylinder or an electromagnetic cylinder, or the like (shown in a single black box in FIG. 1, which represents them as being conventional), out of the position shown in FIGS. 1 and 2, and into the position shown in FIG. 3 in which it is pivoted in a clockwise direction. In this position of guide cylinder 50 and guide curve 54, cam roller 46 is not engaged in guide 56 but is instead guided along a back edge of directrix 62 under guide 56 such that push rod 44 does not move along the path provided by guide 56, and wherein the ejection means is moved towards axle 16 without supplying a vertical component to the piston during the movement of the apparatus. As a result, no insertion of the product into the container occurs. Afterwards, in such a case, cam roller 46 is guided along and out of guide curve 54 at the location of FIG. 3, and guide cylinder 50 is once again moved back to its normal position shown in FIGS. 1 and 2. When a disruption occurs during the movement of cam roller 46, together with the insertion movement of push rod 44 in guide 56, such as, for example, the insertion movement of push rod 44 is somehow hindered, a higher pressure is exerted on directrix 62 over movable carrier block 42 and cam roller 46. When this pressure exceeds the pressure exerted by spring 92 (FIG. 5), directrix 62 is moved out of its normal position shown in FIG. 1 and is forced to the position shown in dashed lines in FIG. 1. In so doing pivot arm 72 pivots around its axis 80 together with axle 84 which is mounted to pivot together with it, and with it disc 88 such that notch 90 is in position 90' shown in FIG. 5. Bearing 96 is likewise displaced out of notch 90 into position 96'. This causes lever 94 to be raised and thus breaks contact between contacts 98 and 100 in the example shown (see FIG. 5). Instead of breaking contact by means of the lifting of lever 94, contact could, instead, be established. As a result of the contact interruption which results when the lever is raised, the apparatus is stopped, such that the cause of the disruption can be eliminated. To continue operation, a hand wheel 106 positioned in front of cover 86 is used to reset disk 88 to its normal operating position. In this position bearing 96 is repositioned in notch 90 and directrix 62 is moved back to its operational position shown in solid lines in FIG. 1. The apparatus is then again ready for use. When an opposing force is exerted on push rod 44 by guide slot 56, in order to stop the push rod from proceeding, the force acts via block 42 on guide roller 46 to force guiding straight edge 62 into the position illustrated in dotted lines in FIG. 1. The straight edge guide 62 is supported on levers 72 and 74, which upon displacement of straight edge 62, are pivoted about their axes of rotation 80 and 82. Bevel gear 81, as shown in FIG. 6, is connected to shaft 80 and meshes at right angles with a second bevel gear 83, which is connected by shaft 84 to disk 88. When guiding straight edge 62 is forced sideways, shaft 80 rotates disk 88 via gears 81 and 83 and shaft 84, as illustrated in FIG. 6. As shown in FIG. 5, when disk 88 rotates, snap-in ball 96 is forced out of the snap-end groove 90 of disk 88, and acts against the force of spring 92 in order to open switch 98, 100. When this switch is opened the equipment is shut down. FIG. 4 illustrates a further embodiment of the inventive apparatus in cross-section wherein the same elements illustrated in connection with the previous embodiment are identified by the same reference numerals. In this embodiment, instead of pivotably journalled guide cylinder 50, a linearly movable guide block 110 is provided which is milled in the same manner as guide cylinder 50 with a guide curve 54 having curved position 70. In the configuration shown in FIG. 5, cam roller 46 is moved along guide curve 54 in guide 56 between directrix 62 and line portion 60. In the position of block 110 shown in dashed lines in FIG. 4, the block is displaced out of the movement path of cam roller 46, for example by means of a fluid cylinder, a magnet, or the like, such that cam roller 46 moves freely behind block 110 and directrix 62 such that push rod 44 is not activated. Although the invention has been described with respect to particular means, materials and embodiments, it is to be understood that the invention is not limited to the particulars disclosed but extends to all equivalents included within the claims.
An insertion apparatus is provided for inserting continuously supplied products into containers. The insertion apparatus includes an ejection device which moves parallel to products along an endless conveyor system, and a curved directrix which is adapted to guide the ejection device in a direction which effects lateral movement of the products. The directrix is inclined relative to the direction of movement of the products, and a device is provided for bypassing movement of the ejection device with respect to the directrix so that the ejection device will move independently of the movement of the products.
1
FIELD OF THE INVENTION The present invention relates to compositions and methods for inhibiting deposits during calcination of fluxed iron ore pellets. BACKGROUND OF THE INVENTION Crude iron ore cannot be used directly in the steel making process, but must first be concentrated and refined. When the iron content of the ore is increased, the process generally is referred to as concentration, and this can sometimes be accomplished simply by crushing, screening, and washing. Other times, the ore is ground to very small particles before the iron oxides can be separated from the rest of the material, called gangue, which is normally accomplished by magnetic drums. However, even where there is satisfactory concentration, iron ore consisting of fine particles must first be agglomerated into a coarser form, and this process is referred to as agglomeration. The most desirable size for blast-furnace feed is from 6-25 mm, and pelletizing is one of the methods frequently used to achieve this type of coarse iron ore feed. In the pelletizing process, which accounts for about two-thirds of U.S. agglomerate production, the ore must be ground to a very fine size, less than 75 μm. The ground ore is mixed with the proper amount of water, and sometimes with a small amount of bentonite, and this is rolled into small balls 10-20 mm in diameter in a balling drum or disk. These green pellets are dried, then are heated to 1200°-1370° C. to bond the small particles, and finally are cooled. The heating can be done on a traveling grate, or in a shaft furnace, or by a combination of a traveling grate and a rotary kiln. Another of the chief raw materials in the steel making process in addition to the iron ore, is the fluxing material, consisting of lime (CaCO 3 ) and/or dolomite (CaCO 3 --MgCO 3 ). Typically, limestone is crushed and screened to the desired particle size, and burnt lime for steel making is then prepared from the limestone by calcination in a long rotary kiln. It is common to combine the iron ore pelletizing operation described above with the limestone and/or dolomite flux preparation and calcination by adding the limestone and/or dolomite particles directly to the iron ore particles which are to be formed into pellets. This mixture is then heated in the same device, usually a long rotary kiln, often with a traveling grate, so that the pelletizing and limestone and/or dolomite calcination are accomplished in the same step and in the same heating furnace. This combined step is usually referred to as calcination of the iron ore, although the chief result is the hardening of the green iron ore pellets. During the heating of the mixture of particles of limestone and/or dolomite flux and particles of iron ore formed into pellets, which will be referred to as flux pellet kilning, a problem is frequently encountered involving deposits which form on the walls of the rotary kiln or other furnace or heating device being used. These deposits are formed as a result of the flux pellet kilning operation, perhaps as a result of a combination of mechanical adhesion and condensation on the cooler skin of the kiln or furnace surface. The predominant constituent of such deposits is ferric oxide (hematite), with the majority of the remainder being magnetic iron oxide (magnetite). However, there is frequently a significant amount, about 2-10% by weight of the total deposit, of calcium phosphate, Ca 10 (PO 4 ) 6 (OH) 2 (hydroxyapetite). Such deposits create substantial problems in the kilning operation, e.g., large portions of such deposits can break away and become admixed with the pellets being calcined, thus resulting in an unacceptable final product. Also, as a result of the formation of these deposits, significant removal problems are created. For example, there is a significant down time for the kilns, furnaces or other heating devices being used, during which the deposits are mechanically removed by such off-line cleaning methods as compressed air driven jack-hammers, small charges of blasting explosives, or more time-consuming approaches utilizing hammers and chisels, etc. These processes of mechanical removal present serious problems in addition to the down time which they entail. An on-line method of cleaning which is frequently used involves mechanical removal of these deposits by "shooting", in which the deposits are blasted away by repeated discharging of shotguns against the deposits. This procedure poses the obvious risks to the personnel performing it, but also has been known to result in serious damage to the walls of the kiln or other furnace heating device being used. In order to significantly inhibit the formation of these flux pellet kiln deposits, and thereby significantly increase the efficiency of the flux pellet kilning operation, the present invention provides for the administration of a water soluble magnesium compound that undergoes thermal decomposition, preferably to form magnesium oxide at temperatures of about 100°-1200° C. BRIEF DESCRIPTION OF THE PRIOR ART U.S. Pat. No. 4,503,019 discloses the use of blends of magnesium oxide and copper oxychloride for inhibiting and dispersing calcium oxide deposit formation in coal-fired kilns. U.S. Pat. No. 5,221,320 discloses a method of inhibiting the formation of iron oxide containing deposits on the surfaces of heating devices during fluxed iron ore pellet calcination, wherein the flux employed contains phosphate, which consists of a treatment of magnesium hydroxide, copper oxychloride and an alkyl benzene sulfonate suspending agent. The phosphate content, as P 2 O 5 , of the flux in said fluxed iron ore pellet must be less than 1% by weight of the total weight of flux and iron ore in the pellets. None of the above applications in any way suggest the compositions and methods of the present invention. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of inhibiting the formation of iron oxide containing deposits on the surfaces of heating devices during fluxed iron ore pellet calcination comprising treating the atmosphere of said heating device in which said calcination takes place with a deposit-inhibiting amount of an aqueous solution comprising a magnesium compound that undergoes thermal decomposition, preferably to form magnesium oxide, at temperatures of about 100°-1200° C., with temperatures of from about 100°-500° C. particularly preferred. In a preferred embodiment, the present invention comprises treating the atmosphere of the heating device where calcination takes place with a deposit-inhibiting amount of an aqueous solution comprising (1) a magnesium salt, e.g., magnesium acetate, magnesium sulfate, magnesium chloride, or magnesium nitrate (the latter particularly preferred) with (2) a surfactant selected from the group consisting of ethoxylated alkylphenols, (e.g., ethoxylated nonylphenols), phosphate esters (e.g., Triton QS-44, Union Carbide) or nonionic glucosides, particularly preferred (e.g., Triton BG-10). The present invention, being an aqueous solution, is easier to store, handle and feed than a suspension of a water insoluble salt as found in, e.g., U.S. Pat. No. 5,221,320. Suspensions, which have been previously used for the purposes of the present invention are viscous, require stirring to keep the solids suspended, and prove difficult to pump and feed. The present invention is also more effective than prior art methods at equivalent magnesium treatment rates. This is believed to be due to the increased surface area of the magnesium salt decomposition products as compared to the relatively large particle size of magnesium hydroxide particles. It has been found that water soluble magnesium compounds that undergo thermal decomposition, preferably to form magnesium oxide at temperatures of about 100°-1200° C. are effective for inhibiting deposits on the interior of iron ore pellet kilns. The magnesium salt can be formulated as a concentrated solution, and then diluted with water and applied through spray nozzles into the atmosphere of the kiln. Additional product components believed to improve performance are nonionic or anionic surfactants for improved spray atomization due to surface tension reduction and calcium salt inhibitors to inhibit spray nozzle deposition, e.g., CaCO 3 . In a preferred embodiment of the present invention, the magnesium compounds undergo thermal decomposition to form magnesium oxide at a temperature of from about 100°-500° C. An exemplary magnesium compound is magnesium nitrate. Exemplary surfactants are ethoxylated nonylphenols, phosphate esters and nonionic glucosides. Exemplary deposit control agents are 2-phosphono-butane-1,2,4-tricarboxylic acid and 1-hydroxyethylene-1,1-diphosphonic acid. The present invention further relates to a composition for inhibiting the formation of iron oxide containing deposits on the surfaces of heating devices during fluxed iron ore pellet calcination comprising an aqueous solution containing (1) a magnesium salt, e.g., magnesium acetate, magnesium sulfate, magnesium chloride, or magnesium nitrate (particularly preferred) with (2) a surfactant selected from the group consisting of ethoxylated alkylphenols, phosphate esters or nonionic glucosides. Field studies have revealed that a particularly preferred embodiment of the present invention, an aqueous solution of magnesium nitrate and a nonionic glucoside surfactant, is especially effective in inhibiting deposition in a taconite pellet kiln. Specifically, the treatment has virtually eliminated down-time for off-line cleaning, as well as substantially reducing deposit formation and the need for shot-gunning. The aqueous solution containing magnesium is injected into the kiln in an amount of from about 0.001-0.1 pounds of Mg as MgO per ton of pellets, with from about 0.005-0.05 pounds of Mg as MgO per ton of pellets being preferred. While the particularly preferred embodiment described above contains about 63% by weight magnesium nitrate hexahydrate (or 10% Mg as MgO) and 1% by weight nonionic glucoside surfactant, with the balance being water, a more meaningful treatment range is as follows: the water soluble product of the present invention contains from about 1-25% Mg as MgO, with from 5-15% Mg as MgO preferred. While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
A stable aqueous solution comprising a water soluble salt of a magnesium compound is used to reduce deposits in kilns or furnaces used to make iron ore agglomerates, known as pellets, during iron ore calcination.
2
RELATED APPLICATIONS AND CLAIM OF PRIORITY [0001] This application claims priority to U.S. Provisional Patent Application serial No. 60/264,574, entitled METHOD AND APPARATUS FOR TESTING SAMPLES UTILIZING A SAMPLING APPARATUS AND ONE OR MORE SEPARATE DETECTORS, and filed on Jan. 26, 2001, the specification of which is hereby incorporated by reference. [0002] This application claims priority to U.S. Provisional Patent Application serial No. 60/340802, entitled FRACTION COLLECTION SYSTEM AND METHOD, and filed on Dec. 12, 2001, the specification of which is hereby incorporated by reference. [0003] This application claims priority to U.S. patent application Ser. No. ______, entitled THIN FILM ELECTROPHORESIS APPARATUS AND METHOD, filed on Jan. 14, 2002, the specification of which is hereby incorporated by reference. [0004] The specification of U.S. patent application Ser. No. ______, entitled NANOPOROUS MEMBRANE REACTOR FOR MINIATURIZED REACTIONS AND ENHANCED REACTION KINETICS, and filed on Jan. 14, 2002, is hereby incorporated by reference. TECHNICAL FIELD [0005] This document relates generally to analysis of samples, including large scale sampling of biological test samples. More specifically, the present invention relates to a method and apparatus for analyzing fractions or analytes from a sample. BACKGROUND OF THE INVENTION [0006] Large scale testing and analysis is important to many industries, including biotechnology, medical diagnostics, and pharmaceuticals. For example, manufacturers in the biotechnology industries implement automated laboratory systems, such as high throughput processing, to test and analyze large numbers of samples. [0007] In some cases however, analytical or preparatory techniques are not suitable for use with automated processing systems. Consequently, certain procedures are performed separately from the automated system and involve some amount of human intervention, thus increasing the production time and cost. [0008] Capillary electrophoresis (CE), for example, has been used in both analytical and preparative applications. Among the advantages of CE is the ability to quickly separate similar compounds on a nanoliter scale. For example, CE can be used with mixtures of proteins, macromolecules, nucleotides, enantiomers, and chiral molecules. Pharmaceutical, agricultural, and chemical industries routinely use CE in analytical applications, as well as in research and development. [0009] The biotechnology industry, for example, has capitalized on the ability of CE to quickly analyze small volumes of material. Capillary electrophoresis can be used with nucleic acids, separations and analysis. There remains, however, a need for a rapid process that identifies and isolates large volumes of material, such as is generated by pharmacogenomics and the human genome project. [0010] Advances in cloning techniques, for example, have enabled the genomic sequencing of a organisms. A sample of DNA, or a fragment thereof, from a particular organism, can be cloned and then analyzed using CE to determine the DNA sequences. Also, CE may be used to isolate a particular DNA fragment for cloning. For example, CE may isolate a preparative amount of a particular DNA fragment from a mixed DNA population. This purified fragment can then be inserted into recombinant DNA plasmid, which then clones the corresponding protein. [0011] Conventional slab gel electrophoresis (SGE) is unsuitable for high volume analysis of DNA sequences. Each sample derived from SGE is physically cut from the slab and separately analyzed, thus requiring human intervention. Consequently, these and other disadvantages render SGE incompatible with an automated, high throughput system. [0012] Limitations in the speed, volume and efficiency of CE technology have impaired efforts to streamline or automate genomic processes. Thus, there remains a need for faster, higher volume, and more efficient methods of DNA separation, isolation and cloning. In addition, there is a need for an improved system and method for analyzing biological and chemical samples that yields high resolution and rapid results. SUMMARY [0013] The present subject matter is directed to apparatuses, systems and methods for performing high throughput collection of fractions or analytes. In one embodiment, analysis, or detecting, is integrated into the present system. In one embodiment, detection is performed as a subsequent process after having collected the various fractions. [0014] In one embodiment, the present subject matter includes a method of analyzing fractions from one or more samples. Each fraction is a part, or portion, of the original sample from which it is obtained or collected. The original sample can be any material provided for testing, including a biological sample (for example, a pure compound or a mixture of compounds) wherein the identity, or amount of each component of the sample, is unknown. In one embodiment, the method involves providing one or more samples to a sampling apparatus that collects successive fractions from each of the samples at discrete points in time. The discrete points in time may be equally or unequally spaced from one another. In one embodiment, the method involves removing the fractions from the sampling apparatus and then analyzing the fractions with one or more detector systems that are separate from the sampling apparatus. [0015] In one embodiment, the present subject matter includes a fraction analysis system. The system includes an apparatus that collects successive fractions from each of one or more samples at discrete points in time. The system also includes one or more detectors, each of which are separate from the fraction collection apparatus and configured to analyze the successive fractions. [0016] In one embodiment, after removal from the fraction collection apparatus, the collected fractions are available for subsequent processing in another process. The present subject matter may be automated. [0017] In one embodiment, relevant fractions are combined or isolated from the analytical spectra to produce a purified product on a preparatory scale. Analytical and preparatory modes may be performed on the same test sample undergoing one pass through the sampling apparatus. [0018] In one embodiment, the detection system is separate from the collection system. In one embodiment, the detection system, or detector, is integrated with the collection of fractions. [0019] In one embodiment, the present subject matter may be used with multiple detection systems or simultaneously use different detection systems. For example, in one embodiment, a CE instrument simultaneously processes 100 samples, thus producing 100 separate fractionated collections, whereby each collection has 384 individual fractions in a specimen plate. As another example, in one embodiment, the present subject matter allows detecting 25 fractionated collections by a first detection system (e.g. fluorescence), detecting another 25 fractionated collections by a second detection system (e.g. UV-VIS), and detecting the remaining fractionated collections by a third detection system (e.g. mass spectrometry). [0020] In one embodiment, a method of testing or analyzing a sample utilizing continuous sampling techniques enables the direct conversion of analog data into digital signals. The resulting digital data preserves the analog data and allows analysis (e.g., spectral analysis) at a later time, thus allowing uncoupling of the detector system from the sampling apparatus. In one embodiment, an unknown sample is continuously analyzed by a method that includes selecting a predetermined time period and waiting for a period of delay. The delay period is produced, in part, by latency of migration through the present system. The delay period is determined by the sampling rate. The sampling rate is selected to be at least twice the highest frequency of the smallest discrete moiety present in the unknown sample. Pursuant to Nyquist's theorem, the original data is preserved by sampling at twice the highest frequency. In one embodiment, a sampling rate greater than twice the highest frequency is used. Successive fractions are collected at predetermined intervals of time. Fraction collection continues for the predetermined time period. [0021] In one embodiment, the present subject matter includes a time sequenced testing apparatus having a sample clock, a sample injector, a sampling apparatus, a fraction collector, a computer, and a detector. The sample clock is configured to mark a time period sequence. The sample injector is adapted to apply one or more samples to a sampling apparatus. The sampling apparatus provides fractions for collecting. In one embodiment, the sampling apparatus includes a separation pathway such as, for example, a capillary or channel. The fraction collector is coupled with, and coordinated with the output of the sampling apparatus, and is adapted to receive successive fractions wherein the size and number of the fractions are determined by the time period sequence. The computer is adapted to coordinate the sample clock with the fraction collector and the sampling apparatus. The detector is uncoupled from the sampling apparatus and configured to detect the fractions received from the fraction collector after the time period sequence has expired. [0022] In one embodiment, the apparatus also includes a capillary, a cathode electrode, an anode electrode, a power supply, a buffer solution and a plurality of actuators or movers. The capillary is adapted to perform capillary electrophoresis. The cathode and anode electrodes are positioned parallel to respective ends of the capillary. The power supply, adapted for high voltage, is configured to create an electric gradient across the cathode and anode. The buffer solution is comprised of components non-reactive to the sample. The actuators are adapted to facilitate transfer of the capillary and electrode from a sample to the buffer solution, and from the capillary and electrode to the fraction collector. [0023] In various embodiments, the present subject matter allows separating, identifying, and isolating high volumes of samples using nanoliter amounts of sample material while limiting human interaction and achieving high resolution. The present subject matter can be used with DNA separation, isolation and cloning. [0024] Other aspects of the invention will be apparent on reading the following detailed description of the invention and viewing the drawings that form a part thereof. BRIEF DESCRIPTION OF THE DRAWINGS [0025] In the drawings, like numerals describe substantially similar components throughout the several views. Like numerals having different letter suffixes represent different instances of substantially similar components. [0026] [0026]FIG. 1 illustrates a block diagram of a method in accordance with the present subject matter. [0027] [0027]FIG. 2 illustrates a schematic diagram of a CE apparatus in accordance with the present subject matter. [0028] [0028]FIG. 3 illustrates a schematic diagram of a multiple-capillary CE apparatus in accordance with the present subject matter. DETAILED DESCRIPTION [0029] In the following detailed description, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that the embodiments may be combined, or that other embodiments may be utilized and that structural, logical and electrical changes may be made without departing from the spirit and scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined by the appended claims and their equivalents. [0030] By way of overview, the present system includes a separation pathway having an input end coupled to a reservoir, or well, of sample material. The sample material is migrated through the separation pathway and fractions are eluted from the output end of the separation pathway. The eluate is received in a collection reservoir or well. The fractions move through the separation pathway under a migration field. The migration field may be created by an electric potential, a pneumatic source, a vacuum source, or a magnetic source, or other field source. Consider the case of an electric field. In this embodiment, the electric field is created by an electric potential applied by electrodes in contact with the input end and the output end of the separation pathway. In one embodiment, a first electrode is coupled to the input end of the separation pathway and a second electrode is coupled to the collection reservoir. In one embodiment, the collection reservoir includes a plurality of wells, such as for example, a 96-well plate. The second electrode is coupled to each well of the 96-well plate. At a predetermined frequency, the output end of the separation pathway is brought into contact with each successive well of the collection reservoir, thus setting up an electric field within the pathway. Fractions eluted from the separation pathway migrate into the contacted well and when the separation pathway is moved away from the collection reservoir, the migration is halted. A controller coupled to the present system controls the frequency of the contact between the separation pathway and the collection plate. In addition, the controller adjusts the relative positions to cause each successive fraction to be deposited into a different well of the collection plate. In this manner, the migratory field is modulated and each well of the collection plate receives a particular fraction eluted at a particular time. [0031] In one embodiment the controller adjusts the position of the output end of the separation pathway and the collection plate remains stationary. In one embodiment, the separation pathway remains stationary and the controller adjusts the position of the collection plate. In one embodiment, both the separation pathway and the collection plate are adjusted by the controller. In one embodiment, the first and second electrodes are affixed to the input and output ends, respectively, of the separation pathway and the controller modulates the applied voltage. [0032] In one embodiment, a plurality of separation pathways are provided with each pathway having an input coupled to a sample well and each pathway having an output coupled to a multi-well collection plate. For example, in one embodiment, 96 separation pathways are coupled to a 96-well input plate and the output of each separation pathway is coupled to a 96-well collection plate. Thus, the output end includes 96 collection plates. In one embodiment, each of the 96 collection plates are positioned independently and in another embodiment, each of the 96 collection plates are positioned as a group. An actuator coupled to the collection plate may be coupled to, and operated by, the controller. The actuator may include an x-axis actuator and a y-axis actuator or a rotary actuator. The actuator may also be coupled to the output end of each separation pathway. [0033] The intensity of the migration field, in one embodiment is controlled by making, or breaking electrical contact with the collection plate. In one embodiment, the field intensity is controlled by making and breaking contact at the input end. Other arrangements are also contemplated, such as, for example, a pneumatic system in which applied air pressure is used to elute fractions from the separation pathway. In one embodiment, the migration field is provided by a vacuum source. In one embodiment, a magnetic field, produced by current in electrical windings in the proximity of, or surrounding, the separation pathway, is energized to create a migration field. The field magnitude may be modulated between two intensity levels. For example, in one embodiment, the field magnitude is modulated between zero and a particular upper value. As another example, the field magnitude may be modulated between two nonzero values. [0034] A fraction detector, or detector system, may be positioned at the output end of the separation pathway or the collection well. In one embodiment, fractions are collected without use of a detector and subsequent processing includes analysis by a detector. In various embodiments, the detector includes a fluorescent detector, an ultraviolet-visible (UV-VIS) detector, a mass spectrometry detector, an immunoassay detector, an electrochemical detector, a radiochemical detector, a nuclear magnetic resonance (NMR) detector or a surface plasmon resonance (SPR) detector. [0035] Capillary Electrophoresis Testing Method [0036] [0036]FIG. 1 depicts a testing method 100 practiced according to the present invention using CE analysis. It will be appreciated that other separation pathways are also contemplated, including for example, a micro-fabricated or nano-fabricated separation pathway. At 110 , a time period sequence is defined. Nyquist's theorem for sampling serves as a guide for determining a sampling rate. According to Nyquist the sampling rate must be at least twice the highest frequency of the smallest discrete moiety present in the sample in order to reconstruct the original signal. Here, the analog data is preserved digitally by continuous sampling at a rate greater than twice the highest frequency. The sampling rate is thus, a function of the time period. [0037] Consider an example wherein CE is used to separate individual fragments of different size DNA (one base different). The defined time period is determined by choosing a sampling rate that captures no more that one base pair per sampling. Thus, the defined time period captures the smallest discrete moiety in the sampling. The summation of all these time periods over the entire time a sample is analyzed constitutes the time period sequence. The time period sequence may include a finite number of equally spaced time periods. In one embodiment, the time periods differ logarithmically, exponentially, or geometrically. In one embodiment, the sequence of time periods is experimentally determined. The time period sequence may be defined by any method known in the art of continuous sampling. [0038] At 115 , a test sample is introduced into the CE instrument. In one embodiment, the test sample is injected, however, other methods of applying the sample to the CE instrument are also contemplated. The sample may be robotically or manually introduced. It will also be appreciated that other analytical or preparatory devices are also contemplated. For example, immunoassay, or high performance liquid chromatography (HPLC), or other assay techniques may also be used. The sample may include a mixture of proteins, macromolecules, nucleotides, carbohydrates, enantiomers, small molecule libraries or natural compounds. [0039] At 120 , a voltage is applied across the CE capillary. In one embodiment, the medium within the capillary, or separation pathway, and the characteristics of the test sample determine the voltage applied. [0040] At 125 , a time period elapses. The time period is determined by the time period sequence at 110 . During this time period, an electric gradient exists across the separation pathway due to the voltage applied at 120 . The gradient resolves and separates the individual components in the test sample. In one embodiment, a two hour time period is established and fraction collection occurs every 30 seconds after an initial delay period of one hour. [0041] At 130 , the voltage from the capillary is removed following expiration of the time period at 125 . Thus, the present subject matter achieves continuous sampling. In one embodiment, sampling does not occur after removal of the voltage from the capillary and the electric gradient is removed. Thus, a fraction is captured when the voltage is applied. [0042] At 135 , a fraction is collected corresponding to the time period during which the electric gradient exists across the capillary. The collected fraction includes the material collected during the time period in which analysis occurs. In one embodiment, the fraction is collected in an individual well of a standard specimen plate, for example, a 96-well or 384-well specimen plate. The fraction may be manually or robotically collected. Other devices used to hold fractions are contemplated within the present invention. For example, test tubes, blotting paper, or individual vials may be used. [0043] In one embodiment, after collecting a fraction at 135 , the specimen plate is moved into position to receive the next fraction, at 140 . For example, the specimen plate may be moved robotically. In one embodiment, the separation pathway, or capillary, is moved to manipulate the output into the next well of the specimen plate. In one embodiment, the methods from 120 through 140 are repeated through each successive time period 125 until the last time period expires in the time period sequence defined at 110 . The method collects fractions when an electric gradient is applied across the capillary, thus ensuring continuous sampling of the test sample throughout the entire analysis. Consequently, each fraction has been captured within a discrete time period on the specimen plate. In one embodiment, the sampling time is synchronized with the mobility change of the analyte. [0044] After the last time period, at 150 , the last fraction is collected, at 155 . In one embodiment, at 160 , the specimen plate is removed from the CE instrument. After removal from the CE instrument, at 165 , the contents of the specimen plate are detected. In one embodiment, detection includes, for example, charge-coupled device (CCD) arrays using an ultraviolet (UV) or fluorescence monitor may detect the entire specimen plate at one time. Alternatively, the specimen plate may be detected individually or row by row. In one embodiment, the specimen plate undergoes more than one detection process. For example, the specimen plate may be monitored first by V, then fluorescence, and then by mass spectrometry. Other detection modes, such as conductivity, electrochemical, or radioactive means are also contemplated. In one embodiment, the detector includes a fluorescent detector, an ultraviolet-visible (UV-VIS) detector, a mass spectrometry detector, an immunoassay detector, an electrochemical detector, a radiochemical detector, a nuclear magnetic resonance (NMR) detector or a surface plasmon resonance (SPR) detector. [0045] In one embodiment, the method according to FIG. 1 is practiced using a CE instrument that separates individual base pairs of DNA. Once a detector detects the fractions in the specimen plate, a spectra is produced of the separation in which each individual peak corresponds to an individual base pair. From this analytical spectra, desired base pairs may be isolated and the corresponding fraction amplified by polymerase chain reaction (PCR), thus creating preparative amounts of isolated and purified base pairs. [0046] In one embodiment, the CE analysis may be automated. For example, detection, at 165 , may be accomplished using a high throughput system. Further, creating preparatory amounts of a specific fraction in the specimen plate may also occur robotically using a high throughput system. Accordingly, the present subject matter provides for an automated process of testing large numbers of samples in a high throughput system. In one embodiment, detection is uncoupled from the sampling apparatus and both analytical and preparatory modes may be practiced on a single pass though the sampling apparatus. More than one detection device may be utilized on the same specimen plate. In this way, high volumes of samples may be analyzed using multiple detection systems in both an analytical and preparatory mode using a small amount of material. [0047] Capillary Electrophoresis Sampling Apparatus [0048] In accordance with the present invention, a diagram of system 200 is provided in FIG. 2. In the embodiment shown, sampling apparatus 200 includes a CE instrument used to separate, isolate, and resolve mixtures of proteins, macromolecules, nucleotides, enantiomers, and chiral molecules based on the differences in molecular charged to mass ratios. In this embodiment, the CE instrument is configured to sequence DNA fragments and isolate individual base pairs. [0049] In one embodiment, capillary 210 is filled with a molecular sieving matrix, such as polyacrylamide, polyethylene oxide or other types of polymers. Other types of gel may also be used. It will also be appreciated that other CE techniques such as isoelectric focusing, isotachophoresis (ITP), and hydrophrobicity (micellar electrokinetic capillary chromatography, MECC), and other CE techniques may be used. Coupled to capillary 210 is electrode 225 . Electrode 225 includes anode 215 at one end and cathode 220 at the other end of the capillary. By means of power supply 230 , a high voltage is applied across electrode 225 , creating a positive charge at anode 215 and a negative charge at cathode 220 . This in turn creates an electric gradient across capillary 210 . Voltmeter 235 is connected to power supply 230 and indicates the voltage applied to electrode 225 . [0050] In one embodiment, electrode 225 and capillary 210 are positioned inside sample reservoir 255 holding test sample 260 . Injector 250 coordinates injection of test sample 260 into capillary 210 . Other injectors 250 and sample holders 255 may be used to apply sample 260 to capillary 210 . For example, an automated injector system in which the sample holder 255 includes a syringe may also be used. [0051] In one embodiment, sample holder 255 includes an individual well in a 96-well, or larger or smaller, specimen plate. [0052] Vertical sample mover 270 and horizontal sample mover 275 , (also referred to as actuators) are represented in the figure by directional arrows. In one embodiment, mover 270 and mover 275 are positioned to move sample holder 255 , buffer holder 263 , or capillary 210 , such that capillary 210 and electrode 225 are in contact with the contents of reservoir 255 or 263 . For example, vertical and horizontal movers 270 and 275 are operable to move sample container 255 out of contact with capillary 210 and electrode 225 after the test sample is injected. Movers 275 and 270 position buffer container 263 such that buffer solution 265 is in contact with electrode 225 and capillary 210 . Movers 270 and 275 may be manual or robotic. In one embodiment, the actuators include one or more linear or rotary motors. [0053] In one embodiment, computer 240 coordinates the actions of injector 250 , power supply 230 , volt meter 235 , and time period clock 245 , and movers 270 , 275 , 285 and 280 . Computer 240 executes a computer program to coordinate the electric field gradient intensity with the collecting of fractions. In one embodiment, system 200 is configured such that injector 250 applies sample 260 to capillary 210 . Movers 270 and 275 position buffer container 263 such that capillary 210 and electrode 225 is immersed in buffer solution 265 . In this embodiment, the anodic end of electrode 225 is immersed in buffer solution 265 . [0054] Computer 240 , in one embodiment, includes a processor with memory, a user input device (such as a keyboard or mouse), an output device (such as a display or printer). The memory contents can include program memory or data derived from the present subject matter. [0055] In one embodiment, computer 240 instructs power supply 230 to apply a voltage across electrode 225 such that the anodic end 215 of the electrode carries a positive charge while the cathodic end of the electrode 220 carries a negative charge. Thus, an electric gradient forms across capillary tube 210 . The electric gradient is maintained across electrode 210 for a defined time period marked by clock 245 . After the time period marked by clock 245 expires, the voltage supplied by power supply 230 is removed, thereby removing the electric gradient across capillary 210 . Once the electric field is removed, analysis by CE is suspended or interrupted. Interruption of the migration field may include terminating the field or modulating the field between two or more non-zero intensity levels. [0056] During the time period, buffer solution is drawn up from buffer container 263 and drawn through capillary 210 and collected in fraction collector plate 290 in an individual collector well 295 . In one embodiment, fraction collection occurs while the voltage is applied across electrode 225 . Fraction collector plate 290 may include, for example, a 96-well specimen plate, an array of vials, or other specimen plates. [0057] After the time period marked by clock 245 expires and power supply 230 has removed the voltage across electrode 225 , vertical mover 280 and horizontal mover 285 position fraction collector plate 290 such that a next individual collector well 295 is positioned to receive the next fraction from capillary 210 . After fraction collector plate 290 is positioned to receive the next fraction from capillary 210 , clock 245 begins measuring a successive time period triggering application of a voltage across electrode 225 supplied by power supply 230 . During this time period, the next fraction is collected from capillary 210 by the successive individual fraction well 295 . [0058] The time periods marked by clock 245 may be uniform or different for each successive time period. For example, each time period measured may be 30 seconds in duration, or, alternatively, the first time period may be 90 seconds to account for the void volume of the capillary 210 , and successive fractions may be collected on a 30 second basis. As another example, time periods may be measured logarithmically, geometrically or exponentially. In one embodiment, the sampling time is synchronized with the mobility change of the analyte. For example, where mobility of an analyte is half as fast, the time period is twice as long. [0059] In one embodiment, after sampling is complete, movers 280 and 285 transport the fraction collection plate 290 to a detection processing area. A second sample may be analyzed while the first sample is being detected at another processing station. In one embodiment, each fraction collector plate undergoes multiple detection methods after removal from system 200 . [0060] Multiple-Capillary and Capillary Electrophoresis Apparatus [0061] System 300 in accordance with one embodiment of the present subject matter is illustrated in FIG. 3. In this embodiment, system 300 includes multiple capillaries by which multiple test samples are simultaneously analyzed. [0062] The embodiment illustrated in FIG. 3 employs an array of capillaries 330 or separation pathways. The separation pathways may including a plurality of individual capillaries 210 which may include microfabricated or nanofabricated channels. A corresponding array of electrodes 335 , including individual electrodes 225 , are coupled to capillary array 330 such that each electrode 225 is coupled to a corresponding capillary 210 . Each individual capillary 210 and its corresponding electrode 225 is in contact with an individual test sample well 315 . Collectively, these individual test sample wells 315 form an array of sample wells 310 . In one embodiment, this array of sample wells 310 , in which each individual sample well 315 contains a test sample 260 , may be a 96-well sample plate. Other sample arrays are also contemplated. For example, a collection of vials or test tubes may be used. [0063] Each test sample 260 contained in individual sample well 315 may be identical to other test samples contained in sample array 310 or the test samples may vary across the array. For example, each individual sample well within the array of sample wells may contain a different DNA fragment to be sequenced. Conversely, non-redundant, expressed sequence tag (EST) libraries may be constructed used in connection with other high throughput processes. [0064] The 96-well specimen plate does not limit the number of capillaries that may be used in this apparatus at any one time. For example, a 384-well sample plate may be used in which 384 capillaries and 384 varied or identical samples may be simultaneously analyzed. Fractions for each capillary 210 are collected in fraction collector plate array 390 , wherein array 390 includes a plurality of fraction collector plates 290 configured to receive fractions. Each individual capillary 210 corresponds to an individual fraction collection plate 290 . Movers 280 and 285 coordinate positioning of the fraction collector plates relative to the capillaries, to receive successive fractions. [0065] In one embodiment, multiple samples are analyzed and detected at a subsequent processing station. For example, detection may occur as part of a high throughput system such as a CCD array configured for ultraviolet-visible (UV-VIS) or fluorescence detection. In one embodiment, multiple detection systems are used. For example, some fractions may undergo UV-VIS detection while other fractions undergo fluorescence detection and still other fractions undergo both UV-VIS and fluorescent detection. [0066] The present invention may be practiced in both an analytical mode and a preparatory mode. In one embodiment, a sample undergoes CE analysis, thus creating multiple fractions on a specimen plate. At a later time, the specimen plate may be detected using laser-induced fluorescence, thus generating an analytical spectra of the processed sample. From this spectra, certain peaks corresponding to certain fractions may be amplified and duplicated, for example, using PCR or cloning. In this manner, preparatory amounts of certain fractions have been generated from the same specimen plate that provided the analytical data. [0067] In the figure, plate 310 is shown coupled electrically to power supply 230 by electrode 215 . In addition, array 390 is shown coupled electrically to power supply 230 by electrode 220 . Each plate 290 within array 390 is coupled electrically to electrode 220 . In the embodiment shown, plates 310 , 290 and array 390 are electrically conductive, and fabricated of such materials as a metal or conductive ceramic. In one embodiment, plate 310 is fabricated of non-conductive, or semiconductive, material and each well, or reservoir, 315 is lined with an electrically insulative material and electrode 210 is coupled to each well 315 by an individual electrode. In one embodiment, array 390 , or plates 290 , are fabricated of non-conductive, or semiconductive, material and each well or reservoir 295 in plate 290 is lined with an electrically insulative material and electrode 220 is coupled to each well 295 by an individual electrode. [0068] Any number of fractions may be collected without regard to correlating a detected peak to a specific fraction during the analysis. [0069] Alternate Embodiments [0070] In one embodiment, each separation pathway is associated with a particular collection plate having a plurality of collection wells. Thus, 96 collection plates are used in a system having 96 separation pathways. In this manner, each separation pathway is individually controllable relative to the associated collection plate for that pathway. In one embodiment, the separation pathway is stationary and the collection plate is positionable by an actuator. The collection plates are mounted in a frame or otherwise synchronized to move together. In one embodiment, the collection plates are stationary and the separation pathways are positionable by an actuator. In one embodiment, each separation pathway is positioned independently of the position of other pathways. In one embodiment, each collection plate is positioned independently of the position of other plates. In one embodiment, one actuator, or set of actuators, controls movement of a collection plate (or array of collection plates) along a first axis, such as an x-axis. A second actuator, or set of actuators, controls movement of a separation pathway along a second axis, such as a y-axis. Other arrangements of actuators are also contemplated. [0071] The actuators may include one or more linear or rotary actuators, or motors. For example a first linear motor controls movement of a collection plate along an x-axis and a second linear motor controls movement of the plate along a y-axis. Rotary actuators may also be used to control the relative position of the separation pathway relative to the collection plate. The actuators may include a pneumatic cylinder, a lead screw, a hydraulic cylinder, an electric solenoid or a magnetic actuator. [0072] Conclusion [0073] The above-described system provides, among other things, a system, apparatus and method for collection and analysis with high resolution and high throughput. [0074] It will be appreciated that the methods described herein may be performed in different orders than described and that portions of a method may be repeated. [0075] It is to be understood that the above description is intended to be illustrative, and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description. The scope of the invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.
A method of injecting, isolating and separating mixed analytes from one or more samples. The method includes collecting successive fractions from each of a plurality of samples at discrete points in time. Fractions may be analyzed at the time of collecting, or later, using one or more detector systems. In one embodiment, a processor controls the elutions of fractions by modulating the migration field in a separation pathway. The processor also controls distribution of the fraction into a particular collection well of a plurality of collection wells.
1
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a passive diversion device for entertainment and stress relief. In particular, the device has two surfaces separated by a small distance and is configured to provide two equilibrium positions, one having a convex shape and the other having a concave shape when viewed from the same direction. The largest average dimension of the surfaces is substantially greater than the thickness of the device. By applying finger pressure to a surfaces of the device, the surfaces invert from one equilibrium position to the other. [0003] 2. Background Art [0004] Hand held devices for exercise, amusement and stress relief are known in the industry. There are types of hand-held amusement devices that emit sounds. For example, U.S. Pat. No. 724,545 describes a snapping button with a springing snapping leaf. After pushing the leaf, it automatically springs back up to its original position and it emits a snapping sound. U.S. Pat. No. 949,551 describes a somewhat similar device with a convex surface that, after pushing in on the surface, automatically snaps back to its convex position due to the tension of the material. A hole in the device controls the sound emitted by the device. U.S. Pat. No. 1,206,933 describes a stiff plate with a reversible bulge, having a picture on its face, whereby reversal of the bulge causes the plate to emit a sound related to the picture. U.S. Pat. No. 1,026,256 describes a sounding disk made up of a diaphragm secured to a holder. Spaces are left between the holder and diaphragm such that movement of the diaphragm is not obstructed, and a high volume of sound is produced. [0005] There are also hand-held exercise devices that provide stress relief such as U.S. Pat. No. 5,830,109. Such devices are typically digital or spherical in shape and are fabricated with flexible cores. These devices rest comfortably in a user's hand and the user squeezes and/or kneads the device. [0006] Inexpensive amusement devices that also are capable of relieving stress are desirable and continuously sought. SUMMARY OF THE INVENTION [0007] The present invention provides a simple, inexpensive device that can be used for passive entertainment and stress relief through manual manipulation of the device. The device may be manufactured with varying degrees of stiffness, sizes, texture, color and scent so that individuals may chose a device based on personal preferences. The device may additionally be adapted to change color and/or produce sound upon manipulation. [0008] In accord with the invention, an amusement and stress relief device comprises a flexible material formed into a disk-like shape having two opposite surfaces, a center portion and a peripheral portion, wherein the center portion has a convex/concave shape relative to the peripheral portion, and wherein the device is stable in tow positions, a first stable position where a first surface is concave and a second surface is convex and a second stable position where the first surface is convex and the second surface is concave. Preferably, the center portion protrudes out of a plane containing the peripheral portion. The disk-like device preferably has a circular peripheral edge, but can be formed with any shape peripheral edge. [0009] Devices of the invention can be of any color, contain surface images or patterns, contain surface textures, contain scents, change colors, or contain various combinations of such features. BRIEF DESCRIPTION OF THE DRAWINGS [0010] [0010]FIG. 1 is a top view of a preferred embodiment of the invention in the form of a disk. [0011] [0011]FIG. 2 is a side view of the device of FIG. 1 illustrating one equilibrium position and illustrating the second equilibrium position by dashed lines. [0012] [0012]FIG. 3 is a cross sectional side view of the device of FIG. 1. [0013] [0013]FIG. 4 is a cross sectional side view of a flexible, polymeric disk, which can be used to form the device illustrated in FIG. 1. DETAILED DESCRIPTION OF THE INVENTION [0014] With reference to the drawings, a preferred embodiment of the device in accord with the present invention will be described. The device 10 is shown in a preferred disk-like shape. However, the shape of the device may vary, for example, it may be square, octagonal, or triangular. Each device includes a peripheral lip portion 1 and a center portion 2 surrounded by the lip portion 1 . The device has an upper surface 3 and a lower surface 4 , one surface being concave and the other surface being convex. The concavity and convexity of the surfaces 3 , 4 are interchangeable. In other words, the device has two stable equilibrium positions, one being the concave upper surface 3 with convex lower surface 4 and the other being the convex upper surface 3 with concave lower surface 4 . Manual manipulation of the device inverts the surface from one equilibrium position to the other. The concave surface 3 or 4 preferably has a single peak 5 in the middle of the center portion 2 . The device, however, may have more than one peak 5 , provided that the two equilibrium positions as described are present in the device. [0015] The cross-section of the device is substantially uniform in thickness. However, in a preferred device as shown in FIG. 3, the peripheral lip 1 is thicker in cross-section than the center portion 2 . It is believed that the thicker peripheral portion can add stability to the equilibrium positions. The center portion 2 can be of uniform thickness or it can taper such that the thickness of the center portion 2 nearest the peripheral lip 1 is thickest and becomes thinner as it approaches the peak 5 . [0016] The dimensions of the device can vary depending upon both personal preference and the hand size of a user. Preferably, the disk has an overall diameter d (or length l of the longest dimension for non-circular shaped devices) ranging between about 0.75 inch and about 6 inches. The lip portion 1 forms a border around the center portion 2 . The lip is sized such that the ratio of the width w of the lip to the diameter d is a maximum of about ¼. More preferably, w/d is in the range of about {fraction (1/30)} to about ⅕. If the device is not circular, then the largest dimension of the device can be used as a pseudo diameter for considering the ratios discussed herein. [0017] The thickness of the device depends upon a number of variables such as the diameter, the polymeric material being used to form the device including the flexibility of the material and its stiffness or hardness, the tactile response desired, etc. One skilled in the art can determine a suitable thickness by routine experimentation after fixing the other variables. Overall, the device has a substantially uniform cross-sectional thickness t, and the ratio of t/d typically is a maximum of about {fraction (1/10)}. More preferably, the ratio of t/d is in the range of about {fraction (1/80)} to about {fraction (1/15)}. The thickness t c of the center portion 2 for a one inch diameter disk made of ethylene-vinyl acetate preferably is about 0.05 to 0.08 inch. However, the thickness can taper from the periphery of the disk to the center where it can be thinner, as previously discussed. Preferably, the peripheral lip 2 thickness t l is somewhat larger than the center portion 1 thickness t c . The thickness of the peripheral lip portion is determined by appearance, tactile feeling and its affect on the stability of the equilibrium positions of the device. The thickness of the lip can be outside of the range of ratios discussed above, as long as the device exhibits the two equilibrium positions. [0018] The height h p of the peak(s) 5 above the peripheral lip 2 or the plane containing the peripheral edge of the device depends also upon such variables as the desired appearance, the diameter and thickness of the device, the desired tactile response, the material from which it is formed, the desired life, etc. Such height can readily be determined by a routine experimentation after fixing the other variables. As illustrated in FIGS. 2 and 3, the ratio of h p /d preferably is a maximum of about ⅓. More preferably, the ratio of h p /d ranges between about ⅕ and about {fraction (1/10)}. [0019] In one preferred embodiment, the device is disk shaped made of ethylene-vinyl acetate copolymer and has an overall diameter of about 1.0 to 1.5 inches, a peripheral lip width of about 0.2 inch, a cross sectional thickness at the lip portion 1 t l of about 0.030 inch, a cross sectional thickness at the center portion 2 t c of about 0.013 to 0.018 inch, and a peak height h p of about 0.12 to 0.18 inch. Even more preferably, the cross sectional thickness at the center portion 2 tapers from near the lip 1 inwards to the center such that the thickness near the lip 1 is about 0.030 inch and gradually decreases to a thickness t c at the center of about 0.015 inch. [0020] Other diameter disks preferably are formed having similar ratios of dimensions. [0021] The device can be formed in the shape of a square, triangle, octagon and many other shapes. The dimensions of the device for such shapes are similar to a disk of approximately the same surface size. In such other shapes, the length “l” of the longest dimension is equivalent to the disk diameter d, and the thickness, peripheral lip width and height are dimensioned accordingly, as discussed above. [0022] The entire device can formed from a sheet of a thin, flexible material. Thus, after forming the bi-stable device, an individual can invert the top and bottom surfaces 3 , 4 by manual manipulation. Preferably, the device is fabricated of a light, inexpensive polymeric material that is capable of independently retaining its shape at each of the two equilibrium positions. Various materials can be used to provide diverse degrees of stiffness so that individuals have options in choosing the amount of pressure that must be applied to invert the device surfaces 3 , 4 . The surfaces 3 , 4 of the device also can be provided with various textures, such as smooth, ridged, bumpy, etc., each texture providing a different tactile affect when manually manipulated. The device may also be fabricated to emit sounds upon inverting the surfaces 3 , 4 between their convex and concave positions. Generally, such noise making is accomplished by choosing particular device materials that are stiffer to produce a popping or snapping sound when they are inverted. The devices also can be made in varying colors, including pearlescent or iridescent materials, or can incorporate glow in-the-dark materials. Logos, characitures, initials, photographs and other illustrations also can be painted or embossed on the device surfaces 3 , 4 . Scented compositions can be contained in the device material, so as to emit a scent when the device is manipulated. The material also can be heat sensitive, for example, so as to change color as it is manipulated. [0023] The device can be fabricated from the flexible seal found within the cap of certain bottles, such as certain plastic soda bottles. If one opens certain soda bottles, at the interior surface of the cap can be found a disk seal that is a separate component from the cap. This disk seal is typically flat and disk-shaped, with a lip portion 1 and a center portion 2 (see FIG. 4). The lip portion 1 typically has a cross-sectional thickness greater than that of the center portion 2 , and the center portion 2 typically has a substantially uniform thickness as shown in FIG. 4. The exact dimensions of the seal will vary depending upon cap size and bottle type. This disk seal can be formed into a device in accord with the present invention having a bi-stable convex/concave shape by, for example, placing the center portion 2 over the tip of a hard curved surface of appropriate dimension, and pulling on the disk seal at the lip portion 1 until a peak 5 is formed at the center having the desired peak height h p . When the device is formed as such, the center portion 2 , which was initially uniform in thickness t, stretches out and becomes thinner and tapered in cross section from the lip portion 1 towards the peak(s) 5 . [0024] The disk seals found in certain bottle caps are typically formed of a material known as “Compound E04”, which is manufactured by Crown Cork and Seal. The material is flexible, resilient, tough and translucent. “Compound E04” is a polymer made of 18% vinyl acetate copolymer of polyethylene. The material has a tensile strength of 2700 psi, an elongation of 700% and a flexural modulus of 8000 psi. [0025] Any polymeric material having similar properties can be used to manufacture the device beginning. Such materials must have physical characteristics that permit forming a central peak and must be capable of inverting between and retaining opposing concave and convex positions at the peak. When the device having peak(s) 5 are manufactured as described above, by placing a flat polymeric disk over a rounded surface member and exerting force to stretch the device, polymers that have a tensile strength of at least 800 psi, an elongation of at least 100% and a flexural modulus of at least 200 psi are preferred. The properties of the polymer are determined to prevent the device from breaking or splitting during the fabrication process and to provide a device having the bi-stable positions for use. [0026] Some specific examples of polymers that are suitable for the purposes of this invention are those exhibiting the above described characteristics and are described in the MODERN PLASTICS ENCYCLOPEDIA HANDBOOK (published by McGraw-Hill, Inc., 1994), for example: fluoroplastics (such as polymers and copolymers of florinated ethylene and polypropylene); polyamides or nylons; polybutylenes; thermoplastic polyesters (such as polyethylene terephthalate “PET”); polyethylene and ethylene copolymers (such as ethylene-ethyl acrylate “EEA”, ethylene-methacrylate “EMA”, ethylene-vinyl acetate “EVA”, ethylene butyl acrylate “EBA”, ionomers, ethylene-vinyl alcohol copolymers “EVOH”, and ethylene acid copolymers); silicones; thermoplastic elastomers (such as polyolefin blends, thermoplastic copolyesters, and thermoplastic polyurethanes); vinyl polymers and copolymers; and blends thereof. [0027] Alternatively, devices of the present invention can be formed from sheets of the polymer material by stamping the initial shape from a sheet to form a blank, and then forming the concave/convex portion by pulling the blank over a rounded surface. Another alternative is to form a plurality of concave/convex portions by vacuum forming the sheet, and then stamp out devices, each containing a concave/convex portion. Various textures can be formed onto the surface of the sheet by pressure and/or heated rollers or plates. Thus, the surfaces can be dimpled, contain ridges, or have other physical characteristics to provide a texture. [0028] Another method for making the devices of the present invention uses molds for forming and shaping the device in one step by an injection molding process. Those skilled in the art easily may envision further alternative methods for making the devices of the present invention. [0029] In addition to the use of colored polymeric materials, the surfaces 3 , 4 can also be painted in varying colors, and logos, caricatures, initials, photographs and other illustrations can be painted or embossed on the surfaces 3 , 4 . The device can also incorporate chemicals to change colors with changes in temperature or other atmospheric conditions. [0030] The invention including preferred embodiments thereof has been described herein. Such description is for illustrative purposes only, and it is to be understood that changes and variations may be made without departing from the spirit or scope of the invention as set forth in the following claims.
A device is described that possesses an overall shape that comfortably fits into a user's hand, and in particular, can be manipulated by the fingers. The device is fabricated of a pliable material that readily can be manipulated by manual pressure, yet holds its equilibrium positions absent pressure. The device has convex/concave surfaces which can be inverted to provide two stable equilibrium positions. The surfaces of the device may have different textures, such as smooth and ridged. The material of the device can have various colors, and also may be phosphorescent. Floral, fruit, spice and other scents may be added to the material such that the scent emanates from the device as the user manipulates the device.
0
FIELD OF THE INVENTION This invention relates to a method and apparatus for sealing packages or bundles of product cartons on a conveyor line. In particular, the invention pertains to improved sealing apparatus for individually sealing with film a series or succession of product packages rapidly and efficiently. BACKGROUND OF THE INVENTION Many products are shipped and displayed for sale to the public in cartons. Currently, many products are sold in large volumes to small businesses or consumers in warehouse stores and the like. Large volume sales require manufacturers to bundle or attach cartons together using shrinkwrap film and the like. In the sale of facial tissue cartons, for example, it is common to bundle together six, eight, ten or more cartons in a shrinkwrap film package for sale to consumers. Apparatus for shrinkwrapping cartons together must be capable of rapidly, efficiently, and automatically stacking cartons together in a bundle, wrapping them with film, and sealing the bundle. The process must occur rapidly, and usually is most efficiently performed in a series of steps along a conveyor line. Sealing the shrinkwrap film tightly and securely around the bundle of cartons is necessary to provide a tight bundle that will maintain its integrity during shipment of the products. One challenge in shrinkwrapping cartons is to improve the speed of the operation so that more cartons per unit time may be wrapped. Heat sealing of shrinkwrapped film requires physically holding together for a predetermined time period two opposing film surfaces. When sealing a convoy or series of bundles in succession, it is usually necessary to move the cartons along a predetermined path in bundles, and then seal each carton on both ends using a sealing mechanism. Many times the sealing mechanism is capable of holding together in close proximity two film surfaces at the end of a bundle. A method and apparatus that can accurately and quickly perform these steps is highly desirable. SUMMARY OF THE INVENTION An apparatus and method is provided for sealing bundles of cartons that are passed in series along a moving conveyor line. A frame is aligned with the conveyor, and a movable carriage assembly is connected to the frame. Packages or cartons of product are stacked and bundled by film, such as thermoplastic film, in a series of sealing steps. The apparatus includes at least one motor mounted on the frame which is capable of engaging the carriage assembly to facilitate reciprocating (i.e. back and forth) movement of the carriage assembly in relation to the moving packages. A separate computer controlled servo motor may be employed in some embodiments of the invention to drive the opening and closing of seal bars on the carriage assembly to effect sealing of the film at each end of the package. This drive may use a belt to apply force to the seal bars. In one embodiment of the invention, a second motor, such as a servo motor, is mounted on the stationary frame. The motor is adapted to engage the carriage assembly to move the upper and lower seal bars in relation to one another, opening and closing the seal nip. In another embodiment of the invention, the first motor means comprises at least one servo drive. In some embodiments, a pair of servo linear slide modules move the carriage back and forth along the conveyor line. The apparatus may contain a second motor that is controlled by electronic signals generated using a microprocessor. A method of sealing packages with film using a sealing mechanism connected to a reciprocating carriage is disclosed, comprising several steps. First, a first package is provided and surrounded by a film. Then, the step of closing the sealing mechanism upon the film is accomplished, thereby sealing the film on a first end of the first package. A next step involves opening the sealing mechanism. Next, at a predetermined time the carriage is moved in relation to the first package. A next step relates to closing the sealing mechanism upon the film, thereby sealing the film on a second end of the first package. Multiple packages may be sealed in series by repeating the steps of the method. In some applications, the second end of each package is adjacent the first end of the next package in series. The closing of the sealing mechanism upon the film may seal the film on a second end of the first package while simultaneously sealing the first end of a second package. This is so because the packages (bundles of product cartons) may be oriented end-to-end on a conveyor line. BRIEF DESCRIPTION OF THE DRAWINGS A full and enabling disclosure of this invention, including the best mode shown to one of ordinary skill in the art, is set forth in this specification. The following Figures illustrate the invention: FIG. 1 is a drawing of a perspective view of the conveyor line assembly with frame and movable carriage; FIG. 2A shows a side view of the assembly with motor, belt, and pulley system with seal bars in the process of opening (separating) after sealing packages C and D; FIG. 2B depicts the carriage seal bars in the fully open position, with the carriage having traveled down the conveyor line (to the left) to engage the next packages D and E; FIG. 2C shows the seal bars in the closed position during the sealing of film on the ends of packages D and E; FIG. 2D shows the seal bars re-opening to begin their travel across package E to seal the film between packages E and F. DETAILED DESCRIPTION OF THE INVENTION A general description of the invention is provided below, followed by a more detailed description of the apparatus as shown in the Figures. The invention includes an electrical and mechanical drive system for the seal bar module of a shrink wrapping machine. Upper and lower seal bars move in a vertical direction to seal and cut off shrinkwrap film between adjacent bundles of product cartons (i.e. hereinafter stacks of cartons shall be called “packages” or “bundles”). Shrinkwrap film is wrapped around the packages and then is sealed longitudinally along the package train before the seal bars make the transverse seal and separate the film between individual packages. The speed which can be obtained depends upon the package height and spacing, and other variables, but may be in the range of about 40 to about 65 packages (bundles of cartons) per minute. Thus, the assembly has the capability to seal one package per second in some configurations. The mechanical drive system includes seal bars (which move up and down) mounted on a carriage that traverses horizontally along a conveyor line. The carriage, in one embodiment, is mounted upon two linear slide modules mounted on a stationary frame. Each slide has its own gear box and motor. Two sets of timing belts and pulleys move the seal bars in opposite directions to open and close the sealing nip. A gear box and servo motor is mounted on the frame to power the sealing nip closure by way of a serpentine belt and pulley arrangement. Mounting the relatively bulky and heavy servo drives on the frame, rather than on the carriage, enables faster carriage speeds than could be obtained if the servo motor were mounted on the carriage. Turning now to FIG. 1, a shrinkwrap station 21 is shown including a frame 22 and a carriage 23 which reciprocates back and forth along the length of conveyor belt 26 . A package 24 is shown on the right side of FIG. 1 which in this instance comprises a bundle having 12 cartons of facial tissue (two layer stack). A person of skill in the art would recognize that bundles may be comprised of, for example, single cartons, two cartons, six cartons, eight cartons, ten cartons, twelve cartons, or as many as fifty or even one hundred cartons. Numerous bundle arrangements are possible with the assembly of this invention. Carton 25 is shown stacked on the second level or tier of the bundle. On the opposite end of the FIG. 1, a sealing wrap 31 is shown surrounding bundles to be sealed. The frame 22 comprises side strut 27 and end strut 34 . A motor 28 drives a serpentine belt 29 to move pulleys 30 for opening and closing the seal bar assembly. A linear slide module is located on each side of the carriage, and linear slide module 33 can be seen in FIG. 1 . This linear slide module drives the reciprocation of the carriage in a precise and predetermined manner. In one embodiment of the invention, a computer controlled servo controller signals the linear slide modules, resulting in precise and controlled movement of the carriage. In FIG. 2A, package A is shown by numeral 40 , package B is shown by numeral 41 , package C is seen as numeral 42 , package D is numeral 43 and package E is shown by numeral 44 . The identification of the packages in the Figures allows one to see the movement of the packages along the conveyor in FIGS. 2A, 2 B and 2 C. Lower seal bar 46 is adapted to engage upper seal bar 32 when the seal bars are in the closed position. Motor 48 drives conveyor belt 26 to convey the packages along the sealing station. Wheels 49 and 50 support the frame. Belt 51 is driven by the pulleys 30 and supported by pulley 52 to actuate the movement of the upper and lower seal bars and to provide appropriate timing in the movement of the seal bars between open and closed positions. Slide rail 53 provides a vertically oriented rail for guiding the seal bars as they move in a vertical direction. Motor mounts 54 and 55 support their respective motors upon the frame. Frame hubs 56 and 57 assist in providing a reference point to indicate carriage position location relative to the frame. Turning to FIG. 2B, the carriage seal bars may be seen in the fully open position, with the carriage having traveled down the conveyor line (to the left) to engage the next packages D and E. Package F (indicated by numeral 59 ) is shown on the left portion of the conveyor line. Pulleys 60 receive power from serpentine belt 29 . FIG. 2C shows the seal bars in the closed position during the sealing of film on the ends of packages D and E. FIG. 2D shows the seal bars re-opening to begin their travel across package E to seal the film between packages E and F. The process is repeated at a rapid pace for successive packages or bundles. Bundles move to the shrinkwrap station continuously at a constant velocity. The lower seal bar is attached to a two position link using a quick release pin, providing for a 10.76 inch opening for two layer package bundles, and a 6.02 inch opening for single layer codes. The electrical drive system includes linear slides that control the carriage stroke. The horizontal linear displacement of about 8.00 inches allows time for sealing and return strokes. During the seal stroke the carriage moves at a constant velocity for about 250 milliseconds which is the customary time required for making the transverse seal. In general, the sealing velocity must match the bundle or package speed. Typical values for acceleration and deceleration rates are: 240 inches/sec 2 and a velocity of 23.5 inches/sec. During the return stroke a constant carriage velocity is not desired but a minimum return time is required. Typical acceleration/deceleration rates are 250 inches/sec 2 . The seal bar drive motor controls the opening and closing of the seal bars. The seal bars should close quickly, but not before the carriage has reached a constant velocity. Likewise, the seal bars need to open very fast and they are fully open or almost fully open before the carriage starts a return stroke. The seal bar drive motor also controls the nip pressure of the seal bars during sealing of the packages. The nip pressure consists of two elements, a force of 55 pounds to compress the pressure pad and a force of about 145 pounds to create nip pressure for sealing and cut-off. A motor torque of 54 inch-pounds, with a reducer output torque of 320 inch-pounds, is required to produce a total nip force of 200 pounds or about 8.33 pounds per linear inch. In most applications, the two seal bar carriage drive motors (i.e. servo motors controlling carriage reciprocation and servo motors controlling seal bar opening/closing) make simultaneous moves as each moves on opposite ends of the carriage. The move commands may be made by any system, manual or computer controlled. The commands may be powered and instructed by electrical impulses from any reliable source. A desirable system is to use computer or microprocessor controlled signals to control the motion of the carriage assembly. Servo controller software available from Allen Bradley Company (Allen Bradley product code #1494) of 1201 South Second Street, Milwaukee, Wis. may be used advantageously. The servo controller software acts as an “electronic cam” in controlling the carriage seal bar mechanism. Software is designed to constantly compensate for the position of the carriage, thereby allowing for precise movement to the exact position at the time necessary to enable smooth and efficient operation of the assembly. In one embodiment of the invention, the primary control of the shrinkwrap assembly resides in an Allen Bradley (AB) PLC 5/E processor. The primary function of the PLC is to serve in a gateway/pass-through capacity. The PLC also hosts the programming controlling the shrink wrapper and alarming logic. The PLC provides parameter move commands to a 1394 Allen Bradley servo controller which controls four axis modules. A person of skill in the art, upon assembling the apparatus and purchasing the Allen Bradley products detailed herein is capable of efficiently operating the apparatus and method of this invention. The assembly may have at least two modes of operation. These two modes are automatic mode and manual mode. In the automatic mode, all systems run automatically. For the diverter section (not shown in Figures), this includes counting and diverting the necessary amount of product into the upper and lower infeed conveyors for both single and double layer codes. For the flying bar section (not shown in the Figures), this includes separating transporting, and orientating the product through the shrink wrapper system at the proper speed and control. For the seal section, this includes providing bundle spacing and necessary temperature to seal the wrapped packages. It also includes operation of the seal bars to seal packages at the correct placement, and with appropriate timing. For the heat tunnel section, this includes heating and transporting. In the automatic mode, packages are transported through the shrink wrapper, stacked, wrapped, sealed and transported to the next packaging area. In the manual mode, the machine operation can be enabled as needed. Diverter, flying bar conveyor, film feed, vacuum conveyor, seal bar carriage, seal bar, take away conveyor and shrink tunnel conveyors can be jogged in the forward and reverse direction. Manual sealing may be conducted. Full machine jog is allowed for troubleshooting and control adjustment. The diverter area (not shown in the Figures) is contemplated by a person of skill in the art, and is of the type widely used in the industry. The diverter area receives product, groups cartons into the correct product counts, positions the slugs into correct lane and transfers the product to the transport area. Diverter area equipment includes a linear actuator style lane diverter driven by an Allen-Bradley 1394 Servo, an infeed conveyor powered by an Allen-Bradley 1305 controller, a clamping mechanism prior to the infeed of the diverter, an exit gate, and an upper and lower conveyor controlled by Allen-Bradley 1305s. A photoeye in front of the Diverter Clamp (approximately 6 feet) ensures there is sufficient product to fill the Diverter and clamp. The film feed section lifts and rotates rolls of shrink film into the machine, unwinds the shrink film to supply the machine, perforates the shrink film (this allows air to escape as the film is shrinking), maintains constant shrink film web tension and aligns the shrink film web to the film former. The film feed section equipment includes a roll handler, a shrink film surface unwind, a counterweighted dancer, a driven dancer feed nip, a microperf roller and a fife guide. The film former (not shown in the Figures) guides the film over and around the groups of cartons and forms the poly into a tube and seals the top of this tube of polymer film. The film former section includes the mechanical film guides (the former), a motor that raises the top carton guide, a static seal and a heated drag seal. The seal bar section receives product, wraps the product with shrink film, seals the wrapped packages, and transports the wrapped packages to the heat tunnel section. The seal bar section equipment includes a vacuum belt, the seal bar carriage, the transfer belt, and Watlow temperature controllers available from the Watlow company, located at 12001 Lackland Road, St. Louis, Mo. The seal bars may be advantageously positioned by axis modules from an Allen-Bradley 1394 Servo controller. The vacuum conveyor receives and conveys product inside a tube of shrink film. The relative speeds of the flying bar and vacuum conveyors control the spacing between bundles. The shrink tunnel section receives product packages from the seal bar section, conveys and shrinks the shrink film to tightly fit the product by directing heated air on to the passing bundles and transfers bundles to the downstream process. The heat tunnel section equipment includes a transfer conveyor, two hot air zones with heaters, blowers and duct work and Chromalox PID temperature controller available from the Emerson Electric Company located at 701 Alpha Drive, Pittsburgh, Pa. Film unwind speed set point does not change with machine speed. So, the unwind speed must be set at a speed greater then the maximum speed the machine will run for the current grade. Running at a speed which is too slow will cause film breaks. These and other modifications of this invention may be practiced by one of ordinary skill in the art within the spirit of the invention. The invention is particularly set forth in the appended claims. Further, it should be understood that aspects of the various embodiments disclosed in this specification may be interchanged both in whole or in part, without departing from the invention. Furthermore, those of ordinary skill in the art will appreciate that this description is by way of example only, and does not limit the invention as described in the claims.
An apparatus and method is disclosed for sealing in a single package bundles of product cartons which are conveyed in series along a moving conveyor belt. A stationary frame is aligned with the conveyor, and a movable carriage assembly is connected to the frame. Packages or cartons of product are stacked and bundled by film, such as thermoplastic film, in a series of sealing steps. The apparatus includes at least one motor mounted on the stationary frame and capable of engaging the carriage assembly to facilitate reciprocating movement of the carriage assembly in relation to the moving packages. A separate computer controlled servo motor drives the opening and closing of seal bars on the carriage assembly to seal the film at each end of the package.
1
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of U.S. Ser. No. 07/726,654 filed Jul. 12, 1991, now U.S. Pat. No. 5,244,915, which is a continuation-in-part of U.S. Ser. No. 07/576,296, filed Aug. 31, 1990 now abandoned. BACKGROUND OF THE INVENTION Agents acting at central cholecystokinin (CCK) receptors may induce satiety (Schick, Yaksh and Go, Regulatory Peptides 14:277-291, 1986). They are also expected to act as analgesics (Hill, Hughes and Pittaway, Neuropharmacology 26:289-300, 1987), and as anticonvulsants (MacVicar, Kerrin and Davison, Brain Research 406:130-135, 1987). Reduced levels of CCK-peptides have been found in the brains of schizophrenic patients compared with controls (Roberts, Ferrier, Lee, Crow, Johnstone, Owens, Bacarese-Hamilton, McGregor, O'Shaughnessey, Polak and Bloom. Brain Research 288:199-211, 1983). It has been proposed that changes in the activity of CCK neurones projecting to the nucleus accumbens may play a role in schizophrenic processes by influencing dopaminergic function (Totterdell and Smith, Neuroscience 19:181-192, 1986). This is consistent with numerous reports that CCK peptides modulate dopaminergic function in the basal ganglia and particularly the nucleus accumbens (Weiss, Tanzer, and Ettenberg, Pharmacology, Biochemistry and Behaviour 30:309-317, 1988; Schneider, Allpert and Iversen, Peptides 4:749-753, 1983). It may therefore be expected that agents modifying CCK receptor activity may have therapeutic value in conditions associated with disturbed function of central dopaminergic function such as schizophrenia and Parkinson's disease. CCK and gastrin peptides share a common carboxy terminal pentapeptide sequence and CCK peptides can bind to the gastrin receptor of the stomach mucosa and elicit acid secretion in many species including human (Konturek, Gastrointestinal Hormones, Ch. 23, pp 529-564, 1980, ed. G. B. J. Glass, Raven Press, N.Y.). Antagonists of the CCK-B receptor would also be expected to be antagonists at the stomach gastrin receptor and this would also be of value for conditions involving excessive acid secretion. CCK and gastrin peptides have trophic effects on the pancreas and various tissues of the gastrointestinal tract (Johnson, ibid,, pp 507-527), actions which are associated with increased DNA and RNA synthesis. Moreover, gastrin secreting cells are associated with certain gastrointestinal tumors as in the Zollinger-Ellison syndrome (Stadil, ibid., pp 729-739), and some colorectal tumors may also be gastrin/CCK dependent (Singh, Walker, Townsend and Thompson, Cancer Research 46:1612, 1986; and Smith, J. P., Gastroenterology 95:1541, 1988). Antagonists of CCK/gastrin receptors could therefore be of therapeutic value as antitumor agents. The CCK peptides are widely distributed in various organs of the body including the gastrointestinal tract, endocrine glands, and the nerves of the peripheral and central nervous systems. Various biologically active forms have been identified including a 33-amino acid hormone and various carboxyl-terminus fragments of this peptide (e.g., the octapeptide CCK26-33 and the tetrapeptide CCK30-33). (G. J. Dockray, Br. Med. Bull. 38(3):253-258, 1982). The various CCK peptides are thought to be involved in the control of smooth muscle contractility, exocrine and endocrine gland secretion, sensory nerve transmission, and numerous brain functions. Administration of the native peptides cause gall bladder contraction, amylase secretion, excitation of central neurons, inhibition of feeding, anticonvulsive actions and other behavioral effects. ("Cholecystokinin: Isolation, Structure and Functions," G. B. J. Glass, Ed , Raven Press, New York, 1980, pp 169-221; J. E. Morley, Life Sciences 27:355-368, 1980; "Cholecystokinin in the Nervous System," J. de Belleroche and G. J. Dockray, Ed., Ellis Horwood, Chichester, England, 1984, pp 110-127. ) The high concentrations of CCK peptides in many brain areas also indicate major brain functions for these peptides (G. J. Dockray, Br. Med. Bull. 38(3):253-258, 1982). The most abundant form of brain CCK found is CCK26-33, although small quantities of CCK30-33 exist (Rehfeld and Gotterman, J. Neurochem. 32:1339-1341, 1979). The role of central nervous system CCK is not known with certainty, but it has been implicated in the control of feeding (Della-Fera and Baile, Science 206:471-473, 1979). Currently available appetite suppressant drugs either act peripherally, by increasing energy expenditure (such as thyroxine), or in some other manner (such as the biguanides), or act by exerting a central effect on appetite or satiety. Centrally acting appetite suppressants either potentiate central catecholamine pathways and tend to be stimulants (for example, amphetamine), or influence serotonergic pathways (for example, fenfluramine). Other forms of drug therapy include bulking agents which act by filling the stomach, thereby inducing a "feeling" of satiety. CCK is known to be present in some cortical interneurones which also contain gamma-aminobutyric acid (GABA) (H. Demeulemeester et al, J Neuroscience 8, 988-1000, 1988). Agents that modify GABA action may have utility as anxiolytic or hypnotic agents (S.C. Harvey, The Pharmacological Basis of Therapeutics (7th ed.) 1985, pp 339-371, MacMillan). Thus, agents which modify CCK action may have parallel anxiolytic or hypnotic activities. The role of CCK in anxiety is disclosed in TIPS 11:271-273, 1990. SUMMARY OF THE INVENTION The invention relates to novel compounds of the formula ##STR1## and the pharmaceutically acceptable salts thereof wherein R 1 , R 2 , R 9 , A, Ar 2 and w are as defined hereinbelow. In the U.S. Pat. Nos. 5,244,905, 5,264,419, 5,331,006 and 5,340,825 by Horwell, et al, the disclosures of which are incorporated herein by reference, CCK antagonists are disclosed. The invention also relates to a pharmaceutical composition containing an effective amount of a compound according to formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for appetite suppression. The compounds are also useful as anxiolytics, antipsychotics, especially for treating schizophrenic behavior, as agents in treating disorders of the extrapyramidal motor system, as agents for blocking the trophic and growth stimulating actions of CCK and gastrin, and as agents for treating gastrointestinal motility. Compounds of the invention are also useful as analgesics and potentiate the effect of morphine. They can be used as an adjunct to morphine and other opioids in the treatment of severe pain such as cancer pain and reduce the dose of morphine in treatment of pain where morphine is contraindicated. An additional use for compounds such as the iodinated compound is that the suitable radiolabelled iodine-131 or iodine-127 isotope gives an agent suitable for treatment of gastrin dependent tumors such as those found in colonic cancers. I-125 radiolabelled compound can also be used as a diagnostic agent by localization of gastrin and CCK-B receptors in both peripheral and central tissue. The invention further relates to a method of appetite suppression in mammals which comprises administering an amount effective to suppress appetite of the composition described above to a mammal in need of such treatment. The invention also relates to a pharmaceutical composition for reducing gastric acid secretion containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for reducing gastric acid secretion. The invention also relates to a method for reducing gastric acid secretion in mammals which comprises administering an amount effective for gastric acid secretion reduction of the composition described above to a mammal in need of such treatment. The invention also relates to a pharmaceutical composition containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for reducing anxiety. The invention also relates to a method for reducing anxiety in mammals which comprises administering an amount effective for anxiety reduction of the composition described above to a mammal in need of such treatment. The invention also relates to a pharmaceutical composition containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for treating gastrointestinal ulcers. The invention further relates to a method for treating gastrointestinal ulcers in mammals which comprises administering an amount effective for gastrointestinal ulcer treatment of the composition as described above to a mammal in need of such treatment. The invention also relates to a pharmaceutical composition containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for treating psychosis, i.e., schizophrenia. The invention further relates to a method for treating psychosis in mammals which comprises administering an amount effective for treating psychoses of a composition as described above to a mammal in need of such treatment. The invention also relates to pharmaceutical compositions effective for stimulating or blocking CCK or gastrin receptors, for altering the activity of brain neurons, for schizophrenia, for treating disorders of the extrapyramidal motor system, for blocking the trophic and growth stimulating actions of CCK and gastrin, and for treating gastrointestinal motility. The invention also relates to a pharmaceutical composition for preventing the withdrawal response produced by chronic treatment or abuse of drugs or alcohol. The invention further relates to a method for treating the withdrawal response produced by withdrawal from chronic treatment or withdrawal from abuse of drugs or alcohol. Such drugs include benzodiazepines, especially diazepam, cocaine, alcohol, and nicotine. Withdrawal symptoms are treated by administration of an effective withdrawal treating amount of a compound of the instant invention. The invention also relates to a pharmaceutical composition containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for treating and/or preventing panic. The invention also relates to a method for treating and/or preventing panic in mammals which comprises administering an amount effective for panic treatment and/or prevention of the composition described above to a mammal in need of such treatment. The invention further relates to the use of the compounds of formula I to prepare pharmaceutical and diagnostic compositions for the treatment and diagnosis of the conditions described above. The invention further provides processes for the preparation of compounds of formula I. The invention further provides novel intermediates useful in the preparation of compounds of formula I and also provides processes for the preparation of the intermediates. DETAILED DESCRIPTION The compounds of the present invention are derivatives of α-methyl tryptophan differing from natural dipeptides in that the substituent group R 2 is not hydrogen. The compounds of the present invention are represented by the formula ##STR2## or a pharmaceutically acceptable salt thereof wherein: R 1 is a cyclo- or polycycloalkyl hydrocarbon of from three to twelve carbon atoms with from zero to four substituents, each independently selected from the group consisting of: a straight or branched alkyl of from one to six carbon atoms, halogen, CN, OR*, SR*, CO 2 R*, CF 3 , NR 5 R 6 , or --(CH 2 ) n OR 5 , wherein R* is hydrogen, straight or branched alkyl of from one to six carbon atoms, R 5 and R 6 are each independently hydrogen or alkyl of from one to six carbon atoms; and n is an integer from zero to six; A is --(CH 2 ) n CO--, --SO 2 --, --SO--, --NHCO--, ##STR3## --SCO--, --O--(CH 2 ) n CO-- or --HC═CHCO-- wherein n is an integer from zero to six; R 2 is a straight or branched alkyl of from one to six carbon atoms, --HC═CH 2 , --C.tbd.CH, --(CH 2 ) n --CH═CH 2 , --(CH 2 ) n C.tbd.CH, --(CH 2 ) n Ar, --(CH 2 ) n OR*, --(CH 2 ) n OAr, --(CH 2 ) n CO 2 R*, --(CH 2 ) n NR 5 R 6 wherein n, R, R 5 , and R 6 are as defined above and Ar is a mono or polycyclic unsubstituted or substituted carbo- or heterocyclic aromatic or hydroaromatic moiety; R 9 is H, or a straight or branched alkyl of from one to six carbon atoms, --(CH 2 ) n CO 2 R*, (CH 2 ) n OAr', (CH 2 ) n Ar', (CH 2 ) n NR 5 R 6 , wherein n, R*, R 5 , and R 6 are as defined above and Ar' independently taken from Ar and w is zero or 1; Ar 2 is ##STR4## wherein x and y are each independently O, S, N, CH 2 , --CHR 12 , --NR 12 --, --NR 12 CO--, --C═N--, --C═C--, or --C(═O) or a bond; o, p, q, and r are each independently an integer of from 0 to 3, provided that when o, p, q, and r are all simultaneously zero, Ar 2 becomes ##STR5## R 12 , R 13 , and R 14 are each independently halogen, R 2 as is defined above, --(CH 2 ) g --B--D wherein g is an integer of from 0 to 6 wherein B is a bond, --OCO(CH 2 ) n --, --O(CH 2 ) n --, --NHCO(CH 2 ) n --, --CONH(CH 2 ) n --, --NHCOCH═CH--, --COO(CH 2 ) n --, --CO(CH 2 ) n --, --S(CH 2 ) n --, --SO(CH 2 ) n --, --SO 2 (CH 2 ) n --, ##STR6## --NHSO 2 --(CH 2 ) n --, or --SO 2 NH--(CH 2 ) n -- wherein R 7 and R 8 are independently selected from hydrogen and R 2 , or together form a ring (CH 2 ) m wherein m is an integer of from 1 to 5 and n is as defined above; D is --COOR*, --CH 2 OR*, --CHR 2 OR*, --CH 2 SR*, --CHR 2 SR*, --CONR 5 R 6 , --CN, --NR 5 R 6 , --OH, --H, and acid replacements such as tetrazole, ##STR7## wherein s is an integer of from 0 to 2 wherein R*, R 2 , R 5 , and R 6 are as defined above. Other preferred compounds of the instant invention are those wherein R 1 is ##STR8## wherein W, X, Y, and Z are each independently hydrogen, a straight or branched alkyl of from one to six carbon atoms, CF 3 , NR 5 R 6 , --(CH 2 ) n CO 2 R*, or CN, F, Cl, Br, OR*, SR*, wherein R* is hydrogen or a straight or branched alkyl of from one to six carbon atoms and R 5 and R 6 are as defined above and n is an integer of from 1 to 3. A is --NHCO--, --OCO--, --SO 2 --, --S(═O)--, --CH 2 CO--, R 2 is --CH 3 , --CH 2 CO 2 CH 3 , --CH 2 C.tbd.CH, R 9 is hydrogen, when w is 1, Ar 2 is unsubstituted or substituted by one to three substituents each independently selected in the manner indicated above such as ##STR9## and when w is zero, Ar 2 is unsubstituted or substituted in the manner indicated above such as ##STR10## More preferred compounds of the instant invention are those wherein R 1 is 2-adamantyl or 1-(S)-endobornyl, A is ##STR11## R 2 is --CH 3 , X and Y are --CH 2 -- when p, q, and r are 1; and Ar 2 is unsubstituted, or may be substituted by one to three substituents each independently selected from --CH 2 OH, --CH 2 OCOCH 2 CH 2 COOH, --CH 2 OCOCH═CHCO 2 H, --CH 2 NHCOCH 2 CH 2 COOH, --CH 2 NHCOCH═CHCO 2 H, --NHCOCH═CHCO 2 H, --NHCOCH 2 CH 2 CO 2 H, hydroxy, phenyl, CO 2 Me, benzyl, CONHCH 2 CH 2 CO 2 Bz, --CO 2 Bz, CH 2 SCH 2 CO 2 H, --CONHCH 2 CO 2 H, --CONHCH 2 CH 2 CO 2 H, or --CH 2 SCH 2 CO 2 H. Small x and small y can be independently carbonyl. The D and the L configurations are possible at the chiral centers and are included in the scope of the invention: Preferred is when R 2 is --CH 3 [D] configuration. Preferred compounds of the instant invention are: [2-[(2,2-Diphenylethyl)amino]1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo [3.3.1.1 3 ,7 ]dec-2 -yl ester, [2-[(3,4-dihydro-2H-1-benzopyran-3-yl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [2-[(1H-inden-1-ylmethyl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo [3.3.1.1 3 ,7 ]dec-2-yl ester, [2-[[(2,3-dihydro-1-hydroxy-1H-inden-1-yl)methyl]amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[(1,2,3,4-tetrahydro-2-naphthalenyl)amino]ethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [2-[(1,2-diphenylethyl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo3.3.1.1 3 ,7 ]dec-2-yl ester, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[[(1-phenyl-1-cyclopentyl)methyl]amino]ethyl]carbamic acid, tricycle3.3.1.1 3 ,7 ]dec-2-yl ester, [2-(dipentylamino)-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [2-(3-azabicyclo[3.2.2]non-3-yl)-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [1-(1H-indol-3-ylmethyl)-2-(octahydro-1H-indol-1-yl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [2-(decahydro-2-isoquinolinyl)-1-(1H-indol-3-ylmethyl)-1-methyl-2- oxoethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [2-[bis(phenylmethyl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [2-(3-azaspiro[5.5]undec-3-yl)-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamic acid, tricycle[3.3.1.1 3 ,7 ]dec-2-yl ester, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-(2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-2-yl)ethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-(1,3,3-trimethyl-6-azabicyclo[3.2.1]oct-6-yl)ethyl]carbamic acid, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester. Most preferred compounds of the instant invention are: 1. Carbamic acid, [2-[(2,3-dihydro-2-hydroxy-1H-inden-1-yl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]-, 1,7,7-trimethylbicyclo-[2.2.1]hept-2-yl ester (bicyclo ring is 1S-endo (+-isomer), trp center is D, indene ring centers are unknown), 2. Carbamic acid, [2-[(2,3-dihydro-1-hydroxy-1H-inden-2-yl)amino]-1-1H-indol-3-ylmethyl)-2-methyl-2-oxoethyl]-, 1,7,7-trimethylbicyclo-[2.2.1]hept-2-yl ester, [1S*[1α,2β[S-(trans)],4β]]-(Bicyclo system is 1S-endo), 3. Carbamic acid, [2-[(2,3-dihydro-1-hydroxy-1H-inden-2-yl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]-, 1,7,7-trimethylbicyclo-[2.2.1]hept-2-yl ester, [1S-[1α,2β[S*(1S*,2S*)],4α]]-[Bicyclo system is 1S-endo, all other centers are R], 4. Carbamic acid, 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[(1,2,3,4-tetrahydro-1-oxo-2-naphthalenyl)amino]ethyl]-, 1,7,7- trimethylbicyclo[2.2.1]hept-2-yl ester (Bicyclo system 1S-endo; TRP center R; naphthyl center (-) or (+)), (Isomer II), 5. Carbamic acid, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[(1-2,3,4-tetrahydro-1-oxo-2-naphthalenyl)amino]ethyl]-, 1,7,7-trimethylbicyclo[2.2.1.1]hept-2-yl ester (Bicyclo system 1S-endo; TRP center R; naphthyl center (+) or (-)), (Isomer I), 6. Carbamic acid, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[(1,2,3,4-tetrahydro-1-naphthalenyl)amino]ethyl]-, tricyclo[3.3.1.1 3 ,7 ]-dec-2-yl ester, (±)-, 7. Carbamic acid, [1-1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[(1,2,3,4-tetrahydro-2-naphthalenyl)amino]ethyl]-, tricyclo[3.3.1.1 3 ,7 ]-dec-2-yl ester, (±)-, 8. Carbamic acid, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-(1,2,3,4-tetrahydro-2-isoquinolinyl)ethyl]-, tricyclo[3.3.1.1 3 ,7 ]-dec-2-yl ester, (R)-, 9. 4-[4-[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]carbonyl]amino]propyl]-2-phenyl-1-piperazinyl]-4-oxobutanoic acid (Isomer II) (Bicyclo system is 1S-endo, phenyl center is S or R, other center is R), 10. 4-[4-[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]carbonyl]amino]propyl]-2-phenyl-1-piperazinyl]-4-oxobutanoic acid (Isomer I) (Bicyclo system is 1S-endo, phenyl center is R or S, other center is R), 11. 1,7,7-trimethylbicyclo[2.2.1]hept-2-ylmethyl)-1-methyl-2-oxo-2-(3-phenyl-1-piperazinyl)ethyl]carbamate (Bicyclo system is 1S-endo, phenyl is RS, other is R), 12. [1S-[1α,2β(S*),4α]]-4-[[[1-[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[[(1,7,7-trimethylbicyclo-[2.2.1]hept-2-yl)oxy]carbonyl]amino]propyl]-4-phenyl-4-piperidinyl]methyl]amino]-4-oxobutanoic acid (Bicyclo system is 1S-endo), 13. 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl[1S-[1α,2β(S*), 4α]]-[2-(4-hydroxy-4-phenyl-1-piperidinyl)-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate (Bicyclo system is 1S-endo, TRP is R), 14. [1S-(1α,2β,4α)]-N-[N-[α-methyl-N-[[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]carbonyl]-D-tryptophyl]-L-prolyl]-β-alanine (Bicyclo system is 1S-endo), 15. Phenylmethyl[1S-(1α, 2β,4α)]-1-[α-methyl-N-[[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)-oxy]carbonyl]-D-tryptophyl]-L-proline (Bicyclo system is 1S-endo), 16. [1S-[1α,2β(S*,R*),4α]]-[1-[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[[(1,7,7-trimethylbicyclo-[2.2.1]hept-2-yl)oxy]carbonyl]amino]propyl]-3-pyrrolidinyl]methyl butanedioate, 17. Mono 1-[3-[(1H-indol-3-yl)-2-methyl-1-oxo-2-[[[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]carbonyl]amino]propyl]-3-pyrrilidinylbutanedioate (Bicyclo system is 1S-endo, pyrrolidine center is RS, other center is R), 18. 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl[2-(3-hydroxy-1-pyrrolidinyl)-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate (ring is 1S-endo, hydroxy center is RS, other center is R), 19. Phenylmethyl (1S-endo)N-[1-[α-methyl-N-[[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]carbonyl]-D-trytophyl]-L-prolyl]-β-alanine, 20. Methyl-N-[α-methyl-N-[[(1,7,7-trimethylbicyclo-[2.2.1]hept-2-yl)oxy]carbonyl]-D-tryptophyl]-L-proline (mixture of 1S-exo and 1S-endo isomers), 21. N-[α-methyl-[[(1,7,7-trimethylbicyclo[2.2.1]-hept-2-yl)oxy]carbonyl]-D-trytophyl]-L-proline (mixture of 1S-exo and 1S-endo isomers), 22. Tricyclo[3.3.1.1 3 ,7 ]dec-2-yl(±)-[1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[(1,2,3,4-tetrahydro-2-naphthalenyl)amino]ethyl]carbamate, 23. Tricyclo[3.3.1.1 3 ,7 ]dec-2-yl(±)-[1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[(1,2,3,4-tetrahydro-1-naphthalenyl)amino]ethyl]carbamate, 24. 2,2,2-trifluoro-1-phenylethyl[2-[[1-(hydroxymethyl)-2-phenylethyl]amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethylcarbamate (Isomer II) (tryptophan center L or D hydroxy center S trifluoromethyl center R), 25. (R)-N-[1-[(methylphenylamino)carbonyl]-3-phenylpropyl]-1H -Indole-4-acetamide, 26. 2-[[[(3-methylphenyl)amino]carbonyl]amino]-N-[2-(phenylmethyl)phenyl]acetamide, 27. [1S-[1α,2β(S*) ,4α]]-1,7,7-trimethylbicyclo2.2.1]-hept-2-yl-[2-(3,4-dihydro-2(1H)-isoquinolinyl)-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate (Bicyclo system is 1S-endo), 28. Tricyclo[3.3.1.1 3 ,7 ]dec-2-yl (±)-[2-[(2,3-dihydro-1H-inden-2-yl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate, 29. Tricyclo[3.3.1.1 3 ,7 ]dec-2-yl (±)-[2-[(2,3-dihydro-1H-inden-1-yl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate, 30. Tricyclo[3.3.1.1 3 ,7 ]dec-2-yl-(R)-[1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-(1,2,3,4-tetrahydro-2-isoquinolinyl)ethyl]carbamate, 31. 4-[[1,2,3,4-Tetrahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2-yloxy)-carbonyl]amino]propyl]amino]-1-naphthalenyl]amino]-4-oxobutanoate, 32. Tricyclo[3.3.1.1 3 ,7 ]dec-2-yl-[2-[(1-azido-1,2,3,4-tetrahydro-2-naphthalenyl)amino]-1(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate, 33. Methyl 3-[[2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1,2,3,4-tetrahydro-1-naphthalenyl]amino]-3-oxopropanoate, 34. Methyl 3-[[2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1,2,3,4-tetrahydro-1-naphthalenyl]amino]-3-oxopropanoate, 35. Methyl 1-[[1,2,3,4-tetrahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1-naphthalenyl]amino-4-oxo-2-butanoate, and 36. Tricyclo[3.3.1.1 3 .7 ]dec-2-yl ester (R) [1-(1H-indol-3-ylmethyl)-2-[(4-methoxyphenyl)amino]-1-methyl-2-oxoethyl]carbamate. Table I below illustrates representative compounds of the invention. Stereochemistry is not shown in the Table I in all instances. The numbers in the first column refer to the numbered compounds on the previous pages. TABLE I__________________________________________________________________________ ##STR12##CompoundNumber R.sup.1 A R.sup.2 R.sup.9 w Ar.sup.2__________________________________________________________________________ ##STR13## OCO Me Null O ##STR14##2 ##STR15## OCO Me (R) H 1 ##STR16##3 ##STR17## OCO Me (R) H 1 ##STR18##4 ##STR19## OCO Me (R) H 1 ##STR20##5 ##STR21## OCO Me (R) H 1 ##STR22##6 ##STR23## OCO Me (R) H 1 ##STR24##7 ##STR25## OCO Me (R, S) H 1 ##STR26##8 ##STR27## OCO Me (R, S) H 1 ##STR28##27 ##STR29## OCO Me H 1 ##STR30##28 ##STR31## OCO Me H 1 ##STR32##29 ##STR33## OCO Me (S) Null 0 ##STR34##36 ##STR35## OCO Me H 1 ##STR36##__________________________________________________________________________ In addition to the compounds of Table I the compounds of the present invention include compounds of formula I wherein the indole moiety is a 2- or 3-indolyl. The compounds include solvates and hydrates and pharmaceutically acceptable salts of the compounds of formula I. The compounds of the present invention can have multiple chiral centers including those designated in the above formula I by an , depending on their structures. Centers of asymmetry may exist on substituents R 1 , R 9 , and/or Ar 2 . In particular the compounds of the present invention may exist as diastereomers, mixtures of diastereomers, or as the mixed or the individual optical enantiomers. The present invention contemplates all such forms of the compounds. The mixtures of diastereomers are typically obtained as a result of the reactions described more fully below. Individual diastereomers may be separated from mixtures of the diastereomers by conventional techniques such as column chromatography or repetitive recrystallizations. Individual enantiomers may be separated by convention method well known in the art such as conversion to a salt with an optically active compound, followed by separation by chromatography or recrystallization and reconversion to the nonsalt form. The compounds of the present invention can be formed by coupling individual substituted α-amino acids by methods well known in the art. (See, for example, standard synthetic methods discussed in the multi-volume treatise "The Peptides, Analysis, Synthesis, Biology," by Gross and Meienhofer, Academic Press, New York.) The individual substituted alpha amino acid starting materials are generally known or, if not known, may be synthesized and, if desired, resolved by methods within the skill of the art. (Synthesis of racemic [DL]-α-methyl tryptophan methyl ester--see Brana, M. F., et al, J. Heterocyclic Chem. 17:829, 1980.) A key intermediate in the preparation of compounds of formula I is a compound of formula ##STR37## wherein R is selected from R 1 , 9-fluorenylmethyl, Bz and other suitable N-blocking groups. These are useful as intermediates in the preparation of compounds of formula I. The compounds wherein R is 1-adamantyl, 2-adamantyl, 4-protoadamantyl, exo-bornyl, endo-bornyl, exo-norbornyl, endo-norbornyl, 2-methylcyclohexyl, 2-chlorocyclohexyl, or camphoryl are novel and are preferred. The disclosure of U.S. Pat. No. 4,757,151 is hereby incorporated by reference. It describes the 9-fluorenylmethyl blocking group. Compounds of formula II are prepared by reacting ROH III wherein R is as defined above, with phosgene or a phosgene substitute to produce a corresponding compound of formula ROCOCl IV and then reacting a compound of formula IV with α-methyltryptophan to produce the desired compound of formula II above. Alternatively, a compound of formula IV can be reacted with an α-methyltryptophan methyl ester to produce ##STR38## which can be converted to a compound of formula II by known means such as hydrolysis with aqueous lithium hydroxide. Scheme I below illustrates procedures for preparing intermediates useful in producing final products of formula I. Key intermediate (2) is prepared from the alcohol form of a radical selected from 1-adamantyl, 2-adamantyl, 4-protoadamantyl, 9-fluorenylmethyl, exo-bornyl, endo-bornyl, exo-norbornyl, endo-norbornyl, 2-methylcyclohexyl, 2-chlorocyclohexyl, and camphoryl. The alcohol is dissolved in a solvent such as methylene chloride. It is then converted to the corresponding chloroformate by reaction with bis(trichloromethyl) carbonate in pyridine at about 0° C. The product is formed by condensation with an amine such as α-methyl-D-tryptophan methyl ester. The reaction is carried out in a solvent such as THF to produce, for example, N-[(2-adamantyloxy)carbonyl]-α-methyl-D-tryptophan methyl ester. This is then treated with lithium hydroxide and stirred at room temperature overnight to produce the corresponding carboxylic acid. This novel key intermediate (2) is useful in the production of compounds of formula I as described hereinafter in Schemes II and III. Schemes IV through VIII correspond to Examples 7 through 17 and illustrate methods of preparing final products of formula I of the instant invention. ##STR39## Whenever R in intermediate of formula II is other than R 1 , it may be removed at an appropriate point in the synthesis by methods known in the art for each respective group and the desired R 1 substituted therefore. BIOLOGICAL ACTIVITY The biological activity of compounds of the present invention was evaluated employing an initial screening test which rapidly and accurately measured the binding of the tested compound to known CCK receptor sites. Specific CCK receptors have been shown to exist in the central nervous system. (See Hays et al, Neuropeptides 1:53-62, 1980; and Satuer et al, Science 208:1155-1156, 1980. In this screening test, the cerebral cortices taken from male CFLP mice weighing between 30-40 g were dissected on ice, weighed, and homogenized in 10 volumes of 50 mM Tris-HCl buffer (pH 7.4 at 0°-4° C.). The resulting suspension was centrifuged, the supernate was discarded, and the pellet was washed by resuspension in Tris-HCl buffer followed by recentrifugation. The final pellet was resuspended in 20 volumes of 10 nM Hepes buffer (pH 7.2 at 23° C.) containing 130 mM NaCl, 4.7 nM KCl, 5 nM MgCl 2 , 1 nM EDTA, 5 mg/mL bovine albumin, and bacitracin (0.25 mg/ml). In saturation studies, cerebral cortical membranes were incubated at 23° C. for 120 minutes in a final volume of 500 μliter of Hepes incubation buffer (pH 7.2) together with 0.2-20 nM tritiated-pentagastrin (Amersham International, England). In the displacement experiments, membranes were incubated with a single concentration (2 nM) of ligand, together with increasing concentrations (10 -11 to 10 -14 M) of competitive test compound. In each case, the nonspecific binding was defined as that persisting in the presence of the unlabeled octapeptide CCK 26-33 (10 -6 M). Following incubation, radioactivity bound to membranes was separated from that free in solution by rapid filtration through Whatman GF/B filters and washed three times with 4 mL of ice cold Tris-HCl buffer. Filters from samples incubated with tritiated-pentagastrin were placed in polyethylene vials with 4 mL of scintillation cocktail, and the radioactivity was estimated by liquid scintillation spectrometry (efficiency 47-52%). The specific binding to CCK receptor sites was defined as the total bound tritiated-pentagastrin minus the amount of tritiated-pentagastrin bound in the presence of 10 -6 octapeptide, CCK 26-33 . Saturation curves for specific tritiated-pentagastrin binding to mouse cortical membranes were analyzed by the methods of Scatchard (Ann. New York Acad. Sci. 51:660-672, 1949, and Hill (J. Physiol. 40:IV-VIII, 1910, to provide estimates for the maximum number of binding sites (B max ) and the equilibrium dissociation constant (K a ). In displacement experiments, inhibition curves were analyzed by either logit-log plots or the iterative curve fitting computer program ALLFIT (DeLean, Munson and Redbard, 1978) to provide estimates of the IC 50 and nH (apparent Hill coefficient) values). (IC 50 values were defined as the concentration of test compound required to produce 50% inhibition of specific binding.) The inhibition constant (K i ) of the test compound was then calculated according to the Cheng-Prusoff equation: ##EQU1## where [L] is the concentration of radiolabel and K a is the equilibrium dissociation constant. The K i values for several representative compounds of the present invention are present in Table II below. TABLE II______________________________________Binding Data K.sub.i (nM) K.sub.i (nM)Compound Number CCK B CCK A______________________________________1 280 N.T.2 111 53003 30 38704 94 76205 59 N.T.6 45 52207 330 N.T.8 450 N.T.36 33 N.T.______________________________________ N.T. = Not tested Compound numbers are from the list of compounds starting on page 17. Compounds of the present invention are expected to be useful as appetite suppressants as based on the tests described hereinbelow. In the Palatable Diet Feeding assay, adult male Hooded Lister rats weighing between 200-400 g are housed individually and trained to eat a palatable diet. This diet consists of Nestles sweetened condensed milk, powdered rat food and rat water which when blended together set to a firm consistency. Each rat is presented with 20-30 g of the palatable diet for 30 minutes per day during the light phase of the light-dark cycle over a training period of five days. The intake of palatable diet is measured by weighing the food container before and after the 30-minute access period (limits of accuracy 0.1 g). Care is taken to collect and correct for any spillage of the diet. Rats have free access to pellet food and water except during the 30-minute test period. After the training period, dose-response curves are constructed for CCK8 for several representative compounds of the present invention (n=8-10 rats per dose level). MPE 50 values (±95% confidence limits) are obtained for the anorectic effects of these compounds. In therapeutic use as appetite suppression agents, the compounds of the instant invention are administered to the patient at dosage levels of from about 200 to about 2800 mg per day. Male Hooded Lister rats (175-250 g) are housed individually and fasted overnight (free access to water). They are anesthetized with urethane (1.5 g/kg IP) and the trachea cannulated to aid spontaneous respiration. The stomach is perfused continuously using a modification of the original method of Ghosh & Schild in "Continuous recording of acid secretion in the rat", Brit. J. Pharmac. 13:54-61, 1956 as described by Parsons in "Quantitative studies of drug-induced gastric acid secretion". (Ph.D. Thesis, University of London, 1969). The cavity of the stomach is perfused at a rate of 3 mL/min with 5.4% w/v glucose solution through both the esophageal and body cannula. The fluid is propelled by a roller pump (Gilson, Minipuls 2), through heating coils to bring its temperature to 37°±1° C. The perfusion fluid is collected by the fundic collecting funnel and passed to a pH electrode connected to a Jenway pH meter (PHM6). An output is taken from the pH meter to a Rikadenki chart recorder for the on-line recording of the pH of the gastric perfusate. Pentagastrin is stored as a frozen aliquot and diluted to the required concentrations with sterile 0.9% w/v NaCl. Novel compounds are dissolved in sterile 0.9% w/v NaCl on the day of the experiment. Drugs are administered IV through a cannulated jugular vein as a bolus in a dose volume of 1 ml/kg washed in with 0.15 ml 0.9% w/v NaCl. Basal pH is allowed to stabilize before administration of compounds is begun. Typically 30 minutes elapses between surgery and the first compound administration. With test compounds, the antagonism is expected to be reversible with full recovery of the response to pentagastrin. The compounds of the instant invention are also expected to be useful as antiulcer agents as discussed hereinbelow. Aspirin-induced gastric damage is assessed in groups of 10 rats each. All animals are fasted for 24 hours before and throughout the experiment. Drug or vehicle are given 10 minutes before an oral dose of 1 ml of a 45-mg/mL suspension of aspirin in 0.5% carboxymethylcellulose (CMC). The animals are sacrificed 5 hours after aspirin administration and the stomachs removed and opened for examination. Gastric damage was scored as follows: ______________________________________Score______________________________________1 Small hemorrhage2 Large hemorrhage3 Small ulcer4 Large ulcer5 Perforated ulcer______________________________________ The specific dosages employed, however, may be varied depending upon the patient, the severity of the condition being treated, and the activity of the compound employed. Determination of optimum dosages is within the skill of the art. The compounds of the instant invention are also expected to be useful as anxiolytic agents as described and discussed below. Anxiolytic activity is assessed in the light/dark exploration test in the mouse (B. J. Jones, et al, Brit. J. Pharmac. 93:985-993, 1988). The pretreatment time is 40 minutes. The compound is given p.o. in 0.1, 1, and 10 mg/kg doses. The apparatus is an open-topped box, 45 cm long, 27 cm wide, and 27 cm high, divided into a small (2/5) area and a large (3/5) area by a partition that extended 20 cm above the walls. There is a 7.5×7.5 cm opening in the partition at floor level. The small compartment is painted black and the large compartment white. The floor of each compartment is marked into 9 cm squares. The white compartment is illuminated by a 100-watt tungsten bulb 17 cm above the box and the black compartment by a similarly placed 60-watt red bulb. The laboratory is illuminated with red light. All tests are performed between 13 hundred hours, 0 minutes and 18 hundred hours, 0 minutes. Each mouse is tested by placing it in the center of the white area and allowing it to explore the novel environment for 5 minutes. Its behavior is recorded on videotape and the behavioral analysis was performed subsequently from the recording. Five parameters are measured: the latency to entry into the dark compartment, the time spent in each area, the number of transitions between compartments, the number of lines crossed in each compartment, and the number of rears in each compartment. In this test an increase in the time spent in the light area is a sensitive measure of, that is directly related to, the anxiolytic effects of several standard anxiolytic drugs. Drugs are dissolved in water or saline and administered either subcutaneously, intraperitoneally, or by mouth (PO) via a stomach needle. The compounds of the instant invention are useful as antipsychotic agents. Compounds are tested for their ability to reduce the effects of intra-accumbens amphetamine in the rat as described hereinafter. Male Sprague Dawley (CD) Bradford strain rats are used. The rats are housed in groups of five at a temperature of 21°±2° C. on a 12 hour light-dark cycle of lights-on between 07 hours 00 minutes and 20 hours 00 minutes. Rats are fed CRM diet (Labsure) and allowed water ad libitum. Rats are anesthetized with chloral hydrate (400 mg/kg SC) and placed in a Kopf stereotaxic frame. Chronically indwelling guide cannulae (constructed of stainless steel tubing 0.65 mm diameter held bilaterally in Parspex holders) are implanted using standard stereotaxic techniques to terminate 3.5 mm above the center of the nucleus accumbens (Ant. 9.4, Vert. 0.0, Lat. 1.6) or 5.0 mm above the central nucleus of the amygdala (Ant. 5.8, Vert. -1.8, Lat. ±4.5) (atlas of De Groot, 1959). The guides are kept patent during a 14-day recovery period using stainless steel stylers, 0.3 mm diameter, which extended 0.5 mm beyond the guide tips. Rats are manually restrained and the stylets removed. Intracerebral injection cannulae, 0.3 mm diameter, are inserted and drugs delivered in a volume of 0.5 μL over 5 seconds (a further 55 seconds was allowed for deposition) from Hamilton syringes attached via polythene tubing to the injection units. Animals are used on a single occasion only. Behavioral experiments are conducted between 07 hours 30 minutes and 21 hours 30 minutes in a quiet room maintained at 22°±2° C. Rats are taken from the holding room and allowed one hour to adapt to the new environment. Locomotor activity is assessed in individual screened Perspex cages (25×15×15 cm (high) (banked in groups of 30) each fitted with one photocell unit along the longer axis 3.5 cm from the side; this position has been found to minimize spurious activity counts due to, for example, preening and head movements when the animal is stationary. Interruptions of the light beam are recorded every 5 minutes. At this time animals are also observed for the presence of any nonspecific change in locomotor activity, e.g., sedation, prostration, stereotyped movements, that could interfere with the recording of locomotor activity. The abilities of compounds to inhibit the hyperactivity caused by the injection of amphetamine into the nucleus accumbens of the rat is measured. An increase in locomotor activity followed the bilateral injection of amphetamine (20 μg) into the nucleus accumbens; peak hyperactivity (50 to 60 counts 5 minutes -1 ) occurs 20 to 40 minutes after injection. Intraperitoneal injection of the rats with a compound (20 mg/kg or 30 mg/kg) or (10 mg/kg) reduces the hyperactivity caused by the intra-accumbens injection of amphetamine. This test is known to be predictive of antipsychotic activity (Costall, Domeney & Naylor & Tyers, Brit. J. Pharmac. 92:881-894). The compounds of the instant invention are expected to prevent and treat the withdrawal response produced when chronic treatment by a drug is stopped or when alcohol abuse is stopped. These compounds are therefore useful as therapeutic agents in the treatment of chronic drug or alcohol abuse. The effect of the compounds of the instant invention is illustrated, for example, in the mouse "light/dark box" test. Five animals are given nicotine, typically in a range of 0.01 to 100 mg/kg i.p.b.d. for 14 days. After a 24-hour withdrawal period, a compound is given typically at a range of 0.01 to 100 mg/kg i.p.b.d. The increased time spent in the light area is a sensitive measure of the effect of the compound as an agent to treat withdrawal effects from nicotine. For preparing pharmaceutical compositions from the compounds of this invention, inert, pharmaceutically acceptable carriers can be either solid or liquid. Solid form preparations include powders, tablets, dispersible granules, capsules, cachets, and suppositories. A solid carrier can be one or more substances which my also act as diluents, flavoring agents, solubilizers, lubricants, suspending agents, binders, or tablet disintegrating agents; it can also be an encapsulating material. In powders, the carrier is a finely divided solid which is in a mixture with the finely divided active component. In tablets, the active component is mixed with the carrier having the necessary binding properties in suitable proportions and compacted in the shape and size desired. For preparing suppository preparations, a low-melting wax such as a mixture of fatty acid glycerides and cocoa butter is first melted and the active ingredient is dispersed therein by, for example, stirring. The molten homogeneous mixture is then poured into convenient sized molds and allowed to cool and solidify. The powders and tablets preferably contain 5 to about 70% of the active component. Suitable carriers are magnesium carbonate, magnesium stearate, talc, lactose, sugar, pectin, dextrin, starch, tragacanth, methyl cellulose, sodium carboxymethyl cellulose, a low-melting wax, cocoa butter, and the like. A preferred pharmaceutically acceptable salt is the N-methyl glucamine salt. The term "preparation" is intended to include the formulation of the active component with encapsulating material as a carrier providing a capsule in which the active component (with or without other carriers) is surrounded by a carrier which is thus in association with it. Similarly, cachets are included. Tablets, powders, cachets, and capsules can be used as solid dosage forms suitable for oral administration. Liquid form preparations include solutions, suspensions, and emulsions. Sterile water or water-propylene glycol solutions of the active compounds may be mentioned as an example of liquid preparations suitable for parenteral administration. Liquid preparations can also be formulated in solution in aqueous polyethylene glycol solution. Aqueous solutions for oral administration can be prepared by dissolving the active component in water and adding suitable colorants, flavoring agents, stabilizers, and thickening agents as desired. Aqueous suspensions for oral use can be made by dispersing the finely divided active component in water together with a viscous material such as natural synthetic gums, resins, methyl cellulose, sodium carboxymethyl cellulose, and other suspending agents known to the pharmaceutical formulation art. Preferably the pharmaceutical preparation is in unit dosage form. In such form, the preparation is divided into unit doses containing appropriate quantities of the active component. The unit dosage form can be a packaged preparation, the package containing discrete quantities of the preparation, for example, packeted tablets, capsules, and powders in vials or ampoules. The unit dosage form can also be a capsule, cachet, or tablet itself, or it can be the appropriate number of any of these packaged forms. Examples are illustrative of methods of preparing the final products. EXAMPLES EXAMPLE 1 Carbamic acid, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-(1,2,3,4-tetrahydro-2-isoquinolinyl)ethyl]-, tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester, (R) ##STR40## To a stirred solution of α-methyl-N-[(tricyclo[3.3.1.1 3 ,7 ]dec-1-yloxy)carbonyl]-R-tryptophan (150 mg, 0.3 mmol) in anhydrous EtOAc (7 mL) was added N,N-dicyclohexylcarbodiimide (86 mg, 0.41 mmol) and pentafluorophenol (77 mg, 0.41 mmol). The reaction mixture was stirred at room temperature for 2 hours and then 1,2,3,4-tetrahydroisoquinoline (51 mg, 0.38 mmol) in EtOAc (2 mL) added. After stirring for 3 days, the reaction mixture was filtered and the filtrate concentrated in vacuo. The residue was chromatographed over reverse phase silica using 4:1 MeOH:H 2 O as eluant to give the desired amide as an amorphous solid (83 mg, 43%); m.p. 95°-100° C.; IR (film) 3300, 2908, 2854, 1696, and 1625 cm -1 ; NMR (CDCl 3 ) δ1.40-1.90 (17H, m), 2.85 (2H, t, J 6 Hz), 3.50 (2H, m), 3.95 (2H, br s), 4.75 (1H, m), 4.85 (2H, br s), 5.15 (1H, br s), 6.97 (1H, s), 7.10 (6H, m), 7.34 (1H, d, J 8 Hz), 7.56 (1, d, J 8 Hz), 8.15 (1H, s); Anal. (C 32 H 37 N 3 O 3 .0.5CHCl 3 ), C, H, N. EXAMPLES 2 AND 3 Carbamic acid, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[(1,2,3,4-tetrahydro-1-oxo-2-naphthalenyl)amino]ethyl]-, 1,7,7-trimethylbicyclo[2.2.1.1]hept-2-yl ester; (Bicyclo system 1S-endo: TRP Center R; naphthyl center (+) and (-)) 1-S-endoBornyloxycarbonyl-α-methyl-R-tryptophan (247 mg, 0.62 mmol) and pentafluorophenol (114 mg, 0.62 mmol) as a solution in EtOAc (15 mL) was treated with dicyclohexylcarbodiimide (130 mg, 0.63 mmol) at 0° C. and left 24 hours at 4° C. The mixture was then filtered and the filtrate added to a stirred mixture of 2-amino-1-tetralone HCl salt (122 mg, 0.62 mmol) and triethylamine (63 mg, 0.62 mmol) in EtOAc (10 mL) at 0° C. The combined mixture was left stirring at room temperature for 18 hours before 4-dimethylamino pyridine (20 mg, 0.16 mmol) was added and the mixture left a further 48 hours. The reaction mixture was then washed with H 2 O (10 mL), 1M HCl (10 mL), and H 2 O (10 mL). The organic phase was dried over MgSO 4 and concentrated in vacuo. The residue was chromatographed over silica gel twice, once using 1% MeOH in CH 2 Cl 2 , then the two diastereoisomers were separated using 25% EtOAc in n-hexane as eluants, to give Isomer I as a white solid (110 mg, 33%), and Isomer II as a noncrystalline solid (100 mg, 30%). EXAMPLE 2 ##STR41## Isomer I m.p. 106°-112° C. (MeOH/H 2 O); [α]20D+33.2° (c=0.27, MeOH); IR (film) 1699 and 1663 cm -1 ; NMR (CDCl 3 ) δ0.82 (3H, s), 0.85 (3H, s), 0.90 (3H, s), 1.07 (1H, dd, J 13.5 and 3 Hz), 1.20-1.30 (2H, m), 1.64 (3H, s), 1.65-1.90 (4H, m), 2.30-2.45 (1H, m), 2.75-2.79 (1H, m), 2.98 (1H, br d, J 16 Hz), 3.20-3.35 (1H, m), 3.43 (1H, d, J 14 Hz), 3.51 (1H, d, J 14 Hz), 4.56 (1H, dt, J 13.5 and 5 Hz), 4.70-5.00 (1H, br), 4.90 (1H, br d, J 9 Hz), 5.37 (1H, br s), 7.05-7.40 (7H, m), 7.51 (1H, t, J 7 Hz), 7.61 (1H, d, J8 Hz), 7.98 (1H, d, J 8 Hz), 8.20 (1H, s); Anal. C 33 H 39 N 3 O 4 .0.75H 2 O; C, H, N. EXAMPLE 3 ##STR42## Isomer II m.p. 106°-111° C.; [α]20D-12° (c=0.1, MeOH); IR (film) 1697 and 1662 cm -1 ; NMR (CDCl 3 ) δ0.85 (6H, s), 0.89 (3H, s), 1.03 (1H, dd, J 14 and 3 Hz), 1.10-1.30 (2H, m), 1.61 (3H, s), 1.65-1.90 (4H, m), 2.30-2.40 (1H, m), 2.65-2.75 (1H, m), 2.96 (1H, br d, J16 Hz), 3.20-3.30 (1H, m), 3.41 (1H, d, J 15 Hz), 3.49 (1H, d, J 15 Hz), 4.57 (1H, dt, J 14 and 5 Hz), 4.89 (1H, d, J 9 Hz), 5.37 (1H, br s), 7.00-7.40 (8H, m), 7.53 (1H, dt, J 7 and 1 Hz), 7.60 (1H, d, J 8 Hz), 7.96 (1H, 0, J 8 Hz), 8.18 (1H, br s); Anal. C 33 H 32 N 3 O 4 m 0.5 Hz; C, H, N. EXAMPLE 4 ##STR43## A solution of the acid (Schemes II or III, No. 1) (199 mg, 0.50 mmol) and pentafluorophenol (92 mg, 0.5 mmol) in EtOAc (20 mL) was cooled to 0° C. and a solution of N,N'-dicyclohexylcarbodiimide (108 mg, 0.525 mmol) in EtOAc (5 mL) was added. This was stirred for 24 hours at 0° C., filtered, and trans-2(R)amino 1-(R)hydroxy indane (75 mg, 0.5 mmol) added. This mixture was stirred at room temperature for 24 hours and then the solvent was removed in vacuo. The residue was chromatographed using 2% MeOH in CH 2 Cl 2 as eluant to give the product as a white solid (191 mg, 72%), m.p. 100°-103° C. (MeOH/H 2 O); IR (film) 3368, 2954, 1696, and 1651 cm -1 ; NMR (CDCl 3 ) δ0.82 (3H, s), 0.86 (3H, s), 0.90 (3H, s), 0.97 (1H, dd, J 14 and 3 Hz), 1.05-1.35 (2H, m), 1.63 (3H, s), 1.65-1.90 (3H, m), 2.30-2.40 (1H, m), 2.60 (1H, dd, J 15 and 8.5 Hz), 3.15 (1H, rid, J 15 and 8.5 Hz), 3.30 (1H, d, J1 15 Bz), 3.53 (1H, d, J 15 Hz), 4.15-4.25 (1H, m), 4.70-4.80 (1H, br s), 4.89 (1H, d, J 10 Hz), 4.98 (1H, d, J 6.5 Hz), 5.16 (1H, brs), 6.75-6.85 (1H, brs), 7.07 (1H, d, J 2 Hz), 7.10-7.40 (7H, m), 7.62 (1H, d, J 8 Hz), 8.17 (1H, s); MS (FAB) m/e 3321.1 (100), 530 (83). Anal. C 32 H 39 N 3 O 4 .0.25H 2 O; C, H, N. EXAMPLE 5 ##STR44## Method exactly as for Example 4 (Scheme III No. 2), except using trans 2(S) amino 1(S) hydroxy indane: yield 157 mg, 85%); m.p. 97°-103° C. (MeOH/H 2 O); IR (film) 3369, 2954, 1696, and 1659 cm -1 ; NMR (CDCl 3 ) δ0.76 (3H, s), 0.82 (3H, s), 0.88 (3H, s), 0.94-1.00 (1H, m), 1.10-1.30 (2H, m), 1.55 (3H, s), 1.60-1.80 (3H, m), 2.20-2.37 (1H, m), 2.60 (1H, brs), 2.77 (1H, dd, J 15.5 and 7 Hz), 3.12 (1H, dd, J 15.5 and 7 Hz), 3.38 (1H, d, J 15 Hz), 3.51 (1H, d, J 15 Hz), 4.60-4.70 (1H, m), 4.71 (0.5H, brs), 4.81 (0.5H, brs), 5.03 (1H, g, J 5 Hz), 5.08 (1H, s), 6.48 (1H, d, J 8 Hz), 7.00-7.40 (8H, m), 7.62 (1H, d, J 8 Hz), 8.1 (1H, brs); Anal. C 32 H 39 N 3 O 4 .0.25H 2 O; C, H, N. EXAMPLE 6 ##STR45## Method exactly as for Example 4 (Scheme III No. 2) except using 1-amino-2-hydroxyindane, yield 183 mg, 69%; m.p. 99°-106° C. (MeOH/H 2 O); IR (film) 3339, 1699, and 1657 cm -1 ; NMR (CDCl 3 ) δ0.81 (3H, 2xs, separation 1 Hz), 0.85 (3H, s), 0.89 (3H, 2xs, separation 2 Hz), 0.90-1.00 (1H, m), 1.10-7.35 (2H, m), 1.60-1.85 (6H, m), 2.30-2.40 (1H, m), 2.85-2.95 (1H, m), 3.20-3.60 (3H, m), 4.20-4.30 (1H, m), 4.38 (0.5H, s), 4.50 (0.5H, s), 4.85-4.93 (1H, m), 5.07 (1H, q, J 7 Hz), 5.18 (0.5H, s), 5.28 (0.5H, s), 6.65 (1H, d, J 5.5 Hz), 6.80 (0.5H, d, J 7.5 Hz), 6.85 (0.5H, d, J 7.5 Hz), 7.05-7.25 (6H, m), 7.37 (1H, d, J 8 Hz), 7.62 (1H, d, J 8 Hz), 8.24 (1H, brs); Anal. C 32 H 39 N 3 O 4 .0.5H 2 O; C, H, N. EXAMPLE 7 ##STR46## Method exactly as for Example 4, except using 2Adoc-α-Me-RS-TrpOH (7) and 1-aminotetralin; yield 228 mg, 87%; m.p. 108°-116° C. (MeOH/H 2 O); IR (film) 3400-3200, 2907, 2855, 1704, 1652, and 1493 cm -1 ; NMR (CDCl 3 ) δ1.45-1.55 (2H, m), 1.59 (3H, s), 1.70-2.05 (16H, m), 2.70-2.80 (2H, m), 3.36 (0.5H, d, J 14.5 Hz), 3.37 (0.5H, d, J 14.5 Hz), 3.54 (0.5H, d, J 14.5 Hz), 3.57 (0.5H, d, J 14.5 Hz), 5.05-5.15 (1H, m), 5.16 (0.5H, s), 5.19 (0.5H, s), 6.34 (0.5H, d, J 6 Hz), 6.38 (0.5H, d, J 6 Hz), 7.00-7.25 (7H, m), 7.3 (1H, d, J 8 Hz), 7.63 (1H, d, J 8 Hz), 8.17 (1H, s); MS (FAB) m/e 526.3 (100, 396.1 (33), 33.1 (31); Anal. C 33 H 39 N 3 O 3 .0.25H 2 O; C, H, N. EXAMPLE 8 ##STR47## Method exactly as for Example 4, except using 2-Adoc-α-Me-RS-TrpOH (7) and 2-aminotetralin; yield 210 mg, 795, m.p. 97°-101° C. (MeOH/H 2 O); IR (film) 3400-3200, 2911, 2855, 1700, 1651, and 1495 cm -1 ; NMR g(CDCl 3 ) δ1.50-2.00 (16H, m) , 1.57 (1.5H, s) , 1.58 (1.5H, s), 2.42 (0.5H, d, J 7.5 Hz), 2.48 (0.5H, d, J 7.5 Hz), 2.70-3.05 (3H, m), 3.27 (0.5H, d, J 14.5 Hz), 3.29 (0.5H, d, J 14.5 Hz), 3.51 (0.5H, d, J 14.5 Hz), 3.54 (0.5H, d, J 14.5 Hz), 4.15-4.25 (1H, m), 4.80 (1H, d), 5.16 (0.5H, s), 5.21 (0.5H, s), 6.10- 6.20 (1H, brs), 6.99-7.21 (7H, m), 7.36 (1H, d, J 8 Hz), 7.61 (1H, d, J 8 Hz), 8.12 (1H, s), MS (FAB) m/e 526.3 (100), 396.2 (25), 330.2 (33); Anal. C 33 H 39 N 3 O 3 .0.75H); C, H, N. EXAMPLE 9 Butanoic acid, 4-oxo-4-[[1,2,3,4-tetrahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1. 3 ,7 ]-dec-2-yloxy)carbonyl]amino]propyl]amino]-1-naphthalenyl]amino] ##STR48## Step 1. Carbamic acid, [2-[(1-azido-1,2,3,4-tetrahydro-2-naphthalenyl)amino]1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]1-tricyclo[3.3.1.1 3 ,7 ]dec-2-yl ester (See Scheme V) ##STR49## A solution of 2-adamantyloxycarbonyl-α-methyl-R-tryptophan (3.00 g, 7.57 mmol) and pentafluorophenol (1.39 g, 7.57 mmol) in EtOAc (80 mL) was cooled to 0° C. and treated with N,N'-dicyclohexylcarbodiimide (1.56 g, 7.57 mmol). This reaction mixture was stirred for 30 minutes at 0° C., filtered, and the filtrate treated with (+) trans-2-amino-1-azido-1,2,3,4-tetrahydronaphthalene (1.56 g, 8.32 mmol) and allowed to warm to room temperature. After 48 hours the reaction mixture was washed with 1M citric acid solution (2×2 mL), saturated NaHCO 3 solution (2×20 mL), and H 2 O (2×20 mL). The organic phase was dried over MgSO 4 and the solvent evaporated in vacuo. The residue was separated by reverse phase silica gel chromatography using 4:1 MeOH:H 2 O as eluant to give the product 5 as a noncrystalline white solid (3.71 g, 86%), m.p. 105°-110° C. [α]D D 20 =+39.4° (c=0.5, MeOH); IR (film) 3500-3200, 2909, 2855, 2097, 1702, 1657, and 1493 cm -1 ; NMR (CDCl 3 ) δ1.40 (1H, s), 1.45 (2.5H, s), 1.55 (1.5H, s), 1.65-1.90 (13H, m), 2.00-2.20 (1H, m), 2.60-2.75 (1H, m), 2.81 (0.5H, b, J 5.4 Hz), 2.87 (0.5H, 5, J 5.3 Hz), 3.17- 3.27 (1H, m), 3.49 (0.5H, d, J 14.8 Hz), 3.56 (0.5H, d, J 14.7 Hz), 4.18 (0.5H, d, J 4.6 Hz), 4.25-4.35 (1.5H, m), 4.60-4.70 (1H, m), 5.04 (1H, s), 6.40-6.45 (0.5H, m), 6.46-6.55 (0.5H, m), 6.94 (1H, s), 7.05-7.30 (6H, m), 7.36 (1H, d, J 7.8 Hz), 7.55-7.65 (1H, m), 8.11 (1H, s); MS m/e (FAB) 567 (5), 173 924), 146 (28), 135 (100) and 109 (39). Step 2. (Scheme V, No. 6) ##STR50## A solution of thiazide from Step 1 (Scheme V, No. 5) (1.20 g, 2.11 mmol) in absolute EtOH (150 mL) was treated with Lundar catalyst (0.6 g, 50% w/w) and put under an atmosphere of hydrogen at a pressure of 50 psi for 12 hours at room temperature. This was then filtered over gypsum and evaporated in vacuo to give the amine as a syrup (1.14 g, 100%). This was used immediately in Step 3. Step 3 A solution of the amine from Step 2 (Scheme V, No. 6) (0.2 g, 0.37 mmol) in EtOAc (15 mL) was treated with succinic anhydride (0.044 g, 0.44 mmol) and stirred at reflux with N,N-dimethyl amino pyridine (0.061 g, 0.50 mmol) for 18 hours. This mixture was then evaporated to dryness and the residue chromatographed over reverse phase silica using 5:1; MeOH:H 2 O as eluent to give the product (Example 1) as a white solid (0.157 g, 66%), m.p. 137°-150° C.; [α] D 20 =+32° (c=0.5, MeOH); IR (film) 3500-3200, 2910, 2856, 1712, 1651, and 1531 cm -1 ; NMR (DMSO-d 6 +D 20 δ1.23 (1.5H, s), 1.29 (1.5H, s), 1.35-1.55 (2H, m), 1.60-2.00 (14H, m), 2.20-2.55 (4H, m), 2.70-2.85 (2H, m), 3.10-3.60 (2H, m), 3.85-4.00 (1H, m), 4.60-4.70 (1H, m), 5.00-5.10 (1H, M), 6.60-6.70 (1H, m), 6.85-7.25 (7H, m), 7.31 (1H, d, J 8 Hz), 7.46 (1H, d, J 8 Hz), 7.30-7.55 (1H, m), 8.23 (1H, d, J 9 Hz); Analysis for C 37 H 44 N 4 O 6 : Calcd: C, 67.92; H, 7.00; N, 8.56. Found: C, 67.96; H, 6.87; N, 8.65. EXAMPLE 10 ##STR51## Method exactly as for Example 9 except using glutaric anhydride in Step 3 instead of succinic anhydride, m.p. 130°-142° C.; [α] D 21 =410.8° (c=0.5, MeOH); IR (film) 3500-3200, 2919, 2854, 1710, 1651, and 1527 cm -1 ; NMR (CDCl 3 ) δ1.25 (1.5H, s), 1.35 91.5H, s), 1.40-1.55 (2H, m), 1.15-2.05 (16H, m), 2.10-2.25 (2H, m), 2.50-2.55 (4H, m), 2.75-2.85 (2H, m), 3.90-4.05 (1H, m), 4.55-4.70 (1H, m), 5.00-5.10 (1H, m), 6.55-6.70 (1H, m), 6.85-7.15 (7H, m), 7.31 (1H, d, J 8 Hz), 7.45-7.55 (1.5H, m), 7.60-7.65 (10.5H, m), 8.15-8.25 (1H, m). EXAMPLES 11 AND 12 Scheme VI, No. 7a and 7b Propanoic acid, 3-[[2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1,2,3,4-tetrahydro-1-naphthalenyl]amino]-3-oxo-, methyl ester (Isomer I) and Propanoic acid, 3-[[2-[[3-1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2 -yloxy)carbonyl]amino]propyl]amino]-1,2,3,4-tetrahydro-1-naphthalenyl]amino]-3-oxo-, methyl ester (Isomer II) ##STR52## A solution of the amine from Example 10, Step 2 (Scheme V, No. 6) (0.20 g, 0.4 mmol) in EtOAc (15 mL) was treated with methylmalonylchloride (0.06 g, 0.44 mmol) followed by triethylamine (0.03 g, 0.37 mmol) and stirred for 30 minutes at room temperature. This was then evaporated in vacuo and the residue separated by silica gel chromatography using 1:1 n-hexane:EtOAc as eluent to give two diastereoisomers separated as isomer I (0.05 g and Isomer II (0.06 g) (total yield 46%). Isomer I: (Example 11, Propanoic acid, 3-[[2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1,2,3,4-tetrahydro-1-naphthalenyl]amino]-3-oxo-, methyl ester), m.p. 140-°145° C.; [α] D 24 =+38.4° (c=0.25, MeOH); IR (film) 3500-3200, 2907, 2857, 1760-1700 (br), 1651, and 1491 cm -1 ; NMR (CDCl 3 ) δ1.50-2.15 (19H, m), 2.75-2.87 (1H, m), 2.90-3.05 (1H, m), 3.35 (2H, s), 3.40 (2H, s), 3.74 (3H, s), 3.95-4.05 (1H, m), 4.82 (1H, s), 5.15 (1H, b, J 10 Hz), 5.34 (1H, s), 6.86 (1H, d, J 7.5 Hz), 7.00-7.35 (9H, m), 7.65 (1H, d, J 8 Hz), 8.17 (1H, s); MS m/e (FAB) 641 (10), 263 (10), 173 (39), and 135 (100). Analysis for C 37 H 44 N 4 O 6 : Calcd: C, 69.35; H, 6.92; N, 8.74. Found: C, 69.22; H, 6.86; N, 8.72. EXAMPLE 12 Propanoic acid, 3-[[2-[[3-1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 , 7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1,2,3,4-tetrahydro-1-naphthalenyl]amino]-3 -oxo-, methyl ester, Isomer II M.p. 142°-183.5° C.; [α] D 24 =+26.8° (c=2.5, MeOH); IR (film) 3500-3200, 2910, 2854, 1760-1600 (br), 1651 and 1536 cm -1 ; MR (CDCl 3 ) δ1.45-2.05 (18H, m), 2.15-2.30 (1H, m), 2.80-2.90 (1H, m), 2.95-3.10 (1H, m), 3.24 (1H, d, J 17 Hz); 3.31 (1H, d, J 17 Hz), 3.39 (1H, d, J 15 Hz), 3.45 (1H, d, J 15 Hz), 3.73 (3H, s), 3.95-4.10 (1H, m), 4.81 (1H, s), 5.17 (1H, t, J 7 Hz, 5.23 (1H, s), 6.93 (1H, d, J 7 Hz), 6.97 (1H, d, J 2 Hz), 7.05-7.30 (6H, m), 7.34 (1H, d, J 8 Hz), 7.38 (1H, d, J 9 Hz), 7.60 (1H, d, J 8 Hz), 8.15 (1H, s); MS m/e (FAB) 641 (8), 263 (10), 173 (40), and 135 (100). Analysis for C 37 H 44 N 4 O 6 .0.25 H 2 O: Calcd: C, 68.87; H, 6.95; N, 8.68. Found: C, 68.98; H, 7.08; N, 8.33. EXAMPLE 13 Scheme VI, No. 11 2-Butanoic acid, 1-[[1,2,3,4-tetrahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]-dec-2-yloxy)carbonyl]amino]propyl]amino]-1-naphthalenyl]amino]-4-oxo-, methyl ester ##STR53## A solution of the amine from Example 9, Step 2 (Scheme V, No. 6) (0.6 g, 1.1 mmol) in EtOAc (25 mL) was treated with methylpentafluorophenyl fumarate (0.5 g, 1.7 mmol) and the resultant mixture stirred 18 hours at room temperature. The solvent was then removed in vacuo and the residue chromatographed over silica gel using 3: 1 EtOAc: hexane as eluent to give the product as a white, noncrystalline solid and a mixture of two diastereoisomers (0.35 g, 50%); m.p.=234°-236° C.; [α] D 20 =+10.4° (c=0.5, MeOH); IR (film) 3500-3200, 2912, 2854, 1715, 1646, and 1538 cm -1 ; NMR (CDCl 3 ) δ1.34 (1.5H, s) 1.45-2.20 (17.5H, m), 2.70-2.90 (2H, m), 3.16 (0.5H, d, J 14.5 Hz), 3.27 (0.5H, d, J 6.5 Hz), 3.32 (0.5H, d, J 7 Hz), 3.42 (0.5H, d, J 14.5 Hz), 3.72 (1.5H, s), 3.74 (1.5H, s), 3.90-4.10 (1H, m), 4.75-4.85 (1H, m), 5.10-5.30 (2H, m), 6.70-7.35 (12H, m), 7.53 (0.5H, d, J 8 Hz), 7.60 (0.5H, d, J 8 Hz), 8.31 (0.5H, s), 8.37 (0.5H, s). Analysis for C 38 H 44 N 4 O 6 .0.25H 2 O: Calcd: C, 69.44; H, 6.82; N, 8.52. Found: C, 69.55; H, 6.71; N, 8.49. EXAMPLE 14 Scheme VIII, No. 20 Butanoic acid, 4-oxo-4-[[1,2,3,4-tetrahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3,3,1,1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1-naphthalenyl]amino] ##STR54## Step 1. Phenylmethyl (±)-trans-(1,2,3,4-tetrahydro-2-iodo-1-naphthalenyl)carbamate (Scheme VII, No. 13) ##STR55## A solution of 1,2- dihydronaphthalene (10.0 g, 76.8 mmol) and iodine (19.5 g, 76.8 mmol) in anhydrous ether (200 mL) was treated with silver cyanate (17.27 g, 115.2 mmol) at 10° C. This mixture was stirred for 30 minutes, allowed to warm to room temperature, and left stirring a further 18 hours, then put under reflux for 1.5 hours. This suspension was then filtered, the filtrate evaporated to dryness in vacuo. Benzyl alcohol (100 mL) was then added and the reaction mixture stirred for 3 hours at room temperature. Excess benzyl alcohol was distilled off in vacuo and the residue crystallized and recrystallized from methanol to give the benzyl urethane (19.12 g, 61%) as a white solid; m.p. 141.2° C. (MeOH); IR (film) 3500-3200, 1697, and 1518 cm -1 ; NMR (CDCl 3 ) δ2.05-2.25 (2H, m) , 2.75-2.85 (1H, m), 2.90-3.05 (1H, m), 4.55-4.70 (1H, br s), 5.05-5.25 (4H, m), 7.05-7.35 (9H, m). Analysis for C 18 H 18 INO 2 : Calcd: C, 53.9; H, 4.45; N, 3.44. Found: C, 53.29; H, 4.42; N, 3.45. Step 2. Phenylmethyl (±)-cis-(2-azido-1,2,3,4-tetrahydro-1-naphthalenyl)carbamate (Scheme VII, No. 14) ##STR56## A solution of the benzyl urethane from Step 1 (Scheme VII, No. 13) (7.62 g, 18.7 mmol) in DMF (100 mL) was treated with sodium azide (1.46 g, 22.5 mmol) and the resulting mixture stirred 18 hours at room temperature. The solvent was then removed in vacuo and the residue suspended between H 2 O and EtOAc. The organic phase was washed with saturated NaHCO 3 solution (2×20 mL), brine (2×20 mL), and H 2 O (2×20 mL) and then dried over MgSO 4 , filtered, and the solvent removed in vacuo. The residue was crystallized and recrystallized from MeOH to give the azide (2.94 g, 49%), m.p. 103.7° C. (MeOH); NMR (CDCl 3 ) δ2.00-2.25 (2H, m), 2.70-2.85 (1H, m), 2.95-3.10 (1H, m), 4.05-4.20 (1H, br s), 5.00-5.25 (4H, m), 7.05-7.40 (9H, m); IR (film) 3500-3200, 2101, 1697, and 1505 cm -1 . Step 3. Phenylmethyl (±)-cis-(2-amino-1,2,3,4-tetrahydro-1-naphthalenyl)carbamate (Scheme VII, No. 15) ##STR57## A solution of the azide from Step 2 (Scheme VII, No. 14) (2.00 g, 6.20 mmol) in absolute EtOH (150 μL) was treated with Lindlar catalyst (1.0 g, 50% w/w) and put under an atmosphere of hydrogen at a pressure of 50 psi for 2 hours at 25° C. This mixture was then filtered over gypsum and the filtrate evaporated to dryness in vacuo. The residue was separated by column chromatography over silica gel using 10% MeOH in CH 2 Cl 2 as eluant to give the amine which was recrystallized from ether (1.3 g, 67%), m.p. 102°-145° C. (Et 2 O); IR (film) 3500-3200, 1710, 1530, and 1454 cm -1 ; NMR (CDCl 3 ) δ1.70-1.95 (2H, m), 2.75-3.00 (2H, m), 3.15-3.25 (1H, m), 4.80 (3H, s), 4.91 (1H, d, J 4 Hz), 5.10 (1H, d, J 12.5 Hz), 5.16 (1H, d, J 12.5 Hz), 7.05-7.40 (9H, m). Analysis for C 18 H 20 N 2 O 2 : Calcd: C, 72.94; H, 6.80; N, 9.45. Found: C, 72.84; H, 6.81; N, 9.44. Step 4. Carbamic acid, [1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2-[[1,2,3,4-tetrahydro-1-[[phenylmethoxy)carbonyl]amino]-2-naphthalenyl]amino]ethyl]tricyclo[3.3.1,1 3 ,7 ]dec-2-yl ester (Scheme VII, No. 16) ##STR58## A solution of 2-adamantyloxycarbonyl-α-methyl-1-tryptophan (5.94 g, 15.1 mmol) and pentafluorophenol (2.78 g, 15.1 mmol) in EtOAc (150 mL) was treated at 0° C. with N,N'-dicyclohexylcarbodiimide (3.11 g, 15.1 mmol). This mixture was stirred for 2 hours at 0° C., filtered, and the amine prepared in Step 3 (Scheme III, No. 15) (5.17 g, 16.6 mmol) was added to the filtrate. This mixture was then stirred for 48 hours at room temperature before being washed with 1M citric acid solution (2×20 mL), saturated NaHCO 3 solution (2×20 mL), and H 2 O (2×20 mL). The organic phase was dried over MgSO 4 , filtered, and the filtrate evaporated to dryness in vacuo. The residue was separated by chromatography over reverse phase silica gel using MeOH:H 2 O (4:1) as eluant to give the product (7.21 g, 70%). Step 5. Tricyclo[3.3.1.1 3 ,7 ]dec-2yl[1R-[1α,2α(R*)]] and [1S-[1α,2α(S*)]]-[2-[(1-amino-1,2,3,4-tetrahydro-2-naphthalenyl)amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate (Scheme VII, No. 17) ##STR59## A solution of the benzyl urethane from Step 4 (Scheme VII, No. 16) (1.0 g, 1.5 mmol) in absolute EtOH (150 mL) was treated with 10% palladium on carbon (0.2 g, 20% w/w) and put under an atmosphere of hydrogen at a pressure of 50 psi at 25° C. for 4 hours. The mixture was then filtered over celite and the filtrate evaporated to dryness in vacuo to give the product (0.79 g, 100%), which is used immediately in the next step. Step 6. [1R-[1α,2α(R*)] and [1S-[1α,2α(S*)]]-4-[[decahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1-naphthalenyl]amino]-4-oxobutanoic acid (Scheme VIII, No. 20) ##STR60## A solution of the amine prepared in Step 5 (Scheme VII, No. 17) (0.4 g, 0.73 mmol) in EtOAc (30 mL) was treated with succinic anhydride (0.09 g, 0.9 mmol) and the resulting solution stirred 18 hours at room temperature. The mixture was then washed with 1M HCl solution (20 mL), saturated NaHCO 3 solution (2×20 mL), and H 2 O (2×20 mL). The organic phase was dried over MgSO 4 , filtered, and the filtrate evaporated to dryness in vacuo. The residue was separated over reverse phase silica gel using MeOH:H 2 O (3:1) as eluant to give the product as a noncrystalline white solid (0.27 g, 57%), m.p. 213°-238° C.; IR (film) 3500-3200, 2911, 2852, 1696, 1661, and 1515 cm -1 ; NMR (DMSO-d 6 , D 2 O) δ1.27 (1.5H, s), 1.35 (1.5H, s), 1.36-1.50 (2H, m), 1.67-2.06 (14H, m), 2.17-2.40 (4H, m), 2.60-2.95 (2H, m), 3.12 (0.5H, d, J 14.5 Hz), 3.18-3.34 (1H, m), 3.39-3.55 (0.5H, m), 4.00-4.15 (1H, br s), 4.57- 4.67 (1H, br s), 5.12 (0.5H, d, J 4.4 Hz), 5.15 (0.5H, d, J 4.4 Hz), 6.85-6.98 (1H, m), 6.97-7.24 (6H, m), 7.30 (0.5H, d, J 8 Hz), 7.31 (0.5H, d, J 8 Hz), 7.40-7.55 (1H, m). EXAMPLE 15 Scheme VIII, No. 21 Pentanoic acid, 5-oxo-5-[[1,2,3,4-tetrahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1-naphthalenyl]amino]-1S-[1.alpha.,2α(S*)]] and [1R-[1α,2α(R*)]] ##STR61## Method exactly as for Example 14 except using glutaric anhydride in Step 6 instead of succinic anhydride (yield 0.29 g, 60%), m.p. 196°-206° C.; IR (film) 3500-3200, 2924, 2856, 1712, 1659, and 1515 cm -1 ; NMR (DMSO-d 6 , D 2 O) δ1.27 (1.5H, s), 1.31 (1.5H, s), 1.37-1.53 (2H, m), 1.57-2.25 (20H, m), 2.60-2.95 (2H, m), 3.10 (0.5H, d, J 14.5 Hz), 3.28 (0.5H, d, J 16.3 Hz), 3.37 (0.5H, d, J 16.3 Hz), 3.39-4.50 (0.5H, m), 3.97-4.18 (1H, br s), 4.53-4.66 (1H, br s), 5.13 (0.5H, d, J 4 Hz), 5.17-5.23 (0.5H, br s), 6.83-7.24 (7H, m), 7.31 (1H, d, J 7.3 Hz), 7.44 (0.5H, d, J 8.5 Hz), 7.46 (0.5H, d, J 8 Hz). EXAMPLE 16 Scheme VIII, No. 18 Propanoic acid, 3-oxo-3-[[1,2,3,4-tetrahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo-[3.3.1.1 3 ,7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1-naphthalenyl]amino]-, methyl ester ##STR62## A solution of the amine as prepared in Example 14, Step 5 (Scheme VII, No. 17) (0.8 g, 1.5 mmol) and methyl malonyl chloride (0.24 g, 1.77 mmol) in EtOAc (60 mL) was treated with triethylamine (0.15 g, 1.48 mmol) and the resulting mixture stirred 18 hours at room temperature. This mixture was then washed with 1M citric acid solution (3×20 mL), saturated NaHCO 3 solution (2×20 mL), and H 2 O (2×20 mL). The organic phase was dried over MgSO 4 , filtered, and filtrate evaporated in vacuo to dryness. The residue was then purified by reverse phase silica gel chromatography using MeOH:H 2 O (3:1) as eluant to give the product, m.p. 130.7°-154.9° C. EXAMPLE 17 Scheme VIII, No. 22 2-Butenoic acid, 4-oxo-4-[[1,2,3,4-tetrahydro-2-[[3-(1H-indol-3-yl)-2-methyl-1-oxo-2-[[(tricyclo[3.3.1.1 3 .7 ]dec-2-yloxy)carbonyl]amino]propyl]amino]-1-naphthalenyl]amino]-, methyl ester ##STR63## A solution of the amine as prepared in Example 14, Step 5 (Scheme VII, No. 17) (0.8 g, 1.5 mmol) in EtOAc (60 mL) was treated with methyl(pentafluorophenyl)fumarate (0.65 g, 2.22 mmol) and stirred for 12 hours at room temperature. The mixture was evaporated to dryness in vacuo and the residue separated by reverse phase silica gel chromatography using MeOH:H 2 O (3:1) as eluant to give the product (0.52 g, 56%), m.p. 142.6°-146.1° C. EXAMPLE 18 Tricyclo[3.3.1.1 3 .7 ]dec-2-yl ester (R) [1-(1H-indol-3-ylmethyl)-2-[(4-methoxyphenyl)amino]-1-methyl-2-oxoethyl]carbamate ##STR64## Step 1 N,N 1 -dicyclohexylcarbodiimide (0.460 g, 2.24 mmol) was added to a stirred solution of 2-Adoc-R-α-Me-Trp-OH (0.810 g, 2.04 mmol) and 1-hydroxybenzotriazole monohydrate (0.380 g, 2.45 mmol) in EtOAc (80 mL). The mixture was stirred for 1 hour at room temperature and the N,N 1 -dicyclohexylurea filtered off. 2-anisidine (0.280 g, 2.24 mmol) was added followed by 4-dimethylaminopyridine (0.024 g, 0.20 mmol) and the mixture stirred at room temperature for 72 hours. The EtOAc solution was washed with 5% citric acid (2×25 mL), saturated NaHCO 3 solution (2×25 mL) 5% citric acid (25 mL), and once with brine (25 mL). The EtOAc was dried over MgSO 4 , filtered and the solvent removed in vacuo. The residue was purified by chromatography on silica using 67% n-hexane/33%EtOAc as eluant giving the product as a white solid (0.584 g, 57%); mp 111°- 115° C.; [α] D 20 +39.8° (C=0.12, acetone); IR(film) 3327, 2914 1701, and 1671 cm -1 ; δNMR (CDCl 3 ) 1.43-1.55 (2H, m) , 1.64 (3H, s) , 1.66-1.99 (12H, m), 3.35 (1H, d, J 14.7 Hz), 3.57 (1H, d, J 14.6 Hz), 3.77(3H, s), 4.87 (1H, s), 5.23 (1H, m), 6.82 (2H, d, J 9.0 Hz), 6.99 (1H, s), 7.06-7.10 (1H, m), 7.15-7.20 (1H, m), 7.29-7.36 (3H, m), 7.60 (1H, d, J 7.9 Hz), 8.18 (1H, b), 8.32 (1H, s). Analysis calculated for (C 30 H 35 N 3 O 4 ): C, H, N.
Novel α-substituted Trp dipeptoid derivatives cyclized at the C-terminal useful as agents in the treatment of obesity, hypersecretion of gastric acid in the gut, gastrin-dependent tumors, or as antipsychotics are disclosed. Further, the compounds are antianxiety agents and antiulcer agents. They are agents useful for preventing the response to the withdrawal from chronic treatment with or use of nicotine, diazepam, alcohol, cocaine, caffeine, or opioids. The compounds of the invention are also useful in treating and/or preventing panic attacks. Also disclosed are pharmaceutical compositions and methods of treatment using the compounds as well as processes for preparing them and novel intermediates useful in their preparation. An additional feature of the invention is the use of the compounds in diagnostic compositions.
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CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part to a non-provisional application Ser. No. 09/848,492 titled, “Controlled Engine Shutdown for a Hybrid Electric Vehicle” filed May 3, 2001. The entire disclosure of Ser. No. 09/848,492 is incorporated herein by reference in its entirety. BACKGROUND OF INVENTION 1. Field of Invention The present invention relates generally to a hybrid electric vehicle (HEV), and specifically to a method and system to control an HEV engine shutdown. 2. Discussion of Prior Art The need to reduce fossil fuel consumption and emissions in automobiles and other vehicles predominately powered by internal combustion engines (ICEs) is well known. Vehicles powered by electric motors attempt to address these needs. Another alternative solution is to combine a smaller ICE with electric motors into one vehicle. Such vehicles combine the advantages of an ICE vehicle and an electric vehicle and are typically called hybrid electric vehicles (HEVs). See generally, U.S. Pat. No. 5,343,970 to Severinsky. The HEV is described in a variety of configurations. Many HEV patents disclose systems where an operator is required to select between electric and internal combustion operation. In other configurations, the electric motor drives one set of wheels and the ICE drives a different set. Other, more useful, configurations have developed. For example, a series hybrid electric vehicle (SHEV) configuration is a vehicle with an engine (most typically an ICE) connected to an electric motor called a generator. The generator, in turn, provides electricity to a battery and another motor, called a traction motor. In the SHEV, the traction motor is the sole source of wheel torque. There is no mechanical connection between the engine and the drive wheels. A parallel hybrid electrical vehicle (PHEV) configuration has an engine (most typically an ICE) and an electric motor that work together in varying degrees to provide the necessary wheel torque to drive the vehicle. Additionally, in the PHEV configuration, the motor can be used as a generator to charge the battery from the power produced by the ICE. A parallel/series hybrid electric vehicle (PSHEV) has characteristics of both PHEV and SHEV configurations and is sometimes referred to as a “powersplit” configuration. In one of several types of PSHEV configurations, the ICE is mechanically coupled to two electric motors in a planetary gear-set transaxle. A first electric motor, the generator, is connected to a sun gear. The ICE is connected to a carrier. A second electric motor, a traction motor, is connected to a ring (output) gear via additional gearing in a transaxle. Engine torque can power the generator to charge the battery. The generator can also contribute to the necessary wheel (output shaft) torque if the system has a one-way clutch. The traction motor is used to contribute wheel torque and to recover braking energy to charge the battery. In this configuration, the generator can selectively provide a reaction torque that may be used to control engine speed. In fact, the engine, generator motor and traction motor can provide a continuous variable transmission (CVT) effect. Further, the HEV presents an opportunity to better control engine idle speed over conventional vehicles by using the generator to control engine speed. The desirability of combining an ICE with electric motors is clear. There is great potential for reducing vehicle fuel consumption and emissions with no appreciable loss of vehicle performance or drive-ability. The HEV allows the use of smaller engines, regenerative braking, electric boost, and even operating the vehicle with the engine shutdown. Nevertheless, new ways must be developed to optimize the HEV”s potential benefits. One such area of HEV development is implementing a controlled engine shutdown in an HEV. If the engine shuts down in an uncontrolled manner, its starts and stops throughout a given HEV drive cycle can increase tailpipe emissions from inconsistent amounts of residual fuel (vapor and puddles) in the intake manifold from one shutdown to the next. The amount of residual fuel depends on the amount of liquid fuel flow from the injectors, as well as the amount of fuel vapor introduced by the vapor management valve (VMV) and exhaust gas recirculation valve (EGR) prior to the shutdown. Vapor management valves (VMV) are widely used in evaporative emission control systems to reduce the fuel vapor build up in the fuel system. Fuel vapor in the fuel tank and lines is captured in a vapor storage canister (typically a charcoal material), and then drawn out into the engine's intake manifold via the VMV. The amount of fuel vapor introduced into the intake manifold, and thus into the engine cylinders to be combusted, is proportional to how much the VMV is opened and how much intake manifold vacuum is available. Exhaust gas recirculation valves (EGR) are widely used in tailpipe emission control systems to recirculate a portion of the hot exhaust gases back into the intake manifold, thereby diluting the inducted air/fuel mixture and lowering combustion temperatures to reduce the amount of NOx (oxides of nitrogen) that are created. The amount of exhaust gases re-circulated into the intake manifold, and thus into the cylinders, is proportional to how much the EGR valve is opened and how much intake manifold vacuum is available. Though mostly made up of inert byproducts of the previous combustion event, the exhaust gases partially contain some unburned fuel vapor. During engine shutdown in an HEV drive cycle, the fuel injectors, VMV, and EGR valves may be flowing at different rates depending on when the shutdown occurs, and thus may contribute fuel vapor and puddle amounts to the intake manifold that vary from one engine shutdown to the next. This, in turn, leads to inconsistent amounts of residual fuel left in the intake manifold from one subsequent engine restart to the next. Because of the many engine shutdowns and starts in an HEV, it is important to minimize the amount of tailpipe emissions during these events. Nevertheless, with an inconsistent amount of residual fuel vapor and puddles, it becomes difficult to deliver the proper amount of fuel through the injectors from one engine start to the next during the course of a drive cycle. Thus, tailpipe emissions may vary from one engine start to the next during a drive cycle. A controlled engine shutdown routine can also reduce evaporative emissions following a “key-off” engine (and vehicle) shutdown at the end of a drive cycle. One significant contributor to evaporative emissions in conventional vehicles during a “soak” (i.e., the time between drive cycles where the vehicle is inactive and the engine is off) is residual fuel vapor that migrates to the atmosphere from the intake manifold through the vehicle's air induction system. By reducing the residual fuel from the intake manifold, evaporative emissions can be reduced during the vehicle “key-off” soak periods following a drive cycle. To accomplish this, a “power sustain” function is needed to continue to provide power to HEV controllers, ignition system, and fuel system (pump and injectors) for a period of time after “key-off.” This allows the generator to continue to spin the engine (after injectors are ramped/shut off) while the spark plugs continue to fire until residual fuel (vapor and liquid) is flushed from the intake manifold into the combustion chamber to be combusted (even if partially), and then moved on (delivered) into the hot catalytic converter to be converted. Although controlled engine shutdowns are known in the prior art, no such controlled engine shutdown strategy has been developed for an HEV. U.S. Pat. No. 4,653,445 to Book, et al., discloses a control system for engine protection to different threatening conditions. Examples of such conditions include fire, the presence of combustible gas or fuel, rollover or excessive tilt, low oil pressure, low coolant level, engine overheating, or engine overspeed. Book”s engine shutdown system receives warning signals for fault conditions that initiate engine shutdown. Book also includes a method to divide fault signals into either a fast shutdown response or a delayed shutdown response. This method only applies to convention ICE vehicles. U.S. Pat. No. 4,574,752 to Reichert, Jr., et al., also discloses an engine shutdown device for a conventional ICE and is particularly suited to stationary engine applications. It describes a controlled timed shutdown to reduce engine wear or system damage if problems arise in an external device powered by the engine. When Reichert”s method detects a fault in a peripheral device driven or controlled by the engine, it uses a relay, a fuel shutoff control, an engine throttle control, and a timer to shutdown the engine. Prior art also reveals other developments to reduce fuel waste, emissions and dieseling during controlled engine shutdown for a conventional ICE. U.S. Pat. No. 4,366,790 to DeBoynton, discloses a by-pass system that stops fuel flow to an engine when combustion is not required. When this normally open by-pass valve is closed during events such as deceleration or engine shutdown, only filtered air at a reduced vacuum is allowed into the engine manifold. This prevents fuel waste. See also generally, U.S. Pat. No. 5,357,935 to Oxley, et al. Other systems have developed to maximize the amount of exhaust gas recirculation when an ICE is switched off to reduce emissions and dieseling. U.S. Pat. No. 4,367,720 to Miyoshi, et al. U.S. Pat. No. 4,312,310 to Chivilo, et al., discloses an emissions prevention control system that stops engine fuel intake during idle conditions or deceleration and continues to spin the ICE with an auxiliary power unit such as an electric motor or hydraulic pressure. The motor keeps the engine spinning to allow subsequent fast start-up when normal driving conditions resume. Although the prior art discloses engine shutdown systems for conventional ICEs, they do not meet the engine shutdown needs of an HEV. Thus, a system is needed that controls HEV engine shutdowns to preserve the HEV goal of reduced emissions. SUMMARY OF INVENTION Accordingly, an object of the present invention is to provide a controlled engine shutdown process for a hybrid electric vehicle (HEV). It is a further object of the present invention to provide a method and system to control HEV engine shutdowns so as to achieve the HEV goal of reduced emissions (tailpipe and evaporative). It is a further object of the present invention to provide a method and system to control HEV engine shutdowns that have specific controllers within a vehicle system controller and/or engine controller to: shut (“ramp”) off fuel injectors; control engine torque via a throttle plate; control engine speed; stop spark delivery by disabling an ignition system; stop purge vapor flow by closing a VMV; stop exhaust gas recirculation flow by closing an EGR valve; and flush or clean out an engine intake manifold of residual fuel (vapor and puddles) once all sources of fuel are halted (injectors, VMV, and EGR valve). It is a further object of the present invention to abort engine shutdown if the engine is commanded to run and the fuel injector ramping has not yet begun. It is a further object of the present invention to shut off spark by disabling the ignition system when engine speed is less than a calibratable threshold. It is a further object of the present invention to shut (“ramp”) off fuel injectors in a calibratable manner, such as all injectors off at once, one injector off at a time, or two injectors off at a time. It is a further object of the present invention to provide a power sustain system for controlled engine shutdown to complete in a “key-off” shutdown. Other objects of the present invention will become more apparent to persons having ordinary skill in the art to which the present invention pertains from the following description taken in conjunction with the accompanying figures. BRIEF DESCRIPTION OF DRAWINGS The foregoing objects, advantages, and features, as well as other objects and advantages, will become apparent with reference to the description and figures below, in which like numerals represent like elements and in which: FIG. 1 illustrates a general hybrid electric vehicle (HEV) configuration. FIG. 2 illustrates a possible strategy of the controlled engine shutdown sequence for an HEV. FIG. 3 illustrates stage one of the controlled engine shutdown sequence for an HEV. FIG. 4 illustrates a basic schematic of the vehicle system control, engine control unit, and a transaxle management unit. FIG. 5 illustrates stage two of the controlled engine shutdown sequence for a hybrid electric vehicle. DETAILED DESCRIPTION The present invention relates to electric vehicles and, more particularly, hybrid electric vehicles (HEVs). FIG. 1 demonstrates just one possible configuration, specifically a parallel/series hybrid electric vehicle (powersplit) configuration. In a basic HEV, a planetary gear set 20 mechanically couples a carrier gear 22 to an engine 24 via an one way clutch 26 . The planetary gear set 20 also mechanically couples a sun gear 28 to a generator motor 30 and a ring (output) gear 32 . The generator motor 30 also mechanically links to a generator brake 34 and is electrically linked to a battery 36 . A traction motor 38 is mechanically coupled to the ring gear 32 of the planetary gear set 20 via a second gear set 40 and is electrically linked to the battery 36 . The ring gear 32 of the planetary gear set 20 and the traction motor 38 are mechanically coupled to drive wheels 42 via an output shaft 44 . The planetary gear set 20 , splits the engine 24 output energy into a series path from the engine 24 to the generator motor 30 and a parallel path from the engine 24 to the drive wheels 42 . Engine 24 speed can be controlled by varying the split to the series path while maintaining the mechanical connection through the parallel path. The traction motor 38 augments the engine 24 power to the drive wheels 42 on the parallel path through the second gear set 40 . The traction motor 38 also provides the opportunity to use energy directly from the series path, essentially running off power created by the generator motor 30 . This reduces losses associated with converting energy into and out of chemical energy in the battery 36 and allows all engine 24 energy, minus conversion losses, to reach the drive wheels 42 . A vehicle system controller (VSC) 46 controls many components in this HEV configuration by connecting to each component”s controller. An engine control unit (ECU) 48 connects to the engine 24 via a hardwire interface. The ECU 48 and VSC 46 can be based in the same unit, but are actually separate controllers. The VSC 46 communicates with the ECU 48 , as well as a battery control unit (BCU) 50 and a transaxle management unit (TMU) 52 through a communication network such as a controller area network (CAN) 54 . The BCU 50 connects to the battery 36 via a hardwire interface. The TMU 52 controls the generator motor 30 and traction motor 38 via a hardwire interface. It is in the VSC 46 and ECU 48 that coordination of a controlled engine 24 shutdown takes place to meet the objects of the present invention. At a predetermined moment when the VSC 46 determines it is best for the vehicle to run without the engine, such as low torque demand or a “key-off” from an operator, the VSC 46 initiates engine 24 shutdown by issuing a command to the ECU 48 . One possible engine 24 shutdown routine, that is the preferred embodiment of the present invention, is illustrated in FIGS. 2, 3 and 5 . FIG. 2 shows a general strategy of the controlled engine shutdown sequence for an HEV. In FIG. 2 at Step 102 , the VSC 46 determines whether the engine 24 is needed. If the engine 24 is not needed (such as during a low-torque demand or a “key-off” from the operator) the strategy generates a command at Step 104 to the VSC 46 to begin stage one 106 of the engine 24 shutdown sequence. Stage one 106 controls engine 24 speed and engine 24 torque. Once stage one 106 is determined complete at step 108 , the strategy issues a command for the ECU 48 to begin stage two 110 of the engine 24 shutdown sequence. In stage two 110 , the strategy generates a command for the ECU 48 to shut-off a purge valve at Step 112 to stop purge flow from a vapor management valve. Next, the strategy generates a command for the ECU 48 to shut-off an exhaust gas recirculation (EGR) valve at Step 114 to stop exhaust gas recirculation. Next, the strategy generates a command for the ECU 48 to an injector stop timer to shut (“ramp”) off injectors based on a calibratable delay at Step 116 . Once the strategy determines that all the injectors are off at Step 118 , the strategy generates a command for the ECU 48 to flush an intake manifold of residual fuel at Step 120 when all sources of fuel are halted. Once the strategy determines that the intake manifold is flushed at Step 122 , the strategy generates a command for the ECU 48 to shut-off the engine 24 at Step 124 . This can be accomplished by disabling the ignition system so that no sparking occurs from the spark plugs (not shown). FIG. 3 specifically illustrates stage one 106 of a HEV engine shutdown routine, and deals with the overall coordination of the engine shutdown by controlling the engine speed and torque (via electronic throttle control) prior to invoking stage two 110 of the engine shutdown sequence, while power is sustained to the controllers, ignition system, and fuel system (pump and injectors) if an optional “power sustain” feature is implemented for “key-off” engine shutdowns. FIG. 5 illustrates stage two 110 , that is a more specific control of the engine components, such as fuel injectors, vapor management valve (VMV), and exhaust gas recirculation (EGR) valves, as well as the ability to “flush” the intake manifold of residual fuel if the optional “power sustain”feature is implemented for “key-off” engine shutdowns. Stage one 106 is illustrated in this preferred embodiment as being handled in the VSC 46 , while stage two 110 is handled in the ECU 48 . These “stages” do not necessarily need to be located in the controllers used in this illustrative example. FIG. 3 (stage one 106 ) is a timeline going from left to right, as follows: DES_ENG_TORQUE 98 =the desired engine 24 torque command from the VSC 46 to the ECU 48 ; control of desired engine torque directly controls engine throttle position, if a torque based electronic throttle controller system is used; in this case, with a known engine 24 map, a desired engine 24 brake torque can be broken down into desired engine 24 indicated torque, then to desired engine 24 airflow, and then finally to desired engine 24 throttle position. ACTUAL_ENG_SPEED 94 =the actual engine 24 speed as measured by a crankshaft position sensor (not shown), read by the ECU 48 , and sent to the VSC 46 . DES_ENG_SPEED 90 =the desired engine 24 speed command from the VSC 46 to the TMU 52 ; the TMU 52 has the generator motor 30 in “speed” control for most driving and the VSC 46 sets the target speed of the generator motor 30 via this DES_ENG_SPEED 90 command. Generator motor 30 and engine 24 speed are always proportional to each other because they are mechanically coupled in the planetary gear set 20 . ENGINE_MODE 72 =the mode command from VSC 46 to ECU 48 ; 0=engine 24 commanded to be off, 1=engine 24 commanded to be on; this is what starts stage two 110 of the engine shutdown routine as illustrated in FIG. 5 . ENGINE_RUNNING 64 =flag indicating whether the engine 24 is running (i.e., making combustion and torque); 0=engine 24 not running (off), 1=engine 24 is running (on). This flag is set to 0 in stage two 110 of the engine shutdown routine as illustrated in FIG. 5 when conditions are met, and then sent from the ECU 48 to the VSC 46 . Stage two routine indicator 110 =this routine begins when ENGINE_MODE 72 =0. Illustrated with specificity in FIG. 5 . GEN_MODE 92 =the mode command from the VSC 46 to the TMU 52 ; 1=speed control, 0=spin engine to a stop (0 speed). POWER_SUSTAIN_TMR 74 =timer that begins when the key is turned “OFF” and then runs until a calibratable power sustain delay time is met (POWER_SUSTAIN_DLY 78 ) or when ENGINE_RUNNING 64 =0, depending on which option is implemented. POWER_SUSTAIN_FLG 76 =flag set inside the VSC 46 that, when=1, sustains power to all the controllers, the ignition system, and the fuel system (pump and injectors); flag is set to 1 when the key is turned “OFF”, and cleared to 0 when POWER_SUSTAIN_TMR 74 exceeds POWER_SUSTAIN_DLY 78 or when ENGINE_RUNNING 64 =0, depending on which option is implemented. FIG. 4 shows schematically the interaction of the VSC 46 with the TMU 52 and the ECU 48 as described above. FIG. 5 (Stage two 110 ) is also a timeline read from left to right, as follows: ENGINE_MODE 72 =the mode command from VSC 46 to ECU 48 that is set in stage one 106 , as illustrated in FIG. 3; 0=engine 24 commanded to be off, 1=engine 24 commanded to be on; this is what starts stage two 110 of the engine shutdown routine as illustrated in FIG. 5 . INJ_STOP_TMR 56 =(IF OPTION A 58 )=timer that begins when the command to do the shutdown is given (ENGINE_MODE 72 =0) and then runs until all the injectors are shut (“ramped”) off; each injector is shut off based on a calibratable delay relative to when the shutdown command was given. (IF OPTION B 60 )=timer that begins when the command to do the shutdown is given (ENGINE_MODE 72 =0) and then gets reset each time one of the injectors is shut off; each injector is shut off based on a calibratable delay relative to when the last injector was shut off. SHUTDOWN_PG_DIS 66 =flag requesting that a purge valve be unconditionally shut off for the shutdown process. SHUTDOWN_EGR_DIS 68 =flag requesting that the exhaust gas recirculation (EGR) valve be unconditionally shut off for the shutdown process. INJON 126 =actual number of fuel injectors commanded ON (maximum is 4 for this 4-cylinder illustrative example). MAN_FLUSH_TMR 62 =timer that begins when all the injectors have been COMMANDED OFF (via INJON 126 =0) to allow for the intake manifold to be flushed of residual fuel (vapor and liquid). ENGINE_RUNNING 64 =flag indicating whether the engine 24 is running (i.e., making combustion and torque); 0=engine 24 not running (off), 1=engine 24 is running (on). This flag is set to 0 when a manifold “flushing” process is complete (MAN_FLUSH_TMR 62 >MAN_FLUSH_DLY 88 ) and then sent from the ECU 48 to the VSC 46 . SPK_ENG_MODE 70 =spark shutoff command; 0=disable ignition system (i.e., do not allow spark plugs to fire), 1=enable ignition system (i.e., allow spark plugs to fire). This command is set to 1 when ACTUAL_ENG_SPEED 94 falls below a calibratable threshold (SPK_SPD_THRESHOLD 96 ). Stages one 106 and two 110 of the engine 24 shutdown routine have the following calibratable parameters (Note: While this example applies only to a four cylinder engine 24 , it can easily be adapted to other engines with different cylinder configurations using the same type of parameters.): INJDLY43 80 =time delay from receiving the engine 24 shutdown command (ENGINE_MODE 72 =0) to when ONE injector is shut off (either OPTION A 58 or OPTION B 60 ). INJDLY32 82 =time delay from receiving the engine 24 shutdown command (ENGINE_MODE 72 =0) to when TWO injectors are shut off (OPTION A 58 ), or=time delay from one injector having been shut off (INJON 126 =3) to when TWO injectors are shut off (OPTION B 60 ). INJDLY21 84 =time delay from receiving the engine 24 shutdown command (ENGINE_MODE 72 =0) to when THREE injectors are shut off (OPTION A 58 ), or=time delay from two injectors having been shut off (INJON 126 =2) to when THREE injectors are shut off (OPTION B 60 ). INJDLY10 86 =time delay from receiving the engine 24 shutdown command (ENGINE_MODE 72 =0) to when ALL FOUR injectors are shut off (OPTION A 58 ), or =time delay from three injectors having been shut off (INJON 126 =1) to when ALL FOUR injectors are shut off (OPTION B 60 ). MAN_FLUSH_DLY 88 =time delay from when the engine 24 has stopped fueling (INJON 126 =0) to when the intake manifold has been sufficiently cleaned of residual fuel (vapor and liquid); the engine 24 will continue to be spun by the VSC 46 until this calibratable delay has expired. SPK_SPD_THRESHOLD 96 =engine speed below which the ignition system is disabled (i.e., spark plugs are not fired). POWER_SUSTAIN_DLY 78 =time delay from when POWER_SUSTAIN_TMR 74 begins counting to when POWER_SUSTAIN_FLG 76 is cleared to 0. The engine 24 shutdown routine of the present invention accomplishes the HEV objectives described in the prior art review. First, the routine unconditionally disables purge and EGR (i.e., shuts the valves immediately) via SHUTDOWN_PG_DIS 66 and SHUTDOWN_EGR_DIS 68 to close off these sources of fuel. Second, the routine shuts (“ramps”) off the fuel injectors (the primary source of fuel) in a controlled and calibratable manner (e.g., all injectors shut off at once, or two at a time, or one at a time) via INJON 126 . Additionally, an abort command is added to the shutdown process if injector shut off (“ramping”) has not yet begun. For example, the shutdown would abort if INJON 126 >=4 (or the total number of engine cylinders) and ENGINE_MODE 72 is not=0. Again, shutting off these three sources of fuel helps to create a repeatable and consistent fuel condition in the intake manifold (vapor and liquid) at the end of engine shutdown so that it is easier to control the amount of fuel for optimal air/fuel ratio during the following engine restart. And finally, if engine shutdown is implemented with a power sustain system (POWER_SUSTAIN_TMR 74 , POWER_SUSTAIN_FLG 76 , and POWER_SUSTAIN_DLY 78 ) to the controllers, the ignition system, and the fuel system (pump and injectors), the VSC 46 can continue to spin the engine 24 even though the injectors are off (INJON 126 =0) to “flush” residual fuel out of the intake manifold into the cylinders, combust the fuel (even if partially) in the combustion chamber by the continued firing of the spark plugs, and then converting the combustion byproducts once delivered to the hot catalytic converter. The ENGINE_RUNNING 64 flag is set to 0 once the flushing process is complete and the routine shuts off engine 24 spark completely once ACTUAL_ENG_SPEED 94 has fallen below a calibratable level (SPSPD_THRESHOLD 96 ). Typically, even with the “power sustain” option active, the engine 24 will continue to spin for only a few seconds (2 or 3) after “key-off” so that the driver does not perceive a problem with the engine 24 continuing to run when not expected. The above-described embodiment(s) of the invention is/are provided purely for purposes of example. Many other variations, modifications, and applications of the invention may be made.
A method and system to control engine shutdown for a hybrid electric vehicle (HEV) is provided. Tailpipe emissions are reduced during the many engine shutdowns and subsequent restarts during the course of an HEV drive cycle, and evaporative emissions are reduced during an HEV “soak” (inactive) period. The engine shutdown routine can ramp off fuel injectors, control engine torque (via electronic throttle control), control engine speed, stop spark delivery by disabling the ignition system, stop purge vapor flow by closing a vapor management valve (VMV), stop exhaust gas recirculation (EGR) flow by closing an EGR valve, and flush the intake manifold of residual fuel (vapor and puddles) into the combustion chamber to be combusted chamber to be combusted. The resulting exhaust gas byproducts are then converted in the catalytic converter.
1
FIELD OF THE INVENTION The present invention relates to storage pockets and in particular to an easy access storage pocket for a golf bag where golf balls and other accessories are accessible with a single hand. Storage bags exist in vast numbers of different sizes and shapes for various paraphernalia. The bags generally include a primary compartment and frequently include secondary compartments for items associated with or complementary to the items stored in the primary storage space. The secondary compartments are typically arrayed around the exterior of the primary storage space. Straps and handles may also be provided to facilitate transport of the bag. Some common exemplary storage bags are backpacks, briefcases, duffle bags, clothes bags, electronics cases/pouches, fishing tackle bags and golf bags, to name a few. Depending upon the stored items, the closure mechanisms provided can vary. Frequently used fasteners are zippers, grommets with lacing, mating strips of hook/loop fastener material, snaps, clasps, draw fasteners, interlocking plastic clips and various other interlocking assemblies. The type of fastener selected frequently depends upon construction of the bag/case. Each fastener secures an opening to a primary or secondary storage space. The relative of ease of access to the storage space varies with the type of fastener. The present invention discloses a closure/fastener assembly that provides a secure fastening, yet permits ready access to the adjoining storage space. The closure assembly finds particular advantage with storage compartments/pockets arrayed about fabric containers such as a golf bag. The closure is secured to a peripheral edge of a compartment/pocket that may contain frequently accessed items such as balls and tees. The closure assembly accommodates a one-handed opening/closing operation. The assembly includes mating magnetic pieces that cooperate with a resilient member having shape retaining memory properties fitted to overlapping edge pieces. The magnetic pieces maintain the closure and the resilient member gently resists opening and guides the magnet pieces into alignment during closure. Elastic and other resilient materials can be combined to enhance opening/closing resistance and the rate of return to a closed condition and shape. SUMMARY OF THE INVENTION It is a primary object of the present invention to provide a storage pocket having a flap or cover piece or panel that overlaps and seals to a flap or panel that defines a storage space. It is a further object of the invention to provide a resilient fabric storage pocket having overlapping cover/flap and storage space defining pieces adapted to one-handed opening/closing and which pieces return to shape upon release. It is a further object of the invention to provide a magnetic coupling between the cover/flap and storage pieces. It is a further object of the invention to provide a fastener for a pocket piece that provides a number of magnets at one pocket piece that align to grommets or other complementary magnetic members fitted to an adjoining pocket piece. It is a further object of the invention to provide a resilient member or stay that is supported at one or both of a cover/flap and storage pieces to resist separation and induce the return of the cover and storage pieces to a defined alignment. It is a further object of the invention to provide a resilient member constructed of a tensile material that is shaped and/or supported to provide resilient resistance to opening/closing. It is a further object of the invention to provide a coiled spring member, shaped fiberglass member or other relatively stiff and resilient member arrayed and fitted to one of more pocket pieces to resiliently support and align adjoining pocket pieces. It is a further object of the invention to provide an elastic member fitted to a pocket piece. The foregoing objects are achieved in a presently preferred golf bag assembly, which includes a magnetically fastened accessory pocket. The pocket provides overlapping flaps or panels that are resiliently biased to provide resilient resistance to opening/closing and direct the pocket panels to defined orientations. One or more magnetic members mounted to one pocket panel are aligned to interact with an adjoining panel. Metal grommets that ventilate the pocket and can support pull-tabs cooperate with the magnets to fasten the pocket pieces together. A resilient stay fitted to the peripheral edge of an adjoining storage piece is arranged to gently resist opening and induce the piece back to a preferred alignment upon release of the piece. A spiral wound spring member is presently secured to the pocket panel to provide resistance. In an alternative construction, a formed fiberglass member is fitted to define a U-shape at the pocket panel to resiliently bias the pocket to an open condition. Elastic edging or facing pieces fitted to the cover and/or pocket panels enhance resilience. The numbers, configuration, orientation and/or types of magnets, stays and elastic facing can be varied as desired to enhance access. Still other objects, advantages and constructions of the present invention, among various considered improvements and modifications, will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating a presently preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will become more fully understood from the following detailed description and accompanying drawings, wherein similar reference callouts are used at the various figures, and wherein: FIG. 1 shows a perspective view to a golf bag outfitted with a magnetically fastened pocket assembly of the invention. FIG. 2 shows an enlarged, detailed drawing in partial cutaway and wherein an upper panel piece is extracted and exposed over an edge of a lower panel piece to expose the magnetic fasteners and a soft trim piece. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following description of presently preferred embodiment(s) is provided to describe exemplary constructions of the invention. The description is not intended to limit the invention, its construction, application, or uses. For purposes of clarity, the same reference numbers are used throughout the drawings to identify similar components. Referring to FIG. 1 a view is shown to a golf bag 2 having a club storage space 4 and several accessory storage pockets 6 arrayed about the exterior surface of the bag 2 . The storage space 4 is segregated with dividers 8 into several compartments 10 that retain one or more clubs (not shown) in desired alignments to facilitate club access, yet prevent the clubs from jostling into one another during play and/or transport. The dividers 8 can be constructed from a molded plastic end piece that is covered with a fabric material. The storage pockets 6 conveniently retain a variety of accessories and paraphernalia such as balls, tees, shoes, clothing, umbrella, sunscreen and any number of items a golfer may desire during play. Prominently located on the front of the bag 2 is a “quick grab” pocket 12 intended to contain extra balls and/or tees. A front panel assembly 14 of the pocket 12 is constructed to facilitate opening and/or closing with one hand and protect the stored items from the weather, yet prevent inadvertent release or spillage of the stored items. Although only one pocket is provided several other similar pockets 12 can be arrayed about the bag 2 . The pocket 12 is displaced away from an interior bag wall to provide a hollow storage space 16 . Balls 18 (shown in dashed line), tees and other frequently accessed items can be stored in the pocket 12 . The storage space 16 is accessible in alternative fashions. One means of access to the storage space 16 is a two-way zipper 20 that extends around both sides and the top of the panel assembly 14 to expose the storage space 16 . Alternatively, the storage space 16 is accessible via the front, “quick grab” panel assembly 14 as discussed below. The pocket assembly 12 is constructed in three primary pieces. A side panel piece 22 is sewn to a wall of the bag 2 . The side panel piece 22 is formed, trimmed and/or lined to stand away from an interior rear pocket wall which is defined by a panel assembly 24 that defines the club storage space 4 . A portion of the front of the panel 24 defines an interior rear wall of the pocket 12 . An upper panel piece 26 of the “quick grab” panel 14 spans a portion (e.g. slightly greater that one-half) of the space 16 . A lower panel piece 28 spans the remaining portion of the space 16 and overlaps the upper panel piece 26 at a trimmed edge 30 where an opening 32 is provided. The zipper 20 joins the raised, adjoining edges of the upper and lower pocket panels 26 and 28 to the side panel piece 22 . The opening 32 provides a convenient alternative, one-handed access to the storage space 16 which embodies a primary advantage of the invention. The upper panel piece 26 includes a facing or trim piece 34 that is covered by the lower panel 28 . The trim piece 34 is constructed of a resilient, soft, elastic material that is edged with an elastic facing 36 . Upon accessing the opening 32 and inserting a hand past the edge 30 , the trim piece 34 and facing 36 flex and form about the hand and wrist to permit access to the storage space 16 without abrading the hand and/or wrist. Access can be facilitated upon manipulating a pull tab 38 made of a knotted length of cording that is secured to the panel 26 to facilitate access to the storage space 16 . Upon pulling the tab 38 and drawing the edge 30 away from the panel piece 26 , the fingers are wrapped over the edge 30 and the hand is inserted into the storage space 16 . Secured to the edge 30 is an elastic trim or facing piece 40 . A number of metal grommets 42 are arrayed beneath the facing piece 40 and align with magnets 44 (shown in dashed line and sewn into the panel piece 26 ). A resilient stay member 46 (shown in cutaway) is fitted into the panel 26 beneath the magnets 44 and spans the width of the trim piece 34 . The stay 46 is constructed of a spiral wound spring material and exhibits a tensile memory that permits flexion of the interior, lower edge of the panel piece 26 at the trim piece 34 . The stay 46 is sewn into a stay sleeve 48 . The length and configuration of the sleeve 48 is adjusted to pre-stress the stay 46 to define a preferred orientation at the panels 26 and 28 . The stay 46 can be constructed of a variety of materials (e.g. metal, plastic, nylon, fiberglass or another flexibly resilient material) and can be formed to a variety of shapes (e.g. flat, straight or irregular strips; round; rod; or tubular). The stay 46 desirably exhibits a sufficient rigidity to define a preferred shape at the opening 32 commensurate with the closed and open conditions desired at the pocket 12 and opening 32 . The tensile properties of the material can be defined as desired and the stay(s) 46 can be positioned in any desired alignment to the pocket panels 26 and 28 . Multiple stays 46 may also be provided at one or both panels 26 and/or 28 to further define the storage space 16 , such as by mounting the additional lengths of the stays 46 into the decorative facing pieces 50 and arraying the facing pieces 50 to enhance the desired the shape of the space 16 . Upon inserting the hand into the opening 32 and between the panels 26 and 28 , the trim 34 stretches and the stay 46 flexes. Upon withdrawing the hand and an item selected from the pocket 12 , the trim 34 and stay 46 collectively spring back to shape and re-align the magnets 44 to the grommets 42 . The magnetic field between the magnets 44 and grommets 42 maintains the fastening. The grommets 42 also serve to ventilate the pocket 14 . The magnets 44 can be constructed of a variety of materials and compounds to any desired shape. The magnets 44 are presently constructed to exhibit a preferred field attraction relative to the adjoining fastener member. The magnets 44 can be bonded to the pocket panel(s) 26 and/or 28 as described above or by stitching, with suitable adhesives or other fasteners. In lieu of grommets 42 , solid metallic pieces can also be fitted in pouch(s)/sleeve(s) beneath the adjoining panel piece. From the foregoing, it is to be appreciated the described construction of the “quick grab” pocket assembly 12 is merely exemplary of a presently preferred configuration. From the suggested modifications and others that may be apparent to those skilled in the art, it is to be appreciated the invention can be implemented in still other configurations and to several different pockets. For example, the panel 26 can be fitted to overlap the panel 28 to provide a weatherproof cover with the trim 34 secured to the panel 28 and/or with the tab secured to the panel 26 . The magnets 44 , grommets 42 and stays 46 can be arranged in a variety of desired configurations to enhance the attractive forces and air flow through the storage space 16 . Still further, the magnets 44 and stays 46 might be adapted into other bags, cases or storage assemblies. The scope of the invention should therefore not be construed merely to the foregoing description, but rather should be construed within the broader scope of the following claims.
A magnetically fastened storage pocket for a storage container such as a golf bag. A fabric pocket provides overlapping pocket panels that are arranged to accommodate one-handed opening/closing operations. A fastener assembly includes mating magnetic pieces. Resilient stay member(s) having shape retaining properties and fittings and/or elastic members define and resiliently maintain the pocket shape and align the pocket and magnet pieces.
0
CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of the filing date of U.S. provisional application No. 60/114,218 filed Dec. 30, 1998. FIELD OF THE INVENTION The present invention relates generally to electrically operated power tools and in particular, to portable hand-held power tools which can alternatively operate in either a cordless mode from a self-contained power source or a corded mode from a conventional AC/DC generator power source. BACKGROUND OF THE INVENTION Electrically operated devices that function in a cordless mode typically include a housing which has a chamber for receiving and retaining a removable battery pack. The battery pack completely encloses one or more cells and provides the necessary DC power for operation of the device. Historically, cordless electrically powered devices have included relatively low power devices such as shavers and hand-held calculators. Recently, improvements in battery technology have led to the development of batteries that store more energy and are capable of driving higher power devices. These devices include for example, portable hand-held power tools and appliances operating at power levels from 50 watts up to hundreds of watts. A hand-held power tool is typically powered by a battery pack that comprises a number of batteries connected in series. To provide the higher power levels required by high power devices an increased number of batteries are connected in series resulting in higher input voltages and battery pack volumetric requirements. Cordless power devices permit work operations to be performed in areas where a conventional AC power source is not available or inconvenient to use. However, the effective charge capacity of the battery pack and the availability of replacement battery packs limit the use of cordless devices. When the battery pack is discharged, it must be recharged or replaced with a fully charged pack. Both batteries and battery chargers are expensive in comparison to the power device for which they are intended. Batteries for high power applications cost approximately 30% of the cost of the applicable power device. Additional batteries are required to permit cordless mode operation while a battery is recharged and to replace dead batteries. High power levels drawn from batteries during operation of the power tool, the depth of discharge of the battery, the number of charge/discharge cycles, and the speed with which a battery is recharged all contribute to shortening the usable lifetime of a battery. Fast chargers can cost more than the power tool or appliance that is powered by the battery. There are two basic types of battery chargers, trickle chargers and fast chargers. Trickle chargers are significantly less expensive than fast chargers, however a trickle charger requires approximately ½ day to recharge a battery pack. A fast charger on the other hand can recharge a battery pack within approximately one hour. Therefore, a trade off must be made between using a trickle charger with a large number of battery packs versus using a costly fast charger with very few replacement battery packs. It has recently been proposed to provide portable cordless power tools with an optional corded AC converter module that is connected to an AC power source and designed to replace the battery pack. The corded converter module converts power from the AC source to a regulated low-voltage DC level that is usable by the motor of the power device. Such a device allows a tool operator to use the tool in either the cordless battery mode or the corded AC mode as needed. Thus, the availability of such device enables the operator of a cordless tool to complete a project when the battery pack has been discharged, or to continue to use the tool while the battery pack is charging and a fully charged backup battery pack is unavailable. Hence, by using a corded converter module the need for extra battery packs is minimized. However, the prior art design of a corded converter module is constrained by a number of factors such as the physical envelope, the required output power level, the voltage conversion ratio of the converter, safety requirements to protect the operator from electrical shock, and cost. The envelope of the corded converter module must conform to the envelope of the battery pack with which it is interchangeable. With the increased volumetric requirements for battery packs there is increased volume available for housing a corded converter. The power output level of the converter is directly related to the available volume within the container envelope. The power output levels adequate to drive power devices such as hand held power tools are possible within the physical envelope of commercial battery packs. The voltage conversion ratio of the converter is the ratio between the rectified input voltage and the converter output voltage. The converter output voltage is set to a level roughly equivalent to the battery voltage. The greater the voltage conversion ratio the more difficult it is to accurately regulate the output voltage. The safety regulations are typically met by isolating the operator of the power device from the AC power source. Commercially available systems meet the safety regulations by employing a high frequency power transformer to isolate the output power of the converter module from the relatively high voltage AC input power source. Power transformers are custom devices that are expensive and bulky in comparison with the other electronic devices of the converter module. Attempts to minimize costs of corded converter modules have concentrated on optimizing the output power capability of the converter module for a given power device. By designing the converter module for the minimum output power required to satisfactorily drive the power device, lower cost electronic components can be chosen for the converter. Operators of cordless power tools already faced with the cost of battery packs and battery chargers must also invest in expensive corded converter modules for their power tools. As an alternative many purchase a corded power tool to use in lieu of the cordless tool when an AC power source is nearby. Attempts to minimize the cost of corded conversion modules have been constrained by the cost of using transformer isolation to meet the government safety requirements. Obtaining further cost reductions by reducing the output power level of a corded converter module would result in under-powered power devices. While the prior art can be used to provide corded converter modules for a handheld power tool, it has not proven capable of providing low cost modules that are convenient to use. SUMMARY OF THE INVENTION The present invention decreases costs by meeting the government safety requirements in a unique manner. The invention uses a double insulated casing for the power tool rather than employing transformer isolation. Eliminating the power transformer from the corded converter module significantly reduces the cost and weight of the module. A low cost converter module provides operators of cordless power tools the low cost option of using a corded converter module when AC power sources are available. This eliminates the cost of purchasing a separate corded power device as well as reducing the number of battery packs that must be purchased. Corded power converters designed without power transformers are substantially less expensive than converters designed with power transformers. Additionally, eliminating the power transformer decreases the weight of the converter resulting in improved operator comfort. For a more complete understanding of the invention, its objects and advantages, reference may be had to the following specification and to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1, is a three-dimensional view partially showing the manner of connecting a battery pack to the power device; FIG. 2 is a three-dimensional view partially showing the manner of connecting an AC/DC power converter module to the power device; FIG. 3A is a three-dimensional exploded view of the battery pack; FIG. 3B is a three-dimensional exploded view of the power converter module; FIG. 4 is an end view of the battery pack illustrating an attached terminal block; FIG. 5 is a three-dimensional view of the power tool terminal block that mates to the battery pack terminal block; FIG. 6 is a two-dimensional view of the interface between the battery pack terminal block and the power tool terminal block; FIG. 7 is a two-dimensional view of the interface between the AC/DC power converter module and the power tool terminal block; FIG. 8 is a block diagram of a power converter assembled and contained within the AC/DC power converter module of FIG. 2; FIG. 9 is a schematic diagram of the power stage of the power converter of FIG. 8; FIG. 10 is a schematic diagram of the control circuit of the power converter of FIG. 8; FIG. 11 is a signal diagram showing the voltage and current waveforms associated with the power converter; FIG. 12 is a cross-sectional view of an armature of a non-double insulated DC power tool motor; FIG. 13 is a cross-sectional view of an armature of DC power tool motor that employs a first method of double insulation; FIG. 14 is a cross-sectional view of an armature of DC power tool motor that employs a second method of double insulation; FIG. 15 is a cross-sectional view of an armature of DC power tool motor that employs a third method of double insulation; FIG. 16 is cross section through the center of the lamination stack of an armature for a DC power tool motor that employs double insulation; and FIG. 17 is a cross-sectional view of a housing for a DC power tool that employs double insulation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to FIGS. 1 and 2, a dual-mode portable power tool 12 according to the present invention is shown. While the present invention is shown and described with a reciprocating saw 12 , it will be appreciated that the particular tool is merely exemplary and could be a circular saw, a drill, or any other similar portable power tool constructed in accordance with the teachings of the present invention. The power tool 12 includes a DC motor (not shown) that is adapted in the preferred embodiment to be powered by a source having a relatively low voltage such as a 24 volt DC source, although other low voltage DC systems, such as 12 volts or 18 volts, could be used. In a first operating mode shown in FIG. 1, the power tool 12 is powered by a removable battery power supply module 14 . Alternatively, as shown in FIG. 2, the power tool 12 may be powered from a source having a relatively high voltage such as common 115 volt AC line power via an AC/DC power converter module 16 which is adapted to be plugged into the power tool in place of the battery power supply module 14 . Additionally, the power tool 12 may be powered from a relatively high voltage DC generator (not shown) via the AC/DC power converter module 16 . As used in this specification and the accompanying claims, the term relatively high voltage means voltages of 40 volts or greater and the term relatively low voltage means voltages less than 40 volts. With particular reference to FIGS. 3A and 4, the rechargeable battery power supply module 14 of the present invention is illustrated to generally include a housing 18 , a battery 20 which in the exemplary embodiment illustrated is a 24 volt nickel-cadmium battery, and a battery pack terminal block 22 . To facilitate releasable attachment of the battery power supply module 14 to the tool 12 , the upper portion 25 of the housing 18 is formed to include a pair of guide rails 24 . The guide rails 24 are adapted to be slidably received into cooperating channels 13 (FIG. 1) formed in a housing 14 of the tool 12 . To further facilitate removable attachment of the battery power supply module 14 to the tool 12 , the upper portion 25 of the housing 18 further defines a recess 26 . The recess 26 is adapted to receive a latch (not shown) carried by the housing of the tool 12 . The latch is conventional in construction and operation and is spring biased to a downward position so as to engage the recess 26 upon insertion of the rechargeable battery power supply module 14 . Removal of the battery power supply module 14 is thereby prevented until the spring bias of the latch is overcome in a conventional manner insofar as the present invention is concerned. With continued reference to FIGS. 3A and 4, the battery pack terminal block 22 comprises a main body portion 28 constructed of rigid plastic or other suitable material and a plurality of blade-type terminals 30 . In the exemplary embodiment illustrated, the battery pack terminal block 22 includes four blade terminals 30 . Two of the blade terminals 30 comprise the positive and negative terminals for the battery 20 . A third terminal 30 may be used to monitor the temperature of the battery 20 and a fourth terminal may be used to identify the battery type (e.g., 24 volt NiCad). As best shown in FIG. 4, a pair of holes 32 are formed in the two guide rails 24 in the upper portion 25 of the battery pack housing 18 on either side of the row of blade terminals 30 . The function of these holes is described below. Turning now to FIG. 5, the terminal block 34 of the power tool 12 is shown. The main body of the tool terminal block 34 is also constructed of a rigid plastic material and is formed with a row of four U-shaped guideways 36 guiding the four corresponding blade terminals 30 of the battery power supply module 14 when the battery pack is inserted into the tool 12 . Located within the guideways 36 are female connectors 38 that are adapted to engage and make electrical contact with the blade terminals 30 of the battery power supply module 14 . Although the tool terminal block 34 shown is designed to accommodate four female connectors for each of the four battery pack blade terminals 30 , only two female connectors 38 adapted to engage the positive and negative blade terminals 30 of the battery power supply module 14 are used in the tool terminal block 34 , as the remaining two battery pack blade terminals 30 are only used when recharging the battery power supply module 14 . Also connected to the positive and negative female terminals 38 in the tool terminal block 34 are positive and negative male terminals 40 that project through openings 42 in the terminal block on either side of the row of guideways 36 . As will subsequently be discussed below, the male positive and negative terminals 40 are used to electrically connect the tool 12 to the AC/DC converter module 16 . With additional reference to FIG. 6, the interface between the battery terminal block 22 and the tool terminal block 34 is illustrated. As the guide rails 24 of the battery power supply module 14 are slid into the channels 13 in the tool housing, the battery pack terminal block 22 is guided into alignment with the tool terminal block 34 as shown. To further facilitate proper alignment between the two terminal blocks 22 and 34 , the main body portion of the tool terminal block 34 includes a pair of laterally spaced rails 44 that are adapted to be received within the grooves 46 provided in the battery pack housing 18 immediately below the guide rails 24 . Further insertion of the battery power supply module 14 onto the tool 12 results in the positive and negative blade terminals 30 of the battery power supply module 14 passing through the openings in the U-shaped guideways 36 and engaging the female connectors 38 in the tool terminal block 34 . Note that the male positive and negative terminals 40 from the tool terminal block 34 simultaneously project into the openings 32 formed in the rails 24 on the upper portion 25 of the battery pack housing 18 , but do not make electrical contact with any terminals in the battery power supply module 14 . Similarly, the remaining two blade terminals 30 from the battery terminal block 22 project into empty guideways 36 in the tool terminal block 34 . Returning to FIG. 2 with reference to FIG. 3B, the AC/DC converter module 16 according to the present invention is adapted to convert 115 volts AC house current to 24 volts DC. The housing 48 of the converter module 16 in the preferred embodiment is configured to be substantially similar to the housing 18 of the battery power supply module 14 . In this regard, the housing 48 includes first and second clam shell halves joined at a longitudinally extending parting line. An upper portion 50 of the housing 48 includes a pair of guide rails 52 similar to those of the battery power supply module 14 for engaging the channels 13 in the tool housing. The upper portion 50 also defines a recess (not shown) which includes a latch (not shown) for preventing the inadvertent removal of the converter module 16 . The housing 48 also defines a recess 51 in which a fan 45 is adapted for providing cooling airflow to the converter module 16 . Attached to the fan 45 is a fan cover 47 for preventing foreign objects from impeding the operation of the fan 45 . Within the housing 48 several heatsinks 43 provide heat spreading and cooling for selected power converter components. With additional reference to FIG. 7, the interface between the converter module 16 and tool terminal block 22 is shown. The converter module 16 includes a pair of female terminals 54 that are adapted to receive the male terminals 40 of the tool terminal block 22 . In a manner similar to that described above in connection with the installation of the battery power supply module 14 on the tool 12 , the guide rails 52 on the upper portion 50 of the converter housing 48 are adapted to engage the laterally spaced rails 44 on the tool terminal block 34 as the converter module 16 is installed on the tool 12 to ensure proper alignment between the female connectors 54 of the converter module 16 and the male connectors 40 of the tool 12 . Due to the non-isolated nature of the AC/DC converter module 16 in the present invention, the female terminals 54 are recessed within the upper portion 50 of the housing 48 of the converter module 16 to meet safety requirements. In the preferred embodiment, the female terminals 54 are recessed within the housing 48 of the converter module 16 by at least 8 mm. 115 volt AC power is converted to 24 volt DC power by the converter module 16 and delivered to the tool 12 through the female terminals 54 . When the converter module 16 is operatively installed on the tool 12 , the female terminals 38 of the tool terminal block 34 are electrically inoperative. The presently preferred embodiment of the AC/DC power converter module 16 is a fixed-frequency, non-isolated, buck-derived topology; however, the principles of the invention can be extended to variable-frequency converters and topologies other than buck-derived, such as Cük and flyback converters. The power converter module 16 is designed to convert an unregulated AC voltage to a regulated DC voltage that is usable by the power tool 12 . For example, the converter module 16 can convert an input of 120 volts, 60 Hz AC to any low-level DC voltage less than 42 volts that is required by the power tool 12 , such as 24 volts DC. As illustrated in block diagram form in FIG. 8, the power converter module 16 includes a fuse 101 in series with diode bridge 102 . A power plug and cord (refer to FIG. 2) connect from fuse 101 to the other input of diode bridge 102 . The output of diode bridge 102 is applied between high side line 104 and an inrush limiter 103 connected to ground reference line 106 . The rectified output voltage of diode bridge 102 is filtered by the input capacitor 108 . The resulting filtered voltage is nominally 165 volts DC. The input capacitor 108 connects to the drains of parallel power MOSFETs 110 a and 110 b that act as a voltage controlled switch. When MOSFETs 110 a and 110 b are in the ON state the impedance between the drain and source is low. When in the OFF state the impedance between drain and source is very high, effectively preventing current flow. The sources of MOSFETs 110 a and 110 b connect to the junction of output inductor 112 and the cathode of free-wheeling output diode 114 . The other side of output inductor 112 connects to output capacitor 116 . Current sense resistor 118 connects between the output capacitor 116 and the anode of the freewheeling diode 114 . The anode of output diode 114 also connects to ground reference line 106 . The voltage across output capacitor 116 is applied to the output of power converter module 16 across outputs VOUTHI 120 and VOUTLO 122 , which connect to the pair of female terminals 54 . Fan 123 is connected in parallel with output capacitor 116 . Diode bridge 102 , MOSFET 110 , and free-wheeling output diode 114 all mount on heat sinks that provide heat spreading and a thermal path for dissipated power. FIGS. 8 and 10 illustrate the circuitry that provides control and protection functions for power converter module 16 which includes voltage regulated power supply 124 , PWM control 126 , voltage feedback 128 , current limit 130 , and temperature sense 134 . The voltage regulated power supply 124 connects across input capacitor 108 to provide a low power, regulated low voltage output to supply power to the internal circuitry of power converter module 16 . The regulated low voltage output as well as the remainder of the internal circuitry is referenced to ground reference line 106 . VOUTHI 120 connects to voltage feedback 128 which connects to PWM control 126 . The current sense resistor 118 connects to current limit 130 which also is connected to temperature sense 134 . The output of current limit 130 connects to PWM control 126 . The arrangement of components that comprise voltage regulated power supply 124 , PWM control 126 , voltage feedback 128 , current limit 130 , and temperature sense 134 are well known in the art. FIGS. 9 and 10 illustrate the circuitry that provides the power conversion function for power converter module 16 which includes high voltage driver 132 and power stage components. The output of PWM control 126 connects to high voltage driver 132 which level shifts the output of PWM control 126 to drive the gates of MOSFETs 110 a and 110 b . The arrangement of components that comprise high voltage driver 132 are well known in the art. In the presently preferred embodiment of the invention an SGS-Thomson L6381 high-side driver 172 with associated components comprises the high voltage driver 132 . However, other circuit configurations for level-shifting the PWM output are within the scope of the invention, such as discrete component configurations and Motorola high-side driver chips. Referring to FIG. 8, at initial power-on of power converter module 16 , the power plug and cord are connected to an AC power source. The AC voltage is rectified by diode bridge 102 and applied across input capacitor 108 . Current from the AC source surges as it flows through fuse 101 , inrush limiter 103 , diode bridge 102 , and begins to charge input capacitor 108 . The magnitude of the surge in current is limited to a safe level by the action of the inrush limiter 103 which is a high impedance initially, but rapidly changes to a low impedance. In the present embodiment the inrush limiter 103 consists of a triac 152 in parallel with a resistor 150 that is triggered by current flowing through output inductor 112 . However, other well known circuits are also envisioned, such as a series thermistor, and a high valued series resistor in parallel with a controlled semiconductor that is triggered by temperature, time, or current magnitude. As the voltage across input capacitor 108 rises towards its nominal value of 165 volts DC the voltage regulated power supply 124 becomes active and begins to supply voltage to the internal circuitry of the power converter module 16 including PWM control 126 . During the initial charging of input capacitor 108 , the triac 152 remains off forcing return current to flow through resistor 150 , thereby limiting the peak value of the inrushing current. The triac 152 remains OFF until the output of PWM control 126 becomes active driving the MOSFETs 110 a and 110 b to the ON state, at which time current flowing through output inductor 112 couples through a sense winding of inductor 112 to trigger the triac ON. The PWM control 126 in the present embodiment is a Texas Instruments TL494 with the associated components as depicted in FIG. 10 . There are numerous other control chips which could be used, such as UC1845 and SG1625. The output of PWM control 126 is disabled until the regulated output of voltage regulated power supply 124 exceeds 6.4 volts, at which time soft-start mode is enabled. Prior to the beginning of soft-start the oscillator of PWM control 126 begins to operate. The present embodiment switches at a fixed frequency of 40 kHz, although higher or lower frequencies are within the scope of the invention. During steady-state operation of power converter module 16 the PWM control 126 output is a low-voltage square-wave signal having a variable pulse-width, where the pulse-width is adjusted to maintain a regulated output voltage at outputs VOUTHI 120 and VOUTLO 122 . During soft-start the pulse-width of the PWM control 126 output is initially zero, gradually increasing to a steady-state value that results in the output voltage being regulated at a desired voltage. The duration of soft-start mode is controlled by the selection of component values in PWM control 126 and is well known in the art. The purpose of soft-start is to limit the current and voltage stress of the power converter module 16 components during the time period when output capacitor 116 is being charged up to its nominal steady-state value. As the voltage across output capacitor 116 approaches its steady-state value the output of voltage feedback 128 rises towards its steady-state value, resulting in the pulse-width of PWM control 126 attaining a steady-value that regulates the voltage across output capacitor 116 at the desired value. The feedback network in the present embodiment is a lag-lead-lag-lead configuration with well known design requirements to maintain a stable operation of power converter module 16 . During steady-state operation the output from PWM control 126 which is level-shifted by the high voltage driver 132 repetitively drives the MOSFETs 110 a and 110 b into an ON state and an OFF state at the switching frequency. Referring to waveforms vs, iL, and vout of FIG. 11 in addition to FIG. 8, when MOSFETs 110 a and 110 b are in the ON state, the voltage from input capacitor 108 is passed through to the sources of MOSFET 110 a and 110 b , vs, and impressed on the input of output inductor 112 reverse biasing free-wheeling diode 114 . The voltage across output inductor 112 during the ON state is equal to the voltage across input capacitor 108 minus the voltage across output capacitor 116 , vout. The positive voltage across inductor 112 causes current, iL, through inductor 112 to increase at a linear rate. The current splits between VOUTHI 120 and output capacitor 116 with the DC component flowing to VOUTHI 120 and the AC component substantially flowing through output capacitor 116 . Current returning from load 121 flows from VOUTLO 122 through current sensor resistor 118 and input capacitor 108 thereby completing the current path. When the MOSFETs 110 a and 110 b are switched to the OFF state, they present a high impedance to the voltage from input capacitor 108 decoupling that voltage from the remainder of the circuit. During this period free-wheeling diode 114 is active. The current, iL, from output inductor 112 which previously flowed through MOSFETs 110 a and 110 b now flows through free-wheeling output diode 114 . With output diode 114 conducting, the voltage, vs, at the input to output inductor 112 is approximately one diode drop below ground reference line 106 . The voltage across output inductor 112 is equal to negative one volt minus the voltage across output capacitor 116 . The negative voltage across inductor 112 causes current through inductor 112 to decrease at a linear rate. The current again splits between VOUTHI 120 and output capacitor 116 with the DC component flowing through VOUTHI 120 and the AC component substantially flowing through output capacitor 116 . The current returning from load 121 flows from VOUTLO 122 through current sense resistor 118 and free-wheeling output diode 114 , thereby completing the current path. The MOSFETs 110 a and 110 b remain in the OFF state for the remainder of the cycle time period. Again referring to FIG. 8 with additional reference to waveforms vg and vpwm of FIG. 11, the output of PWM control 126 is level-shifted by high voltage driver 132 in order to drive power MOSFETs 110 a and 110 b to either the ON state or the OFF state. During the transition from the OFF state to the ON state, the PWM control 126 output voltage, vpwm, transitions low which causes the output of driver 172 to transition high, thus biasing the base emitter junction of PNP transistor 178 turning it OFF. At the same time NPN transistor 174 turns ON. Current flows through NPN transistor 174 and resistors 176 a and 176 b into the gates of power MOSFETs 110 a and 110 b charging up the internal gate-source capacitance, raising the MOSFETs 110 a and 110 b gate voltage, vg, above ground before returning from the sources of MOSFETs 110 a and 110 b to filter capacitor 168 . The increasing voltage across the gate-source of MOSFETs 110 a and 110 b causes the MOSFETs 110 a and 110 b to begin to turn ON, causing the source voltage of MOSFETs 110 a and 110 b to increase from minus one volt relative to ground reference line 106 to a value approaching the value of voltage across input capacitor 108 and additionally causing the MOSFETs 110 a and 110 b gate voltage, vg, to increase to the value of voltage across input capacitor 108 plus the MOSFETs gate-source voltage. As the source voltage of MOSFETs 110 a and 110 b increases, the decoupling diode 166 becomes reverse biased decoupling the diode 166 from the remainder of the high voltage driver 132 . Filter capacitor 168 remains referenced to the source of MOSFETs 110 a and 110 b and thereby provides the energy required to maintain the gate-source voltage of MOSFETs 110 a and 110 b during the remainder of the ON state. The PWM control 126 output voltage, vpwm, transitions from a low to a high value to initiate the start of the OFF state. The high-side driver 172 inverts and level shifts the signal which causes NPN transistor 174 to turn OFF and PNP transistor 178 to turn ON. The energy stored in the internal gate-source capacitance of MOSFETs 110 a and 110 b discharges through resistor 176 and PNP transistor 178 . When the gate-source voltage of MOSFETs 110 a and 110 b decreases to less than approximately four volts MOSFETs 110 a and 110 b turn OFF. Free-wheeling diode 114 becomes active which causes the voltage at the sources of MOSFETs 110 a and 110 b to decrease to minus one volt. Current then flows through decoupling diode 166 into filter capacitor 168 recharging the capacitor 168 . Parallel zener diode 170 clamps the voltage across filter capacitor 168 to a safe value that does not overstress the gate-source junctions of the MOSFETs 110 a and 110 b . The circuit remains in the OFF state until the output of PWM control 126 once again transitions low. In addition to controlling pulse width to maintain a constant output voltage, PWM control 126 also varies the pulse width in response to an output from current limit 130 to protect power converter module 16 from excessive output current loads. Output current flows through current sense resistor 118 causing a voltage to develop that is proportional to the output current. The voltage across resister 118 is compared to a reference voltage derived from the PWM control reference. When the output current is greater than a pre-determined maximum level the output of current limit 130 causes PWM control 126 to reduce the pulse width of the output. The reduced duty cycle causes the voltage at outputs VOUTHI 120 and VOUTLO 122 to decrease until the resulting output current is less than the pre-determined maximum level. Temperature sense 134 protects power converter module 16 from overtemperature stress of MOSFET 110 and output diode 114 . In the presently preferred embodiment a thermistor is employed as temperature sense 134 to monitor the temperature of heatsinks 43 . If the temperature rises due to overload, debris blocking an air intake, or other fault condition, temperature sense 134 modifies the current limit reference voltage, thereby causing the PWM control 126 to generate a shorter pulse width. The shorter pulse width results in a lower output voltage and output current that corresponds to a lower overall output power. The lower output power causes a reduction in the power dissipated in the components of power converter module 16 , resulting in lower component temperatures. Returning to FIG. 1, although the power tool 12 of the present invention is designed to be powered by a relatively low voltage DC power source (i.e., a DC source less than 50 volts), the housing 201 of the power tool in the preferred embodiment is nonetheless double insulated from the electrical system of the tool. As is well known to those skilled in the art, power tools designed to be operated by a high voltage power source, such as a conventional AC or corded power tool, are typically constructed so that the housing of the tool is double insulated from the electrical system of the tool for safety reasons. In this manner, the operator of the tool is protected against electrical shock in the event of a short in the electrical system of the tool. Cordless or DC powered tools are powered by low voltage power sources and therefore do not require such safety measures. Consequently, conventional DC powered tools do not insulate the housing from the electrical system of the tool. There are of course, many DC powered portable devices that are alternatively powered from high voltage AC house current. To enable this alternative operation, however, AC/DC powered devices universally employ transformers to step down the high AC voltage and thereby isolate the device from the high voltage AC power source. While this solution may be acceptable for relatively low powered devices, such as portable stereos, the power requirements of many portable power tools necessitates the use of large step-down transformers which are not only bulky, but also very heavy. Consequently, DC powered tools that can alternatively be powered from AC house current have rarely been offered commercially. The present invention solves this dilemma by providing a relatively light weight non-isolated AC to DC converter and then constructing the DC powered tool in a manner consistent with the double insulation safety requirements of a conventional AC powered tool. In other words, by eliminating transformer isolation in the present AC/DC power converter module 16 , the DC output voltage supplied to the motor of the power tool is referenced to the 115 volt AC input. Consequently, double insulation of the tool housing from the electrical system of the power tool is required. In addition, as discussed above in connection with the description of FIGS. 5-7, the power tool terminal block 34 according to the present invention is provided with independent male connectors 40 uniquely adapted to make electrical contact with, and thereby receive electrical power from, specially recessed female connectors 54 in the AC/DC converter module 16 . Thus, despite the non-isolated construction of the present AC/DC converter module 16 , all applicable safety requirements for operating a power tool from a relatively high voltage power source are satisfied. FIGS. 12 through 17 depict the effect of employing double insulation within a motor and housing. Double insulation techniques are well known in the art. Double insulated tools are typically constructed of two separate layers of electrical insulation or one double thickness of insulation between the operator and the tool's electrical system. With specific reference to FIG. 12, a cross-sectional view of a non-double insulated DC motor armature 200 is illustrated. The armature 200 consists of a shaft 202 with a core built up over it. The core is composed of many laminations 206 with notches along the outer periphery to hold the armature windings 204 . A gear or chuck (not shown) is built onto the shaft at one end of the armature 206 to provide a means of transferring rotational energy to the working end 208 (see FIG. 1) of the power tool 12 . For example a gear mechanism would convert rotational energy to the forward and back motion used to drive a reciprocating saw. The path from the armature shaft 202 to the gear mechanism or chuck, and finally to the working end is electrically conductive. Therefore any electrical energy that exists on the armature shaft 202 is conducted to the working end, which is exposed to the operator of the power tool 12 . Locations 208 , 210 , and 212 indicate areas of the rotor that could become energized through contact with electrically live assemblies if insulation is not employed. At location 208 the armature shaft 202 could be energized through contact with energized armature laminations 206 . At location 210 the armature shaft 202 could be energized through contact with end turns of the armature windings 204 . At location 212 the armature laminations 206 could be energized through contact to end turns of the armature windings 204 . Referring to FIG. 13, a first method of employing double insulation of the motor armature 220 of a power tool is illustrated. The armature 220 consists of a shaft 222 with a core built up over it. The core is composed of many laminations 226 with notches along the outer periphery to hold the armature windings 224 . A chuck 228 is built onto the shaft at one end of the armature laminations 206 to provide a means of affixing a device such as a drill bit to the working end 208 (see FIG. 1) of the power tool 12 . A molded plastic insulator 230 provides basic insulation between the armature windings 224 and the laminations 226 as well as between the shaft 222 and the windings 224 . A press fit plastic tube insulator 232 encases the shaft 222 providing supplementary insulation to prevent the shaft from becoming energized if the basic insulation breaks down. Referring to FIG. 14, a second method of employing double insulation of the motor armature 220 of a power tool is illustrated. A paper insulator 240 provides basic insulation between the armature windings 224 and the laminations 226 . A second insulator 242 of double thickness, 2 mm, encases the shaft 222 providing reinforced insulation, which substitutes for supplementary insulation, to prevent the shaft from becoming energized through electrical shorts to the laminations 226 or the armature windings 224 . Referring to FIG. 15, a third method of employing double insulation of the motor armature 220 of a power tool is illustrated. An insulator 250 of either paper or molded plastic provides basic insulation between the armature windings 224 and the laminations 226 . An in situ molded thermoset plastic insulator 252 of double thickness encases the shaft 222 providing reinforced insulation, which substitutes for supplementary insulation, to prevent the shaft from becoming energized through electrical shorts to the laminations 226 or the armature windings 224 . Referring to FIG. 16, a cross-section through the center of the lamination stack of the motor armature 220 of a power tool is illustrated. A slot liner insulator 260 provides basic insulation between the armature windings 224 and the laminations 226 . The slot liner insulator is constructed of any suitable electrical insulator material such as paper, coated paper, polyester, and vulcanized fiber. Supplementary insulation is provided by a glass reinforced polyester insulator sleeve 262 which encases the shaft 222 . The insulator sleeve prevents the shaft from becoming energized if the basic insulation provided by slot liner 260 fails. Referring to FIG. 17, a double insulated housing 270 of a power tool is illustrated. As is known in the art, the double insulation methods employed are intended to prevent electrical energy within the housing 270 from energizing the outside surface of the housing 270 . The housing 270 is depicted with a hypothetical metal foil covering 272 on the outside surface to simulate interaction with an operator. Also illustrated are a ring terminal 274 and an insulated wire 276 that includes a conductive wire 278 and wire insulation 280 . Electrical energy exists on both the ring terminal 274 and the conductive wire 278 . Double insulation of the ring terminal 274 is provided by a double thickness, 2 mm, of housing material which serves as a reinforced insulator. The wire insulation 280 provides basic insulation for conductive wire 278 . Supplementary insulation is provided by the housing 270 which prevents electrical energy that breaks through the wire insulation from energizing the outside surface of the housing 270 . The power converter module 16 initially converts the low frequency AC input to a high level DC voltage, then to a high frequency voltage level that is thereafter filtered to the lower voltage supply level of power tool 12 . The power tool employs double insulation of the motor rather than transformer isolation of the power converter 16 , thereby significantly reducing the cost and weight of the power converter module 16 . In addition, the converter module 16 is designed with a comparatively small number of components while providing an efficient conversion process. This further enhances the lightweight, compact features of the converter module 16 . The size of the converter module 16 further permits the use of the converter in power-operated devices, such as the reciprocating saw 12 , which heretofore were too small to support and contain conversion units providing power in a range of at least 50 watts and higher. Further, while the preferred embodiment of the converter module 16 converts a low frequency, high voltage level to a low DC voltage level, the converter can be used to convert a high DC voltage level to a low voltage DC level by applying the high DC level directly to a suitable power cord and plug that connects to the input of converter module 16 . In this manner, the power tool 12 could be operated from the high DC voltage source instead of the low DC voltage of the cells 26 and thereby conserve the charge life of the cells. The converter module 16 could be designed to operate from external AC power sources other than 120 volts at 60 Hz. Without departing from the spirit and scope of the invention, the converter module 16 also could be designed to provide DC output voltage levels in a range of 3.6 to 48 volts. In a particular example, the converter could be adjusted to develop a DC output of 24 volts between the outputs VOUTHI 120 and VOUTLO 122 derived from an external AC source of 220 volts at 50 Hz as applied to a suitable power plug and cord. The converter module 16 could then be used to provide inexpensive dual mode capability for power-operated devices that operate at a DC voltage supply level of 24 volts. The reciprocating saw 12 is merely illustrative of one example of many power-operated, cordless-mode devices that become more versatile because of the inventive cost efficient dual-mode capability. Other examples of power-operated cordless devices which are enhanced by the inventive concept include, but are not limited to, drills, screwdrivers, screwdriver-drills, hammer drills, jig saws, circular saws, hedge trimmers, grass shears, as well as battery-operated household products and the like. Thus it will be appreciated from the above that as a result of the present invention, an inexpensive dual-mode corded/cordless system for power-operated devices is provided by which the principal objectives, among others, are completely fulfilled. It will be equally apparent and is contemplated that modification and/or changes may be made in the illustrated embodiment without departure from the invention. Accordingly, it is expressly intended that the foregoing description and accompanying drawings are illustrative of preferred embodiments only, not limiting, and that the true spirit and scope of the present invention will be determined by reference to the appended claims and their legal equivalent.
A dual-mode system for inexpensively operating electrically powered double-insulated devices ( 12 ), such as hand-held power tools and appliances. The system includes a cordless battery pack ( 14 ) that supplies the power and current demands of the device ( 12 ) in a cordless mode or a non-isolated corded voltage converter ( 16 ) that supplies the necessary power and current demands in a physical envelope commensurate in size and interchangeable with that of the battery pack ( 14 ). The corded voltage converter ( 16 ) is provided with a non-isolated high efficiency power supply that allows the converter ( 16 ) to generate the power and current required by the driven device ( 12 ). The double insulation of the driven device ( 12 ) negates the need for a transformer-isolated voltage converter. Eliminating the power transformer from the converter significantly reduces the cost of the module ( 16 ). Additionally, the need for multiple battery packs and fast rechargers is minimized by the availability of a low-cost converter. The voltage converter ( 16 ) includes an inrush current limiter ( 103 ) and power conditioner for filtering AC or DC input power. The filtered voltage is chopped by a transformerless buck-derived converter. The chopped voltage is rectified and filtered to provide low-voltage DC power to the drive motor of the powered double-insulated device ( 12 ).
1
Prunus incisa named FPMSPL. BACKGROUND OF THE INVENTION The present invention relates to a new and distinct variety of Prunus incisa , which has been given the varietal name ‘FPMSPL’. Nick Dunn discovered the new tree in a production field of Prunus incisa ‘Snow Showers’ as a chance branch sport growing in a cultivated area of a nursery in Tenbury Wells, Worcestershire, England. This cultivated area also contained other seedling and varietal Prunus trees. The new variety differed from these other seedlings and varieties of Prunus trees growing in this area by its variegated white and yellow-green summer foliage color and variegated green, red-purple, grey-orange (brown), orange-red and red-purple (pink) fall foliage color. The parentage of this tree is unknown, but it is definitely a Prunus incisa type tree. Representative varieties within this species include ‘February Pink’, ‘Kojo-no-mai’, ‘Mikinori’, ‘Oshidori Princess’, ‘Pendula’, ‘Praecox’ and ‘Snow Showers’. The original tree was found as a single variegated branch sport from Prunus incisa ‘Snow Showers’ and at that time, grafting wood was collected and grafted on Prunus avium , then planted in a liner field. Having recognized this tree as unique, the inventor transplanted the new tree to a landscape setting adjacent to the nursery property in Tenbury Wells, Worcestershire, England in the spring of 2006, where it has remained since that time. It is now about 5 years old from a grafted liner. Plants of the new variety have been asexually reproduced in Tenbury Wells, Worcestershire, England. The characteristics of the new variety have been found to be strictly transmittable and the variety reliably reproduces true to form from one generation to another. The description of this new Prunus incisa variety is based on observations of five-year old plants growing in Tenbury, Wells, Worcestershire, England. SUMMARY OF THE INVENTION As the original tree of the new variety was observed, the uniqueness of this tree became apparent because of its variegated white and yellow-green summer foliage color, and variegated green, red-purple, grey-orange (brown), orange-red and red-purple (pink) fall foliage color. These characteristics distinguish the new tree from other Prunus of which we are aware, such as Prunus subhirtella ‘Pendula Rosea’ (not patented), Prunus incisa ‘Pendula’ (not patented) and Prunus incisa ‘Snow Showers’ (not patented). The new variety was asexually propagated by cleft grafting in 2006 at the direction of the inventor. The progeny have thus far proven to retain the unique weeping growth habit, variegated white and yellow-green summer foliage color, and variegated green, red-purple, grey-orange (brown), orange-red and red-purple (pink) fall foliage color of the original tree, with the variegation becoming more pronounced on vigorous extension growth and appearing later in the spring on leaves from older branches developing from the center of the leaves. This propagation and observation of the resulting progeny have proven the characteristics of the new variety to be firmly fixed and to reproduce true to type. Furthermore, these observations have confirmed that the new variety represents a new and improved variety of Prunus incisa , Fuji flowering cherry tree. This unique tree differs from the species in its unique weeping growth habit compared to a more upright and spreading growth habit exhibited by the species, variegated white and yellow-green summer foliage color compared to glossy green summer foliage color exhibited by the species, variegated green, red-purple, grey-orange (brown), orange-red and red-purple (pink) fall foliage color compared to orange-red fall foliage color exhibited by the species, and its lack of seeds and fruits compared to the red-purple-black, drupe-shaped fruits typical of the species. Prunus incisa has no known patented or trademarked varieties. The closest Prunus incisa variety similar in growth habit only is Prunus incisa ‘Snow Showers’. This unique tree differs from ‘Snow Showers’ by its white tinged with pink flower color rather than pure white flower color exhibited by ‘Snow Showers’, its variegated white and yellow-green summer foliage color compared to glossy green summer foliage color exhibited by ‘Snow Showers’, variegated green, red-purple, grey-orange (brown), orange-red and red-purple (pink) fall foliage color compared to orange-red fall foliage color exhibited by ‘Snow Showers’, and its lack of seeds and fruits compared to the red-purple-black, drupe-shaped fruits typical of those found on ‘Snow Showers’. The foregoing and other objectives, features, and advantages of the invention will be more readily understood upon consideration of the following detailed description of the invention taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE SEVERAL DRAWINGS The accompanying photographic exhibits depict the shape of the tree, color of the foliage, bark, lenticels, glands, flowers and other characteristics of the new variety as nearly true as is reasonably possible to make the same in a color illustration of this character. Photographic exhibits include the following: FIG. 1 —Photo of the tree without foliage showing unique weeping growth habit/form FIG. 2 —Photo of the tree with leaves showing foliage density FIG. 3 —Photo of variegated new foliage FIG. 4 —Photo of variegated summer foliage color on mature plant FIG. 5 —Photo of Variegated fall foliage color on mature plant (detail) FIG. 6 —Photo of the trunk bark FIG. 7 —Photo of stem/petiole FIG. 8 —Photo of flowers FIG. 9 —Photo of flowers FIG. 10 —Photo showing glands FIG. 11 —Photo of root system (Prunus avium used for grafting) DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The original ‘FPMSPL’ variety of Fuji cherry tree is currently growing at an observation site in Tenbury Wells, Worcestershire, England. It is located in an area of the landscape that has a deep, alluvial soil type and receives approximately 30 inches of rain per year. Tenbury Wells, Worcestershire, England is in a zone comparable to USDA Hardiness Zones 6A-8B. The new tree has not been observed under all growing conditions, and thus, variations may occur. The following is a detailed description of the new variety of Fuji cherry tree with color terminology in accordance with The Royal Horticulture Society (R.H.S.) Colour Chart, © 2001, published by The Royal Horticulture Society in London. The observations are of the original five-year old tree growing in the landscape setting in Tenbury, Wells, Worcestershire, England, and of new progeny which have been recently virus certified and were propagated and growing at Carlton Plants, LLC at 14301 SE Wallace Road in Dayton, Yamhill County, Oreg., USA. Parentage: Discovered as a chance branch sport growing in a cultivated area of a nursery in Tenbury Wells, Worcestershire, England. The parentage of this tree is believed to be by chimera with no pollen parent and no seed parent. Potential for reversion is low. Tree shape: Weeping canopy, with no central leader ( FIGS. 1 and 2 ). Trunk: The trunk is typical of the species with a smooth appearance. At about age 2 years, the initially discovered tree had a diameter of about 0.5 inches in diameter measured 6 inches above the ground. Bark: Bark ( FIG. 6 ) is smooth and light grey-green in color (RHS Fan 4 — 198D). Trunk lenticels: Shape .—Oblong-elongated. Size.— 0.12 inches. Abundance.— 4-5 per inch. Color .—Grey-orange (RHS Fan 4 — 165D). Leaf stomata: Shape .—Irregular. Size.— 0.02 inches. Color .—Green (RHS Fan 3 — 132C). Size and growth rate: Growth rate is slow. The original tree is currently 2 inches in diameter measured at 6 inches above the ground, it is 5 feet high, and 4 feet wide, thus providing an overall height to width ratio of about 1.25:1. Since transplanting to the observation site as a 0.5 inch caliper transplant, the original tree had an average growth in caliper of about 0.25 inches per year and vegetative growth of approximately 36 inches per year over 5 years. Branching habit: Branching is strongly weeping with stiff branch attachments. Primary branches are smooth and slender emerging from the trunk at a 60-degree angle becoming a 90-degree angle parallel to the trunk at 10 inches ( FIGS. 1 and 2 ). Branches: Surface texture is smooth. Color is grey (RHS Fan 4 — 198D). Branch lenticels, on a branch having a 0.25 inch caliper, the average lenticels size is 0.15 inches. Shape is oval-elongated. Color is yellow-green (RHS Fan 3 — 154D) to grey-yellow (RHS Fan 4 — 160 D). Foliage: The tree has leaves that are shaped similar to those of the species. Shape: opposite, simple, ovate to obovate, sharply serrulata, 2 to 3 inches long, 1 to 1.5 inches wide, with 0.15 inch pointed lobes. Sinuses are terminal, 1 to 1.5 inches long and smooth. Mature summer foliage color of upper surface is variegated green and yellow-green and is glossy (RHS Fan 3 — 141A green and RHS Fan 3 — 154 B yellow-green) ( FIG. 4 ); mature summer foliage color of lower surface is variegated green and yellow-green and is glossy (RHS Fan 3 — 141A green and RHS Fan 3 — 154 B yellow-green). Mature fall foliage color of upper surface is variegated green, red-purple, grey-orange (brown), orange-red and red-purple (pink) and is glossy (RHS Fan 3 — 141A green, RHS Fan 2 59B red-purple, RHS Fan 4 174A grey-orange, RHS Fan 1 N34A orange-red and RHS Fan 2 64B red-purple) ( FIG. 5 ); mature fall foliage color of lower surface is variegated green, red-purple, grey-orange (brown), orange-red and red-purple (pink) and is glossy (RHS Fan 3 — 141A green, RHS Fan 2 59B red-purple, RHS Fan 4 174A grey-orange, RHS Fan 1 N34A orange-red and RHS Fan 2 64B red-purple) ( FIG. 5 ). Immature spring foliage color of upper surface is light yellow-green, slightly mottled in appearance and is glossy (RHS Fan 3 145C yellow-green) ( FIG. 3 ); immature spring foliage color of lower surface is yellow-green, slightly mottled in appearance and is glossy (RHS Fan 3 145C). Vein color is green and is predominant on immature spring foliage (RHS Fan 3 131C). Pubescence: location, lower surface on new foliage; color light green (RHS Fan 3 142C). Overall shape — serrulate. Base: cuneate. Apex: truncate. Surface texture: smooth and glossy. Petiole: Average length approximately 1 inch to 1.5 inches. Diameter.— 0.25 inches ( FIG. 7 ). Surface texture is smooth and glossy. Color .—Grey-red on immature petioles (RHS Fan 4 178B). Glands: Predominant, 1-2 per leaf and orange-red in color (RHS Fan 1 N34A) ( FIG. 10 ). Buds: Typical of the species, being rounded. Size.— 0.15 inches to 0.25 inches long. Diameter.— 0.25 inches. Color .—Grey-brown (RHS Fan 4 N199C) to grey-brown (RHS Fan 4 200 D), with ciliate scale margins. Buds are formed prior to leaf emergence and are retained before flowering for 5-7 days. Flowers: Typical of the species are Monoecious with no fragrance. The staminate catkins are pendent and clustered. The individual flowers are white with a pink tinge (RHS Fan 4 155D) and are comprised of a 5-lobed red-purple calyx (RHS fan 2 63A) that encloses 2 to 3 red-purple (pink) stamens (RHS Fan 2 69B). Pistillate flowers are: solitary or on 2 to 3 pendulous spikes from the petioles prior to emergence of the new leaves. Individual pistillate flowers ( FIGS. 8 and 9 ) consist of: an oval-shaped, notched (0.2 inches deep) or lobed calyx surrounding the ovary, with the whole partly enclosed in an involucres. Flowers are 0.5 inches deep and 0.5 inches wide, which is 10-15% larger than the species or the closest known variety, Prunus incisa ‘Snow Showers’. Flowers develop on buds opening April 10 th -20 th with full bloom April 20 th -30 th , approximately 5 days later than the species or the closest known variety, Prunus incisa ‘Snow Showers’ with similar bloom longevity lasting 5-10 days. Fruit: Non-existent, which is atypical of the species and of the closest known variety, Prunus incisa ‘Snow Showers’. Root system: The root system is typical of the species being fibrous with a strong tap root development if on their own root or typical of Prunus avium ( FIG. 11 ) or whatever similar understock may be used if grafted. Pest and disease resistance: Typical of the species — generally healthy and trouble free. Tolerance to pH has been observed between 5.0-7.0 millivolts. Tolerance to other various soil conditions is unknown. Winter hardiness: Observed to be typical of the species — USDA Zones 6A-8B. The terms and expressions which have been employed in the foregoing specification are used therein as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding equivalents of the features shown and described or portions thereof, it being recognized that the scope of the invention is defined and limited only by the claims which follow.
A new cultivar of Prunus incisa named FPMSPL that is characterized by its weeping habit, its variegated white and yellow-green summer foliage color, its variegated green, red-purple, grey-orange, orange-red and red-purple fall foliage color and its lack of seeds and fruits.
0
TECHNICAL FIELD [0001] The present invention generally relates to automobile internal lights and lighting assemblies, and more particularly relates to methods and systems for lighting the automobile interior and energy saving devices that manage such methods and systems. BACKGROUND [0002] Most automobile cabs are equipped with at least one light that illuminates the cab interior. The light allows the automobile occupants to see at night or in a dark environment, and is typically controllable by some sort of switch that an occupant can manipulate when the occupant needs additional lighting. The light is also typically connected to a switch that is automatically turned on when an automobile door is opened in order to provide lighting as an occupant enters or exits the automobile, or when a person is removing cargo from the automobile cab. [0003] In addition to one or more cab lights, most automobiles that have cargo compartments such as trunks equipped with a light to aid a person's vision as they remove their cargo from the compartment. The cargo compartments can typically be opened and closed with a latched door. The cargo compartment light is electrically coupled to a switch that is automatically turned on when the cargo compartment door is opened in order to provide lighting as an occupant removes the cargo from the compartment. [0004] The cargo compartment light switch is also electrically coupled to a timer as a battery saving feature. The timer stops the flow of current to the switch after a predetermined period of time, and consequently deactivates the cargo compartment light. The timer is a valuable feature because people might unload cargo at their destination and then forget to return to the automobile to shut the cargo compartment door. However, the timer can also be a nuisance when a person has too much cargo in the compartment to unload in a single trip. If the timer is set to deactivate the cargo compartment light after a short period, a person will return to the automobile to retrieve a second load, only to be without sufficient lighting to see the cargo that is to be removed. [0005] Accordingly, it is desirable to provide a battery saving system and method for deactivating a cargo compartment light or other interior light to prevent an automobile battery from discharging when an automobile door is left open. In addition, it is desirable to provide a system and method for providing lighting to a person that must intermittently return to the automobile after the battery saving system has caused the light to be deactivated. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description and the appended claims, taken in conjunction with the accompanying drawings and the foregoing technical field and background. BRIEF SUMMARY [0006] A light activation system is provided for automatically illuminating a compartment in an automobile. The system comprises a light adapted to illuminate the compartment, a lighting circuit that activates and deactivates the light, and a distance sensor, electrically coupled to the lighting circuit, and adapted to cause the light to be activated when a person is within a predetermined distance from the compartment. [0007] The light activation system according to another embodiment of the invention further comprises a switch electrically coupled to the lighting circuit and adapted to cause the light to be activated when the compartment is opened, and a first timer electrically coupled to the switch and to the lighting circuit and adapted to cause the light to be deactivated after the switch activates the light for a set time. [0008] A method is also provided for automatically illuminating a compartment in an automobile having a light that is adapted to illuminate the compartment, and a lighting circuit that activates and deactivates the light. The method comprises the step of activating the light when a person is within a predetermined distance from the compartment using a distance sensor that is electrically coupled to the lighting circuit. BRIEF DESCRIPTION OF THE DRAWINGS [0009] The present invention will hereinafter be described in conjunction with the following drawing figures, wherein like numerals denote like elements, and [0010] FIG. 1 is a block diagram of an automatic cargo compartment lighting reactivation system in conjunction with a side view of an automobile according to an embodiment of the present invention; [0011] FIG. 2 is a block diagram of an automatic cargo compartment lighting reactivation system including the system's main components according to an embodiment of the present invention; and [0012] FIG. 3 is a logic diagram of a lighting circuit including the automatic cargo compartment lighting reactivation system main components according to an embodiment of the present invention. DETAILED DESCRIPTION [0013] The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary or the following detailed description. [0014] Various embodiments of the present invention pertain to the use of one or more distance sensors in conjunction with the lighting system in an automobile cargo compartment. It is desirable to have the cargo compartment illuminated while a person is loading or unloading cargo. It is also desirable to allow the person to temporarily leave and then return to the automobile while loading or unloading cargo without worrying whether the cargo compartment lighting remains turned on. Likewise, the person does not typically want to worry about whether the lighting will be turned off when the person is returning to load or retrieve additional cargo, particularly at night or in dark locations such as parking garages. Consequently, coupling one or more distance sensors with the lighting system to illuminate the cargo compartment when a person is near is an ideal way to ensure that a person can always have sufficient lighting when approaching the vehicle and when loading or removing cargo from the cargo compartment. [0015] According to an exemplary embodiment of the invention for illuminating a cargo compartment during cargo loading or unloading, FIG. 1 , an automobile 10 is equipped with a power source 18 that powers a cargo compartment light 30 as well as a distance sensor 16 . The power source 18 is typically the main vehicle battery, but may also be any appropriate type of auxiliary power source. The light 30 is typically disposed inside a cargo compartment 14 such as a trunk, although the light 16 may be installed on the cargo compartment door 12 or any other place in the cargo compartment vicinity from which the light 30 can illuminate the cargo compartment 14 . [0016] A number of distance sensors 16 are typically positioned at strategic locations about the automobile, although for the purposes of the present invention it is only necessary to show a distance sensor 16 near the cargo compartment 14 . The sensor 16 is suitably coupled to a controller 22 that receives power from the power source 18 when the automobile ignition is turned on, and at least for a predetermined period after the automobile 10 is parked with the ignition system turned off. In an exemplary embodiment of the invention, various alarm actuators (not shown) are suitably coupled to the controller 22 , and are used to activate an appropriate combination of visual and/or audible signals when backing up the vehicle to avoid a collision with an object near the automobile 10 . [0017] The sensor 16 may be any type of distance detection sensor that is appropriate for use on an automotive vehicle. One type of appropriate distance detection sensor is configured as an ultrasonic device. In order for an ultrasonic device to function as a distance detector, it is generally coupled to an ultrasonic transmitter/receiver (T/R) device 23 that is incorporated into the controller 22 in an exemplary embodiment of the invention, although other embodiments may also be used. The T/R device 122 is typically configured to transmit ultrasonic pulses via the sensor 16 , and to receive any return pulses from the sensor 16 that may be reflected from an external object, such as another parked or moving vehicle. A processor 25 is also typically incorporated into controller 22 , in conjunction with a memory 24 . The processor 25 is typically configured to calculate the distance from the sensor 26 to an external object, and to determine whether or not the external object is changing position, based on the elapsed time between transmission and reflected reception of ultrasonic pulses from the sensor 26 . [0018] As will be described in greater detail below, the processor 25 recognizes when a moving object is within a predetermined distance boundary with respect to the vehicle 10 . The detection system is conventionally used when parking a vehicle with the automobile transmission in reverse to avoid colliding with another object. In an exemplary embodiment of the invention, the detection system is coupled with the cargo compartment lighting system as illustrated in the block diagram of FIG. 2 and the logic diagram for a lighting circuit of FIG. 3 . [0019] As illustrated in FIG. 2 , a switch in the form of a latch or sensor in the trunk or other cargo compartment 14 is electrically coupled to a compartment light circuit 32 . In a conventional lighting system, opening the cargo compartment 14 will cause the light 30 to be activated, and closing the cargo compartment will cause the light 30 to be inactivated. A first timer 26 is electrically coupled to the cargo compartment 14 and also to the light circuit 32 and conventionally causes the light to be inactivated if the cargo compartment 14 is left open for a set time period. According to the present invention, the distance sensor 16 is also electrically coupled to the light circuit 32 . The distance sensor 16 detects a person approaching the automobile 10 and causes the light 30 to be activated if the person comes within a set radius of the cargo compartment 14 . [0020] According to one exemplary embodiment of the invention, the distance sensor 16 continues to monitor a person's presence near the cargo compartment 14 after activating the light 30 . When the distance sensor 16 detects that the person has moved beyond the set radius of the cargo compartment 14 , the light 30 is inactivated. In another exemplary embodiment, a second timer 18 is electrically coupled to the distance sensor 16 and also to the light circuit 32 and causes the light to be inactivated after the light 30 has been activated by the distance sensor 16 for a set period of time. Preferably, the second timer 18 is reset each time that the distance sensor 16 detects a person within the set radius of the cargo compartment in order to avoid having the light 30 repeatedly activated and inactivated. [0021] Because the cargo compartment 14 is connected to the light circuit 32 , opening and closing the cargo compartment can cause the other features to be activated or deactivated. For example, an exemplary embodiment of the invention includes having the light circuit 32 deactivate or stop responding to the distance sensor 16 if the cargo compartment 14 is closed. Preferably, the distance sensor 16 is deactivated when the cargo compartment 14 is closed in order to avoid battery rundown. In another embodiment of the invention the distance sensor 16 functions independent of the cargo compartment's open or closed state. In such an embodiment, even if the cargo compartment 14 fails to activate the light 30 , the distance sensor 16 still activates the light 30 when a person moves within the set distance of the cargo compartment 14 . [0022] An exemplary logic diagram of the lighting circuit 32 as described above is illustrated in FIG. 3 , with T=cargo compartment 14 (switch on), S=distance sensor 16 (on), L=light 30 (on), t 1 =first timer (timed out) 26 , and t 2 =second timer (timed out) 18 . The logic diagram is merely one example, and modifications of the logic diagram can be made within the principles of the present invention. [0023] In another exemplary embodiment of the invention, a counter 28 may be electrically coupled to the distance sensor 16 . The counter 28 keeps track of the number of light reactivations by the distance sensor 16 . After a predetermined number of reactivations, the counter 28 deactivates the distance sensor 16 . The counter 28 eliminates the concern of battery rundown due to false reactivations by the distance sensor 16 . Such false reactivations may be caused by a moving shrub or passing vehicles or people, for example. [0024] Although the invention is described primarily with reference to a cargo compartment 14 , the same configuration of sensors and timers can be applied to other automobile doors. According to this modification, a person can leave a car door open while loading or unloading loads of cargo without the concern for battery rundown caused by the light being activated while the person is away from the automobile. This and other modifications, as well as the various embodiments of the present invention described above, provide the advantages of illuminating the cargo compartment or other selected area while a person is loading or unloading cargo, and allow the person to temporarily leave and then return to the automobile while loading or unloading cargo without being concerned about whether the area lighting remains turned on. The inventive concept of coupling one or more distance sensors with the lighting system to illuminate the selected area when a person is near the automobile is an ideal way to ensure that a person can always have sufficient lighting when loading or removing cargo from the automobile. [0025] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing the exemplary embodiment or exemplary embodiments. It should be understood that various changes can be made in the function and arrangement of elements without departing from the scope of the invention as set forth in the appended claims and the legal equivalents thereof.
A light activation system is provided for automatically illuminating a compartment in an automobile. The system comprises a light adapted to illuminate the compartment, a lighting circuit that activates and deactivates the light, and a distance sensor, electrically coupled to the lighting circuit, and adapted to cause the light to be activated when a person is within a predetermined distance from the compartment. A method is also provided for automatically illuminating a compartment in an automobile having a light that is adapted to illuminate the compartment, and a lighting circuit that activates and deactivates the light. The method comprises the step of activating the light when a person is within a predetermined distance from the compartment using a distance sensor that is electrically coupled to the lighting circuit.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to power steering apparatuses for applying a steering assist force to a steering mechanism by hydraulic pressure created by a pump driven by an electric motor. 2. Description of Related Art Conventionally, power steering apparatuses for assisting in operating a steering wheel by supplying working oil from an oil pump to a power cylinder coupled to a steering mechanism have been employed. In such power steering apparatuses, the oil pump is driven by an electric motor. A steering assist force corresponding to the rotational speed of the electric motor is produced from the power cylinder. Drive control of the electric motor is achieved by an electronic control unit carrying out on-off control of a motor driving element composed of an FET (Field Effect Transistor). In some circumstances, the steering wheel continues to be violently operated, so that the motor driving element is frequently turned on and off. There are also circumstances that the load on the electric motor is increased, resulting in a large current flow in the motor. In these situations, the motor driving element generates heat. Accordingly, the motor driving element may be destroyed. The electronic control unit is constituted by a computer including a CPU, a RAM, and a ROM, for example, and has low resistance to heat applied from the exterior. When the motor driving element generates heat because the steering wheel continues to be violently operated, therefore, the electronic control unit may be destroyed by the heat generation from the motor driving element. In the conventional power steering apparatus, therefore, there is provided a temperature sensor for detecting the internal temperature of the electronic control unit, for example. If the temperature detected by the temperature sensor is higher than a predetermined temperature, the electronic motor is forced to be stopped. After the temperature detected by the temperature sensor is lowered to not more than the predetermined temperature, the electronic motor which has been forced to be stopped is restarted. Consequently, the motor driving element and the electronic control unit can be prevented from being destroyed by the heat generation. In the above-mentioned conventional control, however, after the electric motor is forced to be stropped, a driver may have a feeling of physical disorder in steering when the internal temperature of the electronic control unit is lowered to not more than the predetermined temperature while the steering wheel is being operated. That is, in a case where the driver is applying torque to the steering wheel, when the internal temperature of the electronic control unit is lowered to not more than the predetermined temperature, the electric motor is restarted in response thereto, thereby suddenly assisting in steering the steering wheel. Accordingly, the driver feels that the steering resistance is rapidly lowered. SUMMARY OF THE INVENTION An object of the present invention is to provide a power steering apparatus capable of preventing a driver from having a feeling of physical disorder in steering. A power steering apparatus according to the present invention uses an electric motor as a drive source, and produces a steering assist force for assisting in steering by oil pressure created by a pump driven by the electric motor, for example. The apparatus comprises a temperature detection section for detecting the temperature in a predetermined portion; a steering angle detection section for outputting steering angle data corresponding to a steering angle; a drive inhibiting circuit for inhibiting the electric motor from being driven when the temperature detected by the temperature detection section is not less than a predetermined upper-limit temperature; a judging circuit for judging, in a state where the electric motor is inhibited from being driven by the drive inhibiting circuit, whether or not the steering angle is included in a predetermined steering angle midpoint range on the basis of the steering angle data from the steering angle detection section when the temperature detected by the temperature detection section is lowered to not more than a predetermined lower-limit temperature; and a re-drive allowing circuit for allowing, when the judging circuit judges that the steering angle is within the steering angle midpoint range, the electric motor to be driven again. According to the present invention, when the temperature detected by the temperature detection section is not less than the predetermined upper-limit temperature, the electric motor is inhibited from being driven by the drive inhibiting circuit. When the temperature detected by the temperature detection section is lowered to not more than the predetermined lower-limit temperature in a state where the motor is inhibited from being driven, it is judged whether or not the steering, angle is within the steering, angle midpoint range. The electric motor is allowed to be driven again by the re-drive allowing circuit, provided that the steering angle is within the steering angle midpoint range. Consequently, the assistance in steering is prevented from being suddenly started while a driver is performing a steering operation, thereby making it possible to prevent the driver from having such a feeling of physical disorder in steering that the steering resistance is rapidly lowered. The steering angle midpoint range is a predetermined range including a steering angle midpoint, which is a steering angle in a case where a vehicle goes straight on. Furthermore, it is preferable that the predetermined portion is the inside of a control unit for controlling the drive of the electric motor. The predetermined portion may be a motor driving element such as an FET for controlling the supply of power to the electric motor. The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a conceptual diagram showing the basic configuration of a power steering apparatus according to an embodiment of the present invention; FIG. 2 is a flow chart for explaining operations performed by a CPU in relation to the drive of an electric motor; and FIG. 3 is a graph showing the relationship between the internal temperature of an electronic control unit and the maximum motor rotational speed of the electric motor. DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a conceptual diagram showing the basic configuration of a power steering apparatus according to an embodiment of the present invention. The power steering apparatus is provided in relation to a steering mechanism 1 of a vehicle, and is for applying a steering assist force to the steering mechanism 1 . The steering mechanism 1 comprises a steering wheel 2 operated by a driver, a steering shaft 3 connected to the steering wheel 2 , a pinion gear 4 provided at a front end of the steering shaft 3 , and a rack shaft 5 . The rack shaft 5 has a rack gear portion 5 a extending along the width of the vehicle and engaged with the pinion gear 4 . Tie rods 6 are respectively coupled to both ends of the rack shaft 5 . The tie rods 6 are respectively coupled to knuckle arms 7 for supporting right and left front wheels FR and FL serving as steering wheels. The knuckle arm 7 is provided so as to be rotatable around a king pin 8 . By this configuration, when the steering wheel 2 is operated so that the steering shaft 3 is rotated, the rotation is converted into a linear motion along the width of the vehicle by the pinion gear 4 and the rack shaft 5 . The linear motion is converted into rotation of the knuckle arms 7 around the king pins 8 , thereby achieving the steering of the right and left front wheels FR and FL. In a halfway portion of the steering shaft 3 , there are interposed a torsion bar 9 , which is distorted depending on the direction and the magnitude of steering torque applied to the steering wheel 2 , and an hydraulic pressure control valve 23 , which changes its valve aperture depending on the direction and the magnitude of the distortion of the torsion bar 9 . The hydraulic pressure control valve 23 is connected to a power cylinder 20 for applying a steering assist force to the steering mechanism 1 . The power cylinder 20 has a piston 21 provided integrally with the rack shaft 5 and a pair of cylinder chambers 20 a and 20 b , which are defined by the piston 21 . The cylinder chambers 20 a and 20 b are connected to the hydraulic pressure control valve 23 , respectively, through oil supply/return lines 22 a and 22 b. The hydraulic pressure control valve 23 is further interposed in a halfway portion of an oil circulation line 24 passing through a reservoir tank and an oil pump 26 . The oil pump 26 is driven by an electric motor 27 , to draw working oil stored in the reservoir tank 25 and supply the drawn working oil to the hydraulic pressure control valve 23 . The excess working oil is returned to the reservoir tank 25 from the hydraulic pressure control valve 23 through the oil circulation line 24 . The hydraulic pressure control valve 23 supplies, when the torsion bar 9 is distorted in one direction, the working oil to one of the cylinder chambers 20 a and 20 b in the power cylinder 20 through one of the oil supply/return lines 22 a and 22 b , while supplying, when the torsion bar 9 is distorted in the other direction, the working oil to the other cylinder chamber through the other oil supply/return line. When the torsion bar 9 is not virtually distorted, the hydraulic pressure control valve 23 enters a so-called equilibrium state. Accordingly, the working oil circulates in the oil circulation line 24 without being supplied to the power cylinder 20 . When the working oil is supplied to either one of the cylinder chambers in the power cylinder 20 , the piston 21 moves along the width of the vehicle. Consequently, a steering assist force is exerted on the rack shaft 5 . Drive control of the motor 27 is achieved by a CPU 31 in an electronic control unit carrying out on-off control of a motor driving element 35 composed of an FET, for example. The electronic control unit 30 comprises a RAM 32 , a ROM 33 and a temperature sensor 34 , which are connected to the CPU 31 through a bus 37 . The RAM 32 provides a work area for the CPU 31 . The ROM 33 stores an operation program of the CPU 31 , and the like. The temperature sensor 34 is provided inside the electronic control unit 30 , to detect the internal temperature of the electronic control unit 30 . Steering angle data outputted from a steering angle sensor 11 is fed to the CPU 31 through an I/O (Input/Output) port 36 connected to the bus 37 . The steering angle sensor 11 is provided in relation to the steering wheel 2 , and outputs steering angle data corresponding to a relative steering angle from an initial value, taking a steering angle of the steering wheel 2 when an ignition key switch of the vehicle is turned on to start the engine as the initial value “0”. Furthermore, an output signal of a vehicle speed sensor 12 for detecting the speed of the vehicle is fed to the CPU 31 through the I/O port 36 . The vehicle speed sensor 12 may directly detect the speed of the vehicle, or may find the speed of the vehicle by calculation on the basis of pulses outputted from wheel speed sensors provided in relation to the wheels. The CPU 31 finds a steering angle speed on the basis of the steering angle data fed from the steering angle sensor 11 . The drive of the motor 27 is controlled on the basis of the steering angle speed found from the steering angle data, the vehicle speed detected by the vehicle speed sensor 12 , and the temperature detected by the temperature sensor 34 . FIG. 2 is a flow chart for explaining operations performed by the CPU 31 in relation to the drive of the electric motor 27 . FIG. 3 is a graph showing the relationship between the internal temperature T of the electric control unit 30 , which is detected by the temperature sensor 34 , and the maximum motor rotational speed N of the electric motor 27 . The CPU 31 in the electronic control unit 30 first refers, when the ignition key switch of the vehicle is turned on, to an output signal of the temperature sensor 34 , to detect the internal temperature T of the electronic control unit 30 (step S 1 ). It is judged whether or not the detected internal temperature T is not less than a first threshold temperature T 1 previously determined (for example, 105° C.) (step S 2 ). If the internal temperature T is less than the first threshold temperature T 1 (NO at step S 2 ), the maximum motor rotational speed N of the electric motor 27 is set to a first rotational speed N 1 previously determined (step S 3 ). When the internal temperature T is not less than the first threshold temperature T 1 , it is then judged whether or not the internal temperature T is not less than a second threshold temperature T 2 (for example, 110° C.) higher than the first threshold temperature T 2 (step S 4 ). When the internal temperature T is less than the second threshold temperature T 2 , that is, the internal temperature T is not less than the first threshold temperature T 1 and is less than the second threshold temperature T 2 , the maximum motor rotational speed N is set in accordance with a straight line P 1 (see FIG. 3 ), which changes almost linearly between the first rotational speed N 1 and the second rotational speed N 2 (N 1 >N 2 ) with respect to the internal temperature T (step S 5 ). When the internal temperature T is not less than the second threshold temperature T 2 , the CPU 31 judges whether or not the internal temperature T is not less than a third threshold temperature T 3 (for example, 12° C.) higher than the second threshold temperature T 2 (step S 6 ). When the internal temperature F is less than the third threshold temperature T 3 , that is, the internal temperature T is not less than the second threshold temperature T 2 and is less than the third threshold temperature T 3 , the maximum motor rotational speed N is set in accordance with a straight line P 2 (see FIG. 3 ), which changes almost linearly between the second rotational speed N 2 and the third rotational speed N 3 (N 2 >N 3 ) with respect to the internal temperature T (step S 7 ). When the maximum motor rotational speed N of the electric motor 27 corresponding to the internal temperature T of the electronic control unit 30 is thus determined, the CPU 31 reads out a motor control map corresponding to the vehicle speed at that time from the ROM 33 on the basis of the output signal from the vehicle speed sensor 12 . The motor control map is referred to in order for the CPU 31 to set a suitable target motor rotational speed corresponding to the steering angle speed, and is provided for each of a plurality of vehicle speed ranges previously determined (for example, a low speed range, an intermediate speed range, and a high speed-range) such that a good steering feeling can be realized. The CPU 31 refers to the motor control map read out of the ROM 33 , to control the drive of the electric motor 27 within the range of the maximum motor rotational speed N set at the steps S 3 , S 5 , and S 7 on the basis of the steering angle speed found from the steering angle data outputted by the steering angle sensor 11 (step S 12 ). In the present embodiment, so-called idle-and-go control is carried out such that the electric motor 27 is rotated at a predetermined low rotational speed in a straight steering state where the steering wheel 2 is not turned, while the rotational speed of the electric motor 27 is increased to a rotational speed corresponding to the steering angle speed when the steering wheel 2 is turned. On the other hand, when the internal temperature T is not less than the third threshold temperature T 3 , the CPU 31 sets the maximum motor rotational speed N to zero (step S 8 ). When the internal temperature T of the electronic control unit 30 is not less than the third threshold temperature T 3 while the electric motor 27 is being driven, for example, the electric motor 27 during the driving is forced to be stopped. In the present embodiment, the processing at the step S 8 corresponds to the function of a drive inhibiting circuit. The CPU 31 sets the maximum motor rotational speed N to zero, and then always monitors an output of the temperature sensor 34 , to repeatedly judge whether or not the internal temperature T of the electronic control unit 30 is lowered to less than the first threshold temperature T 1 (step S 9 ). If the internal temperature T of the electronic control unit 30 becomes less than the first threshold temperature T 1 , it is judged whether or not the steering angle of the steering wheel 2 is within a steering angle midpoint range (for example, −5 to +5°) with reference to the steering angle data fed from the steering angle sensor 11 (step S 10 ). The steering angle midpoint is a steering angle of the steering wheel 2 in a case where the vehicle goes straight on. For example, the electronic control unit 30 samples the steering angle data outputted from the steering angle sensor 11 after the ignition key switch of the vehicle is turned on, to prepare a histogram of steering angle data values. The electronic control unit 30 finds, after steering angle data corresponding to a predetermined number of times of sampling are collected, the most frequent steering angle data, takes the most frequent steering angle data as steering angle data at a steering angle midpoint, and sets a predetermined range including the data as a steering angle midpoint range. The steering angle midpoint range thus set is stored in the RAM 32 contained in the electronic control unit 30 . The electronic control unit 30 judges whether or not the steering angle data from the steering angle sensor 11 is data within the steering angle midpoint range that is held in the RAM 32 . When the steering angle of the steering wheel 2 is not within the steering angle midpoint range it is repeatedly examined whether or not the internal temperature T of the electronic control unit 30 is less than the first threshold temperature, and the steering angle of the steering, wheel 2 is within the steering angle midpoint range until the steering angle of the steering wheel 2 is returned to the steering angle midpoint range. When the steering angle of the steering wheel 2 is returned to the steering angle midpoint range and it is judged that the steering angle of the steering wheel 2 is within the steering angle midpoint range (YES at step S 10 ), the maximum motor rotational speed N of the electric motor 27 is set to the first rotational speed N 1 (step S 11 ), and the drive control of the electric motor 27 is resumed (step S 12 ). Specifically, when the idle-and-go control is carried out as in the present embodiment, the electric motor 27 , which is being stopped, is restarted, to rotate the electric motor 27 at the predetermined low rotational speed. When the drive control of the electric motor 27 is started or resumed, the processing is returned. In the present embodiment the processing at the step S 10 corresponds to the function of the judging circuit, and the processing at the step S 11 corresponds to the function of the re-drive allowing circuit. As described in the foregoing, according to the present embodiment, when the internal temperature T of the electronic control unit 30 is not less than the third threshold temperature T 3 , the drive of the electric motor 27 is stopped. Thereafter, when the internal temperature T of the electric control unit 30 is lowered to less than the first threshold temperature T 1 , it is judged whether or not the steering angle of the steering wheel 2 is within a predetermined steering angle midpoint range. The drive of the electric motor 27 , which is being stopped, is resumed, provided that the steering angle of the steering wheel 2 is within the steering angle midpoint range. Consequently, it is possible to prevent sudden assistance in steering the steering wheel 2 from being provided while the driver is operating the steering wheel 2 , thereby making it possible to prevent the driver from having such a feeling of physical disorder in steering that the steering wheel 2 is rapidly lightened. Although description has been made of an embodiment of the present invention, the present invention is not limited to the above-mentioned embodiment. For example, although in the above-mentioned embodiment, so-called idle-and-go control is carried out such that the electric motor 27 is rotated at a predetermined low rotational speed even in a straight steering state where the steering wheel 2 is not turned, so-called stop-and-go control may be carried out such that the electric motor 27 is stopped in a straight steering state and is started, when the steering wheel 2 is steered at not less than a predetermined steering angle speed, in response thereto. When the stop-and-go control is carried out, the electric motor 27 may be restarted, when the steering wheel 2 is steered after the internal temperature T of the electronic control unit 30 is lowered to less than the first threshold temperature T 1 , and it is judged once that the steering angle of the steering wheel 2 is within the predetermined steering angle midpoint range, in response thereto. Although in the above-mentioned embodiment, the temperature sensor 34 is provided inside the electronic control unit 30 , and the maximum motor rotational speed N of the electric motor 27 is determined on the basis of the internal temperature T of the electronic control unit 30 , the temperature sensor 34 may be provided in relation to the motor driving element 35 , for example, to determine the maximum motor rotational speed N of the electric motor 27 on the basis of the temperature of the motor driving element 35 which is detected by the temperature sensor 34 . Further, the temperature sensor 34 may be provided in relation to the electric motor 27 , to carry out an electric motor control similar to that in the above-mentioned embodiment. Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims. The present invention claims priority benefits under 35 § 119 of Japanese Patent Application No. 11-100408 filed with the Japanese Patent Office on Apr. 7, 1999, the disclosure of which is incorporated hereinto by reference.
Disclosed is a power steering apparatus using an electric motor as a drive source. The power steering apparatus includes a drive inhibiting circuit for inhibiting an electric motor from being driven when the temperature detected by a temperature sensor is not less than an upper-limit temperature, a judging circuit for judging, in a state where the electric motor is inhibited from being driven by the drive inhibiting circuit, whether or not the steering angle is included in a predetermined steering angle midpoint range when the temperature sensor detects a temperature which is not more than a lower-limit temperature, and a re-drive allowing circuit for allowing, when it is judged that the steering angle is within the steering angle midpoint range, the electric motor to be driven again.
1
BACKGROUND OF THE INVENTION The present invention is in the nature of an improvement over mixers of granular material of the general type disclosed in U.S. Pat. No. 3,638,920 and others. These prior art devices utilize screw or auger conveyors to effect mixing of material in a hopper-like container, some including rotary agitator vanes or paddles in combination with auger conveyors. An important object of this invention is the provision of a feed mixer that is highly simplified in structure, that is efficient in its operation, and which utilizes a discharge control arrangement which is effective in preventing leakage of finely ground material from the container. SUMMARY OF THE INVENTION The feed mixer of this invention involves a container having generally vertical side and end walls, and a semi-cylindrical bottom wall portion having a discharge opening therethrough. An agitator in the container includes a central shaft, arms extending radially outwardly from the shaft, and mixing vanes on the radially outer ends of said arms. Means journal the shaft in said end walls for rotation generally on the axis of the radius of the bottom wall, and drive means is included for imparting rotation to said agitator, to mix and blend material in said container. Closure means for the discharge opening includes a plate-like closure member having opposite ends, guide means mounting the closure member for movements toward and away from a closed position underlying said discharge opening. Closure member moving means is connected to one end of said closure member for imparting opening and closing movements thereto, and means on said container bottom portion engages the other one of said closure member ends, and cooperates with said closure member moving means to exert sealing pressure to said closure member against the bottom portion responsive to movement of said closure member to its closed position. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a fragmentary view in side elevation of a granular feed mixer produced in accordance with this invention, some parts being broken away and some parts being shown in section; FIG. 2 is a view in end elevation, as seen from the right to the left with respect to FIG. 1, some parts being broken away and some parts being shown in section; FIG. 3 is an enlarged fragmentary section taken on the line 3--3 of FIG. 2; FIG. 4 is a fragmentary view in bottom plan as seen from the line 4--4 of FIG. 2; and FIG. 5 is a fragmentary view in exploded perspective of one of the mixing vanes of this invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT In the drawings, an open topped container, indicated generally at 11, is shown as comprising a pair of spaced vertical end walls 12 and sidewall structure formed to provide laterally spaced generally vertical sidewalls 13 and a semi-cylindrical bottom portion 14. The walls 12 and 13, with bottom portion 14 are preferably made from relatively rigid sheet metal, the end walls 12 being welded or otherwise rigidly secured to opposite ends of the wall structure 13, 14. A supporting frame structure includes vertically extending legs 15 that are welded to opposite side edge portions of the end walls 12. If desired, the open top of the container 11 may be closed by a suitable lid, not shown. A rotary agitator 16 is disposed within the interior of the container 11, and comprises a shaft 17 that is journaled in bearings 18 that are bolted or otherwise rigidly secured each to a different one of the end walls 12; a pair of elongated bars 19 welded at their longitudinal centers to the agitator shaft 17 in axially spaced relationship thereon and at right angles to each other and paddles or vanes 20 at the opposite ends of the bars 19. The bars 19 define arms 21 the outer ends of which are beveled as indicated at 22. Means for mounting the vanes 20 to the outer ends of the arms 21 comprises a plurality of plate-like mounting members 23 each of which is welded to a different one of the beveled ends 22 of the radial arms 21, clamping plates 24 one for each of the mounting members 23, and nut equipped clamping screws 25 that are adapted to extend through aligned openings 26 and 27 in the mounting members 23 and clamping plates 24 respectively, see particularly FIG. 5. The clamping screws 25 are also adapted to extend through slots 28 in the vanes 20 so as to securedly clamp each vane 20 between its respective mounting members 23 and clamping plates 24. As shown, particularly in FIG. 1, the angular relationship of the beveled ends 22 and mounting members 23 to the radial dimensions of their respective arms 21 disposes the vanes 20 so that one edge of each thereof becomes a leading edge and the opposite edge a trailing edge, relative to the direction of rotation of the agitator 16. The leading edges of the vanes 20 are indicated at 29, the trailing edges being indicated at 30. The slots 28 provided for adjustability of the vanes 20 toward and away from engagement of the leading edges 29 thereof with the inner surface of the semi-cylindrical bottom portion 40, the agitator shaft 17 being disposed on the axis of the radius of the bottom portion 14. It will be noted that with the angular displacement of the vanes 20 with respect to the radial dimensions of the arms 21 disposes the leading edges 29 so that they describe a circle of substantially greater diameter than one which is described by the trailing edges 30 during rotation of the agitator 16. Means for imparting rotation to the agiator 16 in a counterclockwise direction with respect to FIG. 1 includes a gear or sprocket wheel 31 secured to the shaft 17 outwardly of one of the end walls 12, and suitable driving means operatively connected to the gear or sprocket 31, these being well known in the art, and not shown. When the leading edges 29 of the vanes 20 become worn, the vanes 20 may be reversed between their respective mounting members 23 and clamping plates 24 so that the unworn trailing edge 30 becomes the leading edge of each vane 20. The container in walls 12 are formed to provide vertical slots 32 that are disposed centrally between the side walls 13 and which extend downwardly from the upper edges of the end walls 12 to a point slightly below the agitator shaft 17, adjacent portions of the agitator shaft 17 being loosely contained at the bottom portions of the slots 32. Normally, the slots 32 are covered by elongated panels 33 that are secured to the end walls 12 by suitable means such as nut-equipped machine screws or the like 34. When the panels 33 are removed from the end walls 12, and the bearings 18 released from engagement with the end walls 12, the entire agitator structure 16 may be removed upwardly from the interior of the container 11 for service or repairs to the agitator 16 or the interior of the container 11. With the agitator 16 in place as shown, and the panels 33 secured to the end walls 12, the container 11 is secured against leakage of material in the container outwardly through the slots 32. The bottom portion 14 of the container 11 is provided with a pair of laterally spaced generally rectangular discharge openings 35 that are normally closed by a plate-like closure member 36. A flat rigid valve plate 37 is rigidly secured to the container bottom portion 14, the valve plate 37 having openings 38 therethrough that coincide with the discharge openings 35, whereby the valve plate 37 has portions that encompass the discharge openings 35. A pair of laterally spaced parallel guide rails 39 are secured to the valve plate 37 for mounting the closure member 36 for sliding movements between a closed position underlying the openings 35 and 38 as shown by full lines in FIGS. 1, 3 and 4, and an open position away from underlying relationship with the openings 35 and 38, as shown by dotted lines in FIG. 1. Means for imparting movements to the closure member 36 between its open and closed positions comprises a pair of toggles 40 that are spaced apart transversely of the direction of movement of the closure member 36 and in a direction longitudinally or axially of the agitator 16. Each toggle 40 comprises a rigid toggle link 41 having an outer end pivotally secured to a pair of brackets or ears 42 fixed on the closure member 36 adjacent one edge thereof. The inner end of each link 41 is pivotally secured between the inner ends of pairs of rigid links 43, as indicated at 44, the links 43 having outer end portions that are welded or otherwise rigidly secured to axially spaced portions of a rockshaft 45. The rockshaft 45 is journaled at its opposite ends in bearing plates 46 that are bolted to the bottom portions of the end walls 12, the rockshaft 45 being disposed on an axis parallel to the agitator shaft 17, the axes of pivotal connections of the links 41 to the ears 42, and to the axes of the pivotal connections 44 between the links 41 and their respective links 43. Means for imparting movements to the toggles 41 to move the closure member 36 between its open and closed positions comprises an elongated handle member 47 having one end rigidly secured to one end of the rockshaft 45. As shown by full and dotted lines in FIG. 1, the handle member 47, when raised to its dotted line position, causes the toggle links 41 and 43 to swing in directions to move the closure member 36 to its open position. When the handle member 47 is swung downwardly to its full line position of FIG. 1, the toggle links 42 and 43 are moved to a position slightly beyond a dead center relationship at which point the closure member 36 underlies the aligned discharge openings 35 and 38. A generally U-shaped stop strip 48, secured at its opposite ends to the end walls 12, engages the inner end portions of the links 41 and 43 to limit downward movement thereof slightly beyond said dead center relationship between the links 41 and 43. A pair of hook-like stop members 49 are welded or otherwise rigidly secured to the valve plate 37 for limiting closing movement of the closure member 36. The stop members 49 are formed to provide cam surfaces 50 that engage the edge of the closure member 36 opposite the ears 42 during closing movement of the closure member 36 to force the upper or inner surface of the closure member 36 into sealing engagement with the adjacent surface of the valve plate 37. It will be noted that, when the closure member 36 is in its closed position, the toggle links 41 are angularly disposed to press the adjacent edge portion of the closure member 36 into sealing engagement with the valve plate 37 in cooperation with the cam surface 50, so that leakage of material through the discharge openings 35 and 38 is effectively prevented. For the purpose of obtaining a fine adjustment between the toggles 40 and the stop members 49, a pair of nut-equipped stop screws 51 are secured to a pair of the legs 15, the screws 51 engaging outwardly projecting ears 52 on the rockshaft supporting brackets 46. By adjusting the screws 51, the brackets 46 may be swung in either direction with respect to their adjacent legs 15, so as to move the axis of the rockshaft 45 toward or away from the stop members 49. With the mixer herein disclosed, it has been found possible to thoroughly mix granular feed material very rapidly, particularly materials which have heretofore been quite difficult to mix, such as light fluffy bran with other similar material. While a commercial embodiment of feed mixer has been shown and described, it will be understood that the same is capable of modification without departure from the spirit and scope of the invention, as defined in the claims.
A container, having generally vertical end and sidewalls and a semi-cylindrical bottom portion, defines a discharge opening in the bottom portion that is normally closed by an underlying plate-like closure member. Toggle linkage and a closure member engaging cam operate to press the closure member against the bottom portion so as to make sealing contact between the container and the closure member. A feed mixing agitator rotates within the container and includes mixing vanes adjustably mounted on the outer ends of arms extending radially from a rotary shaft journaled in bearings in the end walls of the container.
1
[0001] This invention relates to miscellaneous industrial techniques and to means of transport such as ships and, consequently, to salvage equipments in the sea or in other water environments. [0002] More specifically, it relates to a salvage suit for shipwrecks that lets maintain the wearer totally afloat, and said wearer can move inside the body receptacle; the suit prevents water from entering, insulates the wearer from cold, lets protect the area around the head, and lets collect rain water while the wearer waits being rescued. BACKGROUND OF THE INVENTION [0003] Until now, several salvation equipments are known that mainly include suits or dresses, into which the shipwrecked person's body is protected from aggressive factors that act before (fire, high temperature, etc.) and/or after (staying in water, low temperature, etc.) a shipwreck. [0004] So, we know the suit included in patent document U.S. Pat. No. 1,102,772. This suit has two independent openings: the upper or head opening and the front or chest expansible opening. The latter is based on a precarious tight fitting system that may be freed and flood the suit inner bladder. [0005] The patent document U.S. Pat. No. 1,314,299 shows a suit having inflatable chambers; those chambers do not cover the whole suit, but they are located in areas where bladders are filled with air that the wearer blows. [0006] The patent document U.S. Pat. No. 2,181,150 shows a suit that is partially expansible, but that does not have any expansible sleeve. This suit does not have any mean to cover the head or the face, and it is prepared just to float vertically. [0007] The patent document U.S. Pat. No. 2,761,154 shows a suit into which the wearer enters through an upper opening having expansible capacity, that then may be tightened around the face. Even though the upper end of the suit may be expanded until it has a tubular form, in fact no tubular sleeves are added. This suit also floats vertically. Its materials are waterproof, but they are not thermo-insulating. It also requires inflatable bladders to maintain flotation. [0008] The patent document U.S. Pat. No. 4,242,769 uses small bladders to provide thermo-insulation and floatability, but these bladders are not permanently close and they have to be inflated. Consequently, in order to perform that function, they have to be blown up. [0009] The patent document U.S. Pat. No. 4,599,075 refers to a suit that protects the head and face, that provides hygienic capacity to collect urine and feces, that allows eating solid food and drinking liquids, and inside which the wearer can make certain movements. Those movements allow the wearer taking his arms out of the sleeves and moving his legs towards his trunk, rubbing parts of his body, etc. The movements can be made thanks to bellows or folds, the flexibility and material of which allow the wearer taking his arms out of the sleeves and putting his legs in fetal position. The wearer has to assume this position because of his exposure to cold, as this suit has not adequate protection against extreme temperatures. [0010] The patent document U.S. Pat. No. 4,704,092 shows a garment whose walls comprise two alveolar plastic sheets, with a chamber of air between them, and that include aluminum heat-reflecting layers. This suit has not expansible sleeves in the upper opening and has not armors. [0011] The patent document U.S. Pat. No. 5,560,043 shows a suit that, event though it does not have expansible sleeves, its head opening has two hoods: an outer hood and an inner hood that may overlap. [0012] It is also known the fireproof suit of the patent document AR P040104230 of the same inventor than this one. This suit walls do not have the alveolar plastic layer component, its sewed and sealed gloves are made of rubber and asbestos, it has not a hoisting armor or an expansible outer sleeve capable of protecting and collecting water, and it is a suit that fits to the wearer's body. [0013] It is also known the permanence and salvage suit of the patent document AR P080101604 of the same inventor than this one. This suit walls do not have an outer layer that, with the inner layer, form an insulating hermetic bladder. It also requires using clothes having a vest and a hood that the wearer has to wear before entering into the suit. [0014] Generally, neoprene conventional suits do not protect the wearer adequately from low temperatures. The cold outside liquid (sea, lake, river, etc. water) acts, through the neoprene, on the liquid and humidity existing between the body and the suit, and the temperature can reach 14° C. We have to note that liquids conduct 30 times faster than the air. [0015] We have to add that the wet face exposed losses temperature because of the air accelerated conduction (between 20 and 60 Km/h. or more), cooling water drops that touch the face. This exposition to cold is very negative, and in some suits the following areas are also exposed: feet, wrists, hands and areas around zippers. ADVANTAGES AND PURPOSES [0016] This invention complies with several purposes and it has numerous advantages, to wit: [0017] It allows the shipwrecked person entering into the suit quicker, as he is dressed, and this action is not hindered by the clothes or shoes that he is wearing. [0018] The suit can be worn quicker, and so the shipwrecked ship evacuation can be made quicker. [0019] The same opening that serves to wear the suit has an inner expansible sleeve that serves to contain and cover the head. This inner sleeve has multiple positions to close it, and this lets it act as a hood when it closes around the face, or completely cover the face by closing over it or close around the neck, leaving the head free. [0020] If the outer sleeve is extended and close, the inner sleeve may remain open, and so the wearer can sit like in a kayak, leaving the head, trunk and hands inside the outer sleeve; this lets see and receive the rescue boat, ship or helicopter. When the outer sleeve is fit tight to the waist and the wearer sits like in a kayak, he can also work with his head, trunk and arms outside the suit. [0021] When the outer sleeve is expanded and close, the wearer can look at him into the suit, use the oars supplied in it, drink water and eat food, throw his feces and urine, keeping the hygiene, make exercises, massages, take his vest off or wear it or other clothes, seal a wound, sleep, etc. [0022] The outer sleeve expanded acts as an extra receptacle that lets the wearer remain protected from the waves, rain and winds, obtaining insulation against water. [0023] The adequate management of the expandable sleeves lets take the excess of hot air from the inner receptacle or space, or accumulate heat, and even in case of rain, to collect fresh water between both expandable sleeves. [0024] As both expandable sleeves are easily and quickly open, taking off and leaving the suit in the water is easier when the wearer enters into any rescue means of transport (ship, helicopter, etc.). [0025] As the receptacle is spacious, different movements can be made inside the suit. For example: take the legs out of the suit legs toward the main part of the suit, take the arms out of the sleeves, change the different floating positions in order to be more comfortable, etc. [0026] The capacity of flotation given by the alveolar sheets, the hermetic chambers and the body receptacle keep the suit almost completely out of the water, and this diminishes the area of body contact with the water and prevents the body from being exposed to cold, when the water temperature is low. [0027] At the same time, the wearer protects his face, neck, hands and arms, he has a 100% hermetic barrier against water, and he gets an adequate protection against hypothermia. Consequently, the wearer can stay longer in cold water. [0028] The insulation from the surrounding temperature occurs not just because of the presence of the air contained, but also because of a series of convection (within the covers and alveolar sheets) and transmittance (given by the micro-aluminized that can be double, i.e. two in each sheet) that are reinforced between them. [0029] In convection processes, for example, the use of very low density alveolar layers contributes to diminish the interchange or the leakage speed from the hotter environment. In the air contained in the alveolar layers occurs the following: 1°) There is a convection process; 2°) A space having a very low mass density-area surrounding transmittance is created (Note: A high mass iron inhibits or diminishes transmittance, as opposed to an area without mass, that not only refracts, but also cannot accumulate or conduct in a mass that does not exist). [0030] The potentiation of its thermal insulation through the different processes of convection, lack of conduction and transmittance causes an insignificant interchange of temperature between the wearer body and the water, and this allows him to stay in cold water for longer and, if the wearer was wet when he wore the suit, it lets the body recover its normal temperature. As this suit has a pronounced difference of floatability, more thermal resistance, and maintains a smaller surface of contact with the water, we also do not need to put our legs in fetal position to reduce the area exposed to cold. [0031] This suit allows flotation with almost the whole body out of the water, and this allows swimming on one's back or on one's chest very easily (and so it is easy to face even opposite wind and/or current), being the additional advantage that, in case of a puncture, tearing or flooding, the suit inner bladder is not lost, as we also have the alveolar layers, the hermetic chambers and the body receptacle air. [0032] The thermal insulation occurs not just because of the air contained, but also because of a series of convection processes (inside the fabric and in the alveolus—for example, integrated in the very low density alveolar layers, and so we diminish the interchange or the leakage speed from the hotter environment—and chambers of air existing between their layers) and transmittance (given by the micro-aluminized) that are reinforced between them. The potentiation of its thermal insulation through the several convection and transmittance processes almost annuls the temperature interchange between the wearer body and the water. [0033] As this suit may include aluminum in the form of micro-sheets, this material generates phenomena that help maintaining the shipwrecked person temperature: Internal transmittance inside the hollow fabric. Transmittance toward the outside of the suit. Internal transmittance toward the inside of the suit receptacle. Convection in the area without conductors and projection to the whole insulation system: inside the fabric, the circular convection of the air confined in the alveolus and in their interalveolar spaces contributes to the internal transmittance process inside the layers, contributing to insulation. Consequently, the air confined is empowered because of the radiation and convection (inside each alveolus). [0038] The tests made prove that, in different cold environments and under the wearer body temperature (36° C./37° C.), the suit receptacle temperature is constant at about 33° C. Immersion tests made in water at −2° C. with the head sleeve open during 8 hours (and the consequent heat loss through the head opening) proved that the receptacle temperature is 28° C. As the wearer normally has to stay still inside the receptacle, this is not just a survival temperature, but also a comfortable temperature. As the suit is as spacious as a cabin, it lets the wearer withdraw to the main part of the receptacle and take his arms and legs out of the sleeves and suit legs that are more exposed to getting cold. [0039] The fact that the suit can float, keeping it partially out of the water, and that the receptacle creates a dry environment also contribute to the suit thermal capacity. [0040] This suit has additional advantages: it lets the person swim on his stomach without wetting his face, it has no complex mechanisms (for ex. zippers), its operation is safer, it includes an outer cover that is highly resistant to frictions and to mechanical efforts, it includes a fireproof cover, etc. I—BRIEF DESCRIPTION OF THE DRAWINGS [0041] To clarify and understand better the aim of the invention, it is illustrated with several figures in which it was represented in one of its preferred forms of embodiment, as an illustrative, not limitative example: [0042] FIG. 1 is a top elevational view of this salvage suit. [0043] FIG. 2 is a top elevational view of this salvage suit, with some of its auxiliary elements expanded. [0044] FIG. 3 is a detailed top elevational view of the inner bladder, in one of its possible forms of embodiment, in which the round alveolar compartments can be seen. [0045] FIG. 4 is a top elevational view of a detail of the inner bladder, in another of its possible forms of embodiment, in which rectangular alveolar compartments can be seen. [0046] FIG. 5 includes drawings A, B and C, being: [0047] Drawing A, a cross-sectional view of the inner and outer bladders, as indicated in a cross-sectional plan that appears indicated as A-A in FIG. 3 ; [0048] Drawing B, a cross-sectional view of the inner and outer bladders, as indicated in a cross-sectional plan that appears indicated as B-B in FIG. 4 , and [0049] Drawing C, a cross-sectional view of the inner and outer bladders in another form of embodiment. [0050] FIG. 6 is a perspective view of the salvage suit with its outer sleeve expanded. [0051] FIG. 7 is a perspective view of the top part of the salvage suit in which the head sleeve can be seen folded and surrounded by the protection sleeve. [0052] FIG. 8 is another perspective view of the top part of the salvage suit in which we can see how the expanded head sleeve is accompanied by the protection sleeve to which it is connected by a joint. [0053] FIG. 9 is another perspective view of the top part of the salvage suit that shows the outer sleeve expansion around the head sleeve. [0054] FIG. 10 is a top elevational view of the thermo-insulating device expanded and shown compared to the salvage suit contour. [0055] FIG. 11 includes drawings A, B and C, being: [0056] Drawing A, a top elevational view of the thermo-insulating device expanded, [0057] Drawing B, a top elevational view of the thermo-insulating device folded, not being used, with its wings rolled up, and [0058] Drawing C, a top elevational view of the thermo-insulating device folded, and wrapped. [0059] FIG. 12 is a top elevational view of the thermo-insulation device folded, wrapped, and shown compared to the salvage suit contour. [0060] FIG. 13 is another perspective view of the top part of the salvage suit that shows the expansion of the outer expandable head sleeve supplied with a hood-type helmet. [0061] FIG. 14 is a top elevational view of this salvage suit in which the armor layout is shown. [0062] FIG. 15 is a rear elevational view of this salvage suit in which the armor layout is shown. [0063] FIG. 16 is a top elevational view of the armor out of its normal assembly in the suit. [0064] FIG. 17 is a rear elevational view of this salvage suit in which the suit legs thermo-insulating reinforcement location was shown. [0065] FIG. 18 is a detailed cross-sectional view of a leg suit wall showing the distribution of the inner and outer layers, with the thermo-insulating reinforcement between them. [0066] FIG. 19 is a top elevational view of this salvation suit showing the distribution of some compartments and/or pockets to put different elements. [0067] FIG. 20 is a partial longitudinal sectional view of the suit showing the compartment and/or pocket location. [0068] FIG. 21 includes drawings A and B, being: [0069] Drawing A, a longitudinal sectional view of this suit showing the wearer's location, with his body inside the receptacle, and [0070] Drawing B, a longitudinal sectional view of this suit showing the wearer's location with his head inside the expansible head sleeve. [0071] In the different drawings, the same reference numbers and/or letters indicate the same or corresponding parts. LIST OF MAIN REFERENCES [0072] ( 1 ) Salvation suit [0073] ( 1 a ) Suit mittens ( 1 ). [0074] ( 1 b ) Suit legs ( 1 ). [0075] ( 1 c ) Suit leg belts ( 1 b ) [0076] ( 2 ) Body receptacle. [0077] ( 2 a ) Hermetic chamber. [0078] ( 2 b ) Head opening [through which the body receptacle is accessed ( 2 )]. [0079] ( 3 ) Expansible head sleeve. [0080] ( 3 a ) Head seizing means [it fits the expansible head sleeve opening tight ( 3 )]. [0081] ( 3 b ) Head helmet or cover. [0082] ( 3 c ) Expansible walls. [0083] ( 3 d ) Display opening. [0084] ( 3 e ) Head sign. [0085] ( 4 ) Expansible outer sleeve. [0086] ( 4 a ) Outer seizing means [it fits the expansible outer sleeve opening tight ( 4 )]. [0087] ( 4 b ) Adjoining receptacle [formed by the expansible outer sleeve ( 4 ) around the expansible head sleeve ( 3 )]. [0088] ( 5 ) Protection sleeve. [0089] ( 5 a ) Joint between the expansible head sleeve ( 3 ) and the cover sleeve ( 5 ). [0090] ( 11 ) Inner cover. [0091] ( 12 ) First plastic stratum. [0092] ( 12 a ) First layer of the first plastic stratum ( 12 ). [0093] ( 12 b ) Second layer of the first plastic stratum ( 12 ). [0094] ( 13 ) Thermo-insulating layer. [0095] ( 14 ) Third plastic stratum [0096] ( 14 a ) Third layer of the third plastic stratum ( 14 ). [0097] ( 14 b ) Fourth layer of the third plastic stratum ( 14 ). [0098] ( 14 c ) Sign layer. [0099] ( 15 ) Second alveolar plastic stratum. [0100] ( 15 a ) Alveolar compartment. [0101] ( 15 b ) Alveolar wall. [0102] ( 15 c ) Interalveolar compartments. [0103] ( 20 ) Outer cover. [0104] ( 21 ) Protection cover. [0105] ( 22 ) Top compartment. [0106] ( 30 ) Life rope. [0107] ( 30 a ) Rope anchorage. [0108] ( 31 ) Hoisting front anchorage. [0109] ( 32 ) Help instrument. [0110] ( 33 ) Sign means. [0111] ( 40 ) Thermo-insulating accessory. [0112] ( 41 ) Accessory back ( 40 ). [0113] ( 42 ) Cover wings [0114] ( 42 a ) Rolled or folded cover wings. [0115] ( 43 ) Head wing. [0116] ( 44 ) Closing means. [0117] ( 50 ) Armor. [0118] ( 51 ) Suit leg fastening. [0119] ( 52 ) Waist fastening. [0120] ( 53 ) Front fastening. [0121] ( 54 ) Chest fastening. [0122] ( 55 ) Crossed back fastening. [0123] ( 56 ) Back anchorage. [0124] ( 60 ) Thermo-insulating reinforcement. [0125] ( 61 ) Front compartments or pockets. II—DESCRIPTION OF PREFERRED EMBODIMENTS [0126] In general terms, this invention relates to a salvage suit for shipwrecks that includes a loose body receptacle ( 2 ) that is capable of containing the shipwrecked body as a floating mini-cabin; this body receptacle ( 2 ) is limited by an inner cover ( 11 ) that, formed by plastic layers ( 12 )( 15 )( 14 ), is separate from the outer cover ( 20 ) by a hermetic air chamber ( 2 a ); the body receptacle ( 2 ) is accessed through the head opening ( 2 b ) in which we have a head sleeve ( 3 ) and an outer sleeve ( 4 ) that can be unfolded. DETAILED DESCRIPTION [0127] More specifically, this salvage suit ( 1 ) includes a receptacle ( 2 ) according to the anatomical form of the shipwrecked person. Notwithstanding this, it was conceived to be loose enough to let the wearer move inside said receptacle ( 2 ) that, consequently, is like a floating mini-cabin. [0128] The suit sides ( 1 ) project a couple of top extensions that end in two close mittens ( 1 a ), while the bottom part projects a couple of suit legs ( 1 b ) that end in two close feet. [0129] This body receptacle ( 2 ) is limited by al least two covers ( 11 )( 20 ) that consist in an inner cover ( 11 ) and in an outer cover ( 20 ), separate between them by a hermetic air chamber ( 2 a ). It was foreseen to include a third cover or protection cover ( 21 ) whose composition may give it a delaying capacity against fire or other protection capacities. [0130] The inner cover ( 11 ) includes a first ( 12 ), a second ( 15 ), and a third ( 13 ) plastic strata. Inside the first plastic stratum ( 12 ), we see a first ( 12 a ) and a second ( 12 b ) plastic layers between which there is a thermo-insulating layer ( 13 ) formed by a thermo-insulating material, such as aluminum. [0131] The second plastic stratum ( 15 ) is of alveolar type. It includes several alveolar compartments ( 15 a ) filled with air and hermetically close. These compartments are limited by several alveolar walls ( 15 b ) that connect the first plastic stratum ( 12 ) with the third plastic stratum ( 14 ). In this form of embodiment, the alveolar compartments ( 15 a ) have a round form, and so the walls can also determine the formation of inter-alveolar compartments ( 15 c ). [0132] In the third plastic stratum ( 14 ) there is a third ( 14 a ) and a fourth ( 14 b ) plastic layer, between which there is also a thermo-insulating layer ( 13 ). It was foreseen another form of embodiment in which, outside the thermo-insulating layer ( 13 ), but inside the fourth plastic layer ( 14 b ), there is a sign layer ( 14 c ), for example, painted with a flashy paint. [0133] The outer cover ( 20 ) may include a plastic stratum formed by one or more layers of an appropriate plastic material. [0134] On the other hand, the access to the suit ( 1 ) body receptacle ( 2 ) may occur through a head opening ( 2 b ), whose edges are projected in a head sleeve ( 3 ) that can be unfolded, surrounded by an outer sleeve ( 4 ) that can be unfolded and, in the outside part of said sleeves ( 3 )( 4 ), there is a protection sleeve ( 5 ) that can also be unfolded. [0135] The head sleeve ( 3 ) that can be unfolded may be formed by a transparent plastic stratum and may end in means to seize the head ( 3 a ), that let adjust the sleeve edge ( 3 ) on the wearer's face. It was also foreseen that the referred head sleeve ( 3 ) includes a helmet, hood or cover ( 3 b ) for the head in order to give a better protection and to wear it on the referred wearer's head. For example, it was foreseen to include a “hood”-type helmet ( 3 b ) that covers the head and most of the face. This helmet ( 3 b ) may be structured in a multilayer material that includes plastic, thermo-insulating and protection layers. [0136] An outer sleeve ( 4 ) that can be unfolded surrounds said head sleeve ( 3 ). Said outer sleeve, that can also be transparent, may be unfolded to create an adjoining receptacle ( 4 b ) around said head sleeve ( 3 ). This adjoining receptacle ( 4 b ) has different uses. One of them is the possibility to create a protected environment around the shipwrecked head. Another use is that it may be a receptacle to collect rain water. [0137] In the outside part of said outer sleeve ( 4 ) there is a protection sleeve ( 5 ) made in a fabric similar to that of the suit ( 1 ) protection cover ( 21 ). This protection sleeve ( 5 ) has a joint ( 5 a ) that circumstantially allows connecting it to the head sleeve ( 3 ) that can be unfolded, and so, when the outer sleeve ( 4 ) is folded, they can be unfolded together. [0138] For the materials that form the plastic strata ( 12 )( 15 )( 14 ) it was foreseen the use of compounds such as linear low density polyethylene and bioriented polypropylene. The use of this kind of materials gives high resistance to water and the possibility to form metal layers [microaluminized] that act as thermo-insulating layers ( 13 ). [0139] On the other hand, this suit ( 1 ) includes an armor whose strips form suit leg seizures ( 51 ), trunk seizures ( 52 )( 53 )( 54 )( 55 ), and chest and back anchorages ( 30 a )( 31 ). More specifically, it includes several strips that are arranged around the suit legs ( 1 b ), around the central part of the receptacle ( 2 )—where the body trunk is placed—and around the shoulders. [0140] Said strips form a set of suit leg seizures ( 51 ), a waist seizure ( 52 ), a crossed chest seizure ( 54 ) and a set of chest and back seizures. [0141] Said chest and back seizures include a set of chest seizure sections ( 53 ) that, connected through the waist seizure ( 52 ) and the crossed chest seizure ( 54 ), go over the shoulders. From there, the back seizure sections ( 55 ) extend and cross until they end in the waist seizure ( 52 ). [0142] It was foreseen that, for example, the armor ( 50 ) may be fixed to the inner part of the protection cover ( 21 ). [0143] The armor ( 50 ) also provides at least a set of front anchorages ( 30 a )( 31 ) and a back anchorage ( 56 ). In a form of embodiment, this back anchorage ( 56 ) may be long enough to be normally placed in the front part of the suit ( 1 ) where it has a temporary fixation, so that the wearer can use it in case of need. [0144] It was foreseen the use of a thermo-insulating accessory ( 40 ) that, as an open vest, is put inside the body receptacle ( 2 ). This thermo-insulating accessory ( 40 ) includes a back ( 41 ) from which a head wing ( 43 ) and two side cover wings ( 42 ) are projected. These side cover wings ( 42 ) may be placed rolled or folded ( 42 a ) when they are not being used. To use them, they are folded around the shipwrecked body and they are fastened with a zipper ( 44 ) that keeps them in that position. [0145] It was foreseen the addition of different auxiliary means. For example, a chest compartment ( 22 ) from which a life rope ( 30 ), an auxiliary instrument ( 32 ), etc. can be used. We can also include other anchorages for ropes, seizing ( 1 c ) for the suit legs ( 1 b ), sign means ( 33 ), etc. [0146] It was also foreseen the possibility to include a set of thermo-insulating reinforcements ( 60 ) of the suit leg that are located at the back of each suit leg ( 1 b ). [0147] They are thermo-insulating walls that are located between the inner cover ( 11 ) and the outer cover ( 20 ), at the wearer's knee back part height. The reinforcement includes a first plastic stratum ( 12 ) with at least a thermo-insulating layer ( 13 ), a second alveolar plastic stratum ( 15 ), and a third plastic stratum ( 14 ) with at least a thermo-insulating layer ( 13 ). [0148] It will be apparent that various modifications can be made in this invention as far as certain construction details and form are concerned, without departing from the scope of the invention as defined in the claims below:
The present invention relates to a salvage or safety suit worn by a person escaping a shipwreck. The suit includes a receptacle structured to receive and enclose a person's body and a head opening for entering the receptacle. The receptacle is layered to provide flotation and thermo-insulation properties to the suit.
1
CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of co-pending application Ser. No. 219,822 filed Dec. 24, 1980 entitled "Air-Powered Grain Drill", now abandoned. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention broadly relates to grain or seed drills and, more particularly, to grain drills which are provided with pneumatic means to meter and propel the seeds to open ground furrows. 2. Description of the Prior Art Due to the hunger of the increasing world's population there is a corresponding increasing demand for more food output per acre. A way of meeting this increased demand is by increasing the efficiency of the farmer. One specific way of increasing the farmer's efficiency is by improved seed planting devices. Numerous generations of mechanized seed planting devices have been developed with each being an advance over the preceeding generation. Currently the majority of planting or seeding is carried out by devices called grain drills which consist of seed boxes attached to a rear portion of plows or furrow openers and deposit seeds at preselected intervals into furrows. These prior art grain drills may also be attached to separate wheeled trailers, but this is generally cost prohibitive. Due to the extreme localized weight of the seed and the weight of the grain drill on the rear portion of the grain drill plows these prior art grain drills are only manufactured in relatively small units so to be easily carried. The small size of the seed boxes necessitates frequent refilling. Also the greater number of grain drills increases the cost of initial purchase and repair to the farmer. Several small grain drills can be pulled in squandron hitches, but this is cumbersome to operate. Air powered grain drills have been designed in the past, however each has disadvantages, such as small size, irratic seed delivery and lack of means to selectively block the delivery tubes for specific seeding pattern, for different grains or other seed-like material. Some drills use venturi principles which are open to pick up dirt, dust particles and debris which commonly exist when drilling seed and which have been known to plug such delivery tubes causing underseeding and overseeding. SUMMARY OF THE INVENTION A primary object of the present invention is to provide an air-powered grain drill with a large capacity seed box centrally disposed over a mobile frame work. Another object of the present invention is to provide a grain drill which is carried by a vehicle, i.e. self-propelled or may be trailed behind a vehicle. Another object of the present invention is to provide a grain drill having an air-powered sealed seed distribution system that is non-jamming, will cause little or no injury to the seed, is sealed from dirt and debris and will not leak grain or seed particles during non-seeding periods. Another object is to provide control over the metering system as a function of the speed of traverse across the ground and to provide a grain drill which has means to selectively block the delivery tubes for selected seeding patterns. Other objects of the present invention will become apparent through the reading of the description of the preferred embodiments and viewing of the drawings. Generally, the present invention is comprised of a central framework having a plurality of wheels attached thereto for rolling movement across the surface of the ground and with a plurality of furrow openers trailing behind and from wings on each side of the framework. A plurality of press wheels are attached to the framework and the wings to close the ground over the seed. A large capacity (e.g. enough for a days planting) air tight substantially sealed seed box or bin is disposed above and attached to the framework and is oriented to supply seed into a plurality of metering mechanisms. The metering mechanisms have channels which intersect horizontal pressurized air flow channels within a seed directing device. The seed directing device is in communication with a forced air device, such as a centrifugal blower or fan, which forces air into the horizontal air flow channels and propels the metered seed out of the air flow channels into the outlet seed tubes which extend out to and adjacent the furrow openers. The seed directing device is essentially a longitudinal square or rectangular plenum with a plurality of openings along one side, each opening of which connects with or forms each air flow channel. The outlet of the blower directs pressurized air into the plenum transversely to the axis of the openings. A baffle within the plenum creates substantially equal air flow into each opening. The blower is driven by a power take-off or a separate power source. As the grain drill is moved across the surface of the ground, seed is deposited within each of the furrows at metered intervals and as a function of the speed of travel. The outlet seed tubes provide a relatively straight path for proper and continuous seeding. Each of the metering mechanisms is provided with a gate or other blocking means in order to selectively block seed from entering the metering mechanism for selected seeding patterns. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front elevational view of the apparatus of this invention taken from the tractor side. FIG. 2 is a left side elevational view. FIG. 3 is a right side elevational view. FIG. 4 is top elevational view of the apparatus, including a plan view of the tandem grain drill during the planting position. FIG. 5 is a partial sectional view of the air blower and plenum portions of the seed conveying system. FIG. 6 is a partial sectional view of the seed metering means located downstream of the air-blower and plenum. FIG. 7 is a partial sectional view similar to FIG. 6 of another embodiment. FIG. 8 is a sectional view taken along the line 8--8 of FIG. 6. FIG. 9 is a top schematic like view of the drive mechanism used to operate the seed metering means. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Before explaining the present invention, in detail, it is to be understood that the invention is not limited in its application to the details of construction and arrangement of parts illustrated in the accompanied drawings, since the invention is capable of other embodiment and being practiced or carried out in a variety of ways. Also, it is to be understood that the phraseology or terminology employed herein is for the purpose for description and not of limitation. Referring now to FIG. 1, the apparatus that is shown when viewed from the tractor side looking toward the trailing or rear thereof. Behind the apparatus, not shown in FIGS. 1, 2 or 3, is a trailing seed drill unit of a type that is well known to those skilled in the art. The apparatus comprises a framework 10 which includes a tongue 12 for attachment to the tractor. The framework has attached thereto, a seed bin 14 having one or more openings at its top 16 which are sealably closed by lids 18 and 20. The framework is supported by ground engaging wheels 22 and 24. The seed bin includes ladders 26 and 28 on each side thereof for use by the operator especially during the filling of the seed bin 14. Stands 30 and 32 are provided for the operator to stand during the filling operation and to seal the bin with lids 18 and 20. At the forward side of the apparatus is a blower 40 which, in this instance, is driven by a power take-off shaft 42 from the tractor with the rotary force being transmitted by way of a belt 44 which interconnects sheaves 46 and 48, the latter of which is attached to the shaft 49 of the centrifugal blower 40. The outlet of the blower is directed into a longitudinal plenum 50 which on the backside or downstream side thereof includes a plurality of conveying conduits 52 which direct air therethrough to the metering system, hereafter described, and, which picks-up the seed for delivery to each of the seed drill units for planting. As shown in FIG. 3, an access door 56 is provided to the interior of the bin if required for any reason. Referring now to FIG. 5, the longitudinal plenum 50 is shown in cross-section. The blower 40 being attached thereto has its outlet aligned with an opening 60 on the top side of the plenum wherein the air will enter into the chamber 62. On the rear or downstream side of the plenum 50 are found a plurality of openings 64 to which sleeve 66 and the outlet air conveying conduits 52 are attached. Interiorly of the plenum chamber 62 is a vertical baffle 68 which extends upwardly from the bottom of plenum chamber to a point below the top, yet above the opening 64 leaving a space 70 therein between the opening 64 and the baffle 68. The baffle 68 extends longitudinally within the plenum at least the length of blower opening 60 and is provided to assure and create a substantially equal air pressure traversing through tubes 52, especially in those openings 64 which are closely adjacent the blower outlet opening 60. Referring now to FIG. 6, the seed metering means is shown. At an accessible location in the bottom of seed bin 14 are a plurality of seed cups 80 longitudinally aligned in row A and seed cups 82 aligned in row B. The cups are attached to the bottom of the bin by means of a flange plate 83 and a plurality of fasteners 84, although other means known in the art may be used to secure the cups to the bin. Each cup is identical and includes a P-shaped housing having a loop portion 86 and a stem portion 88 which housing is open at the front of the loop at 90. The bottom of the loop portion includes a straight section 92 and a curved fillet section 94. A star wheel 96 is attached to shaft 98, either as a square shaft or keyed to a rounded shaft for rotation as shown. The star wheel 96 is so located within the loop portion housing 86 so as to provide a substantial seal at the top 100 while permitting grain to pass through the lower portion 102 relative to the bottom plate 92 and 94 so that grain or seed will be carried in the manner shown into the stem conduit 88 which then connects to the air conveying conduit 52 which then carries the seed via conduit 53 to the seed drill. Between each of the seed cups 80 and 82, in the event a square drive shaft is used, a loosely fitting PVC conduit 110 is placed, which has been found to be effective to prevent interference and friction of the rotating shaft 98, as would otherwise occur if exposed to the grain within bin 14. As shown in FIG. 6, a typical seed cup cover 112, e.g. formed of a plastic material, is retained or snapped over the open end of the loop portion in the event selective rows of seed planting is necessary or desired for different corps. Suitable interior baffling 116 is shown as a means to deflect the grain in its downward movement into the opening 90 of the seed cups. FIG. 7 is an alternate embodiment of the invention wherein the seed cups are directed inwardly toward each other, otherwise identical numbers are used herein to identify identical parts as previously described. Suitable power transmission means is used to cause the shaft rotation to occur in the proper feed direction. FIG. 8 is a cross sectional view taken along the lines 8--8 of FIG. 6 and describes the view looking toward the seed cups placed in the bottom of bin 14. As noted, the seed cups 80 are staggered relative to seed cups 82. Each of the drive shafts 98A and 98B are attached to suitable and respective sprockets 120 and 122 driven, in this instance, by a chain 124 as hereafter schematically described in FIG. 9. FIG. 9 is a schematic of one means of driving the metering cup shafts and includes a plate 130 which is pivotally attached to shaft 132 which is suitably held to the framework 10 or to the bin 14. At the other end of the plate 130 is a shaft 134 which is rotatably attached to the plate and includes a small diameter tire 136 frictionally engaged with the ground engaging wheel 22 of the device of this invention. At the other end of the shaft 134 is a sprocket 138 which interconnects by way of chain 140 to sprocket 142 which rotates shaft 132. A sprocket 144 in turn includes a chain 146 which operates to rotate metering sprocket 120 and 122. A speed increaser or reducer 150 may be appropriately interposed to change the speeds of the shafts 98A and 98B. A hydraulic cylinder and piston means 160 is used to engage or disengage the tire 136 from the ground wheel 22. Certain modifications are within the scope of the invention as described and claimed herein. These include a concept of the seed bin and metering apparatus being a self-propelled device instead of being drawn by a tractor as shown herein. In addition, although the embodiments of FIGS. 6 and 7 herein show a variety of ways in which the metering cups may be placed at the bottom of the seed bin, another embodiment includes directing seed cups outwardly of each other. A variety of star wheel embodiments may be utilized in the invention and placed within the seed cups, depending upon the size of the grain and/or the amount of metering desired, merely by removing shaft 98 and replacing the desired star wheel therein.
A pnuematic distributing apparatus for seed or other ground receiving particles which has a mobile framework attached to or powered by a vehicle. A large capacity substantially sealed seed bin is disposed on the framework and feeds grain and/or fertilizer into a metering mechanism which deposits seed into a plurality of seed channels which intersect with corresponding pressurized air flow conduits which direct the seeds into outlet tubes adjacent ground furrow openers and deposit the seed into the furrows. Means are provided to block seed channels for selected seeding patterns.
0
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. patent application Ser. No. 13/182,107 filed on Jul. 13, 2011 (now U.S. Pat. No. 8,226,608), which is a continuation of U.S. patent application Ser. No. 12/767,570 (now U.S. Pat. No. 7,998,116) filed on Apr. 26, 2010, which is a continuation of U.S. patent application Ser. No. 10/591,190 (now U.S. Pat. No. 7,713,238) filed on Aug. 31, 2006, which is a national stage application under 35 U.S.C. §371 that claims the benefit of PCT/DK2006/000195 (published as WO2006/105794) filed on Apr. 6, 2006, which claims priority to the following Denmark patent applications: serial no. PA 2005 00483 filed on Apr. 6, 2005, Ser. No. PA 2005 00542 filed on Apr. 14, 2005, and Ser. No. PA 2005 00817 filed on Jun. 3, 2005. The entire contents of these prior applications are incorporated herein by reference. SUMMARY The present invention relates to a method of dispensing liquid medicine comprising the steps of providing a wearable, disposable dispensing device comprising a syringe having a cylinder and a plunger displaceable in said syringe cylinder for pressing medicine out of said syringe cylinder and a drive mechanism connected to said plunger for displacing said plunger in said cylinder, and an electrical motor connected to a battery and to said drive mechanism for providing a rotary force to said driving mechanism for displacing said plunger, displacing said plunger a certain distance in connection with a cycle of said driving mechanism. Methods of this type are known, wherein the electrical motor is controlled by a control means so as to carry out a certain number of revolutions for each cycle corresponding to the desired distance of displacement of the plunger. In connection with such methods it is important that no more than the predetermined amount of medicine be dispensed per cycle as otherwise life threatening dosages may be dispensed. When utilizing an electrical motor, a short circuit can entail that the motor does not stop after the predetermined number of revolutions or that the motor starts by itself. Security means have been suggested to ensure that the predetermined dosage is not exceeded, for instance monitoring the amount of liquid dispensed per cycle or monitoring the displacement distance of the plunger or the amount of revolutions of the motor per cycle with interruption means being activated if the monitored elements exceed a certain value. There exists a need for a simple and fail-safe method to avoid over-dosage of medicine. One main object of the invention is to meet this need. According to the invention this object is achieved by the cycle comprising rotating said electrical motor in a first direction of rotation and subsequently rotating said electrical motor in the opposite direction of rotation. Hereby, any short-circuit of the motor will not entail continued rotation of the motor in one direction with ensuing continued dispensing of medicine. The invention furthermore relates to a wearable, disposable medicine dispensing device comprising: a syringe having cylinder and a plunger displaceable in the syringe cylinder for pressing medicine out of said syringe cylinder, a drive mechanism connected to said plunger for displacing said plunger in said cylinder, and an electrical motor connected to a battery and to said drive mechanism for providing a rotary force to said driving mechanism for displacing said plunger, and control means adapted for repeatedly reversing the direction of rotation of said electrical motor. In a further aspect, the present invention relates to an actuator comprising: a rotational motor. one or more elongate, flexible elements such as a string, a filament, a strip, a ribbon and combinations thereof, said one or more elements being attached to said motor for rotation thereby and to a displaceable body, such that rotation of said motor twists said one or more elements and shortens the overall length thereof so that said displaceable body is displaced by the shortened element or elements. Such an actuator according to the invention may be used in connection with medicine dispensing devices, but also in any application where a rotational force or movement is to be utilized to displace a body. DESCRIPTION OF DRAWINGS In the following the invention will be described more in detail in connection with two embodiments shown, solely by way of example, in the accompanying drawings, where FIG. 1 shows a first embodiment of a device according to the invention seen in perspective and with the top part of the housing removed, FIG. 2 shows a perspective view of the drive mechanism of the device according to the invention in FIG. 1 , FIG. 3 is an exploded view of some of the drive mechanism elements of the device in FIG. 1 , and FIGS. 4 and 5 are views corresponding to FIG. 2 with the drive mechanism in other positions, and FIGS. 6-9 are views of a second embodiment of the device according to the invention corresponding to FIGS. 1 , 2 , 4 and 5 , respectively. FIGS. 10-14 show a perspective view of a third embodiment of the device according to the invention in different sequential states during a first half cycle during rotation of the electrical motor in a first direction of rotation, FIGS. 15 a, b and c are views of some of the drive mechanism elements of the device in FIGS. 10-14 in different states during the cycle. FIG. 16 . is a schematic perspective view of a first embodiment of an actuator according to the invention, and FIGS. 17 a - b very schematically show a second embodiment of an actuator according to the invention at two different phases of an actuation cycle. DETAILED DESCRIPTION Referring now to FIGS. 1-5 , a wearable disposable dispensing device for medicine referred to generally by the numeral 1 and of the type described in WO 2004/041330 and WO 2004/056412. the disclosure of which is hereby incorporated herein by reference, comprises a housing 2 , where only the bottom half is shown for the sake of clarity, a cylindrical medicine container or carpule 3 having at one end a silicone body for receiving a catheter for dispensing medicine from the interior of the carpule to a human body and being open at the opposite end to receive a flexible piston rod 5 for displacing an internal not shown plunger or piston in the carpule 3 for forcing medicine out through a catheter needle assembly connected to the silicone body 4 . The flexible piston 5 is composed of segments hinged together and outwardly threaded guided by a rail 6 received in recesses in each of the segments of the rod 5 . The not shown outward threads of the segments of the flexible piston rod 5 engage in a thread 8 of ratchet wheel 7 having teeth 9 along the periphery thereof. An electrical motor 10 electrically connected to a battery 11 and control means 12 is provided with a gear 13 meshing with a gear 14 attached to an outwardly threaded spindle or shaft 15 received in an inwardly threaded nut 16 attached a plate 17 provided with two slits 18 and 19 , extending parallel to the axis of said spindle 15 and a third slit 20 , extending at an angle to said axis. Two fixedly arranged pins 21 and 22 are received in the slits 18 and 19 , respectively such that the pins serve as guides to the to and fro displacement of the plate 17 by means of the spindle 15 when the electrical motor 10 rotates first in one directional rotation and thereafter in the opposite directional rotation. A protuberance 23 is arranged on the plate 17 to co-operate with two end stop contacts 24 and 25 electrically connected to the control means 12 for reversing the direction of rotation of the electrical motor when the protuberance 23 contacts one of the end stop contacts 24 or 25 . A pawl 26 is attached to a pivotable elongated body 27 having a pin 28 for being received in the oblique slit 20 and a hole 29 for receiving the pin 21 such that the body 27 is pivotable around the pin 21 . A ratchet 30 is fixedly attached to the housing 2 by means of a pin 31 and is located so as to engage the teeth 9 of the ratchet wheel 7 . The pawl 26 is displaceable from a retracted position where it does not engage the teeth 9 of the ratchet wheel 7 and in an engaged position in which it engages the teeth of the ratchet wheel and rotates the ratchet wheel in a clockwise direction. The displacement of the pawl 26 between the two positions indicated above takes place by the linear displacement of the plate 17 . When the plate 17 is displaced in the direction from the end stop contact 24 to the end stop contact 25 , the oblique slit 20 urges the pin 28 of the elongated body 27 in a direction 10 away from the carpule 3 such that the elongated body 27 pivots around the pin 21 in a clockwise direction, whereby the pawl 26 is moved in towards its retracted position relative to the ratchet wheel 7 . When the protuberance 23 on the plate 17 contacts the end stop contact 25 , the directional rotation of the motor 10 is reversed and the plate 17 is displaced in the direction from the end stop contact 25 towards the end stop contact 24 , whereby the oblique slit 20 forces the pin 28 towards the carpule 3 , whereby the elongated body 27 is forced to rotate in a counterclockwise direction whereby the pawl 26 is brought into contact with one of the teeth 9 of the ratchet wheel and rotates the ratchet wheel in a clockwise direction, while the ratchet rides over one of the other teeth 9 for locking the ratchet wheel against rotation in the counterclockwise direction. Thus, during one cycle of rotation in one direction and the opposite direction of the electrical motor 10 , the ratchet wheel 7 will be advanced by one tooth corresponding to one displacement of the pawl 26 from the retracted position thereof to the engaged position thereof. Referring now to FIGS. 6-9 , in this embodiment a coil spring 40 is attached to a pin 41 fixedly attached to the housing 2 and a pin 42 fixedly attached to the plate 17 . When the plate 17 is moved in the direction from end contact 24 towards the end contact 25 , the spring 40 is in tension, and when the plate 17 moves back in a direction from the end stop contact 25 towards the end stop contact 24 after reversion of the direction of rotation of the motor 10 , the spring 40 will be relaxed and exert a force in the same direction as the motor 10 on the plate 17 and thus reinforcing the force available to rotate the ratchet wheel 7 . Referring now to FIGS. 10-15 , the electrical motor 10 is electrically connected to a battery and control means and the axle of the motor is connected to a pair of twisted strings 35 or a band or similar device, which reduces its length when twisted and increases its length when untwisted, said length variation being provided by the rotation of the motor, i.e. the device is connected to the rotating axle of the motor at one end and connected to a pivotable body 78 at the opposite end. The pivotable body is provided with an extension 78 a comprising a pawl 74 arranged to engage the teeth 9 on the ratchet wheel 7 , as indicated in FIGS. 15 a . 15 b . 15 c . whereby the pivoting of the pivotable body 78 provides a rotation of the ratchet wheel 7 . A second pawl mechanism 72 , 84 is provided to prevent rotation of the ratchet wheel 7 in the opposite direction, again as shown in FIGS. 15 a - 15 c. The displacement of the pawl 74 between the two positions indicated in FIGS. 15 a and 15 b is provided by the reduction of the length of the twisted strings 35 by rotation of the motor and the displacement in the opposite direction is provided by the spring 40 during extension of the twisted strings 35 provided by rotation of the motor in the opposite direction, whereafter further rotation in this direction again reduces the length of the twisted strings 35 , whereby a complete cycle of rotation in one direction of the motor provides a movement of the pivotable body from the position shown in FIG. 15 a to the position shown in FIG. 15 b and back to the position shown in FIG. 15 a . this movement being provided by the twisted strings 35 being untwisted and twisted in the opposite direction during rotation of the motor in one direction. Thus, the rotation of the motor in one direction of rotation provides a full stroke for the pivotable body and thus the pawl mechanism moving the ratchet wheel one step forward and the following rotation of the motor in an opposite direction of rotation provides a further full stroke of the pivotable body and the pawl mechanism. Thus, during one cycle of rotation in one direction and the opposite direction of the electrical motor 10 , the ratchet wheel 7 will be advanced by two teeth corresponding to two displacements of the pawl 74 . The pivotable body 78 comprises a protuberance 78 a which co-operates with two end stop contacts 85 a and 85 b electrically connected to the control means for controlling the reversal of the direction of rotation of the electrical motor when the protuberance 78 a contacts the end stop contact 85 a . Due to the fact that the twisted strings 35 can only provide a pulling force on the pivotable body 78 , a spring 40 is connected to the pivotable body to provide the movement in the direction shown by the arrow in FIG. 10 . In the embodiment shown in the figures spring 40 is a coil spring, however, other types of springs, such as a rod spring could be provided for this purpose. Referring now to FIG. 16 , an actuator according to the invention is referred to generally by the numeral 50 and is identical to the actuator shown in FIGS. 10-14 . This actuator may be employed for any use requiring transformation of a rotation to a linear movement or a rotational force to a linear force. A rotation motor 51 is attached to a pair of elongate, flexible elements such as strings or filaments 52 by means of a rotational body 53 that may or may not function as a fly wheel. The elements 52 are attached to a pin 54 on a pivotable plate. Rotation of the motor in the direction R 1 will twist the strings 52 such that the length thereof is shortened until the pin 54 is displaced linearly in the direction R 2 whereby the plate 55 is rotated around pivot 56 in the direction R 3 . A tension spring 57 is attached to plate 55 at pin 58 and to a not shown frame at pin 59 . Rotation of the plate 55 will expand the spring 57 in the direction R 4 against the spring force thereof. Rotation of the motor 51 in the direction opposite R 1 will at first untwist the elements 52 whereby the length thereof becomes larger with the consequence that the spring 57 rotates the plate 55 in the direction opposite R 3 . Further rotation of the motor 51 in the direction opposite R 1 will twist the elements 52 again an eventually exert a force on said pin 54 in direction R 2 again, the direction of rotation being subsequently reversed again and the cycle starts anew. In case, a smaller interval is desired between each turn of the plate 55 in the direction R 3 , the motor 51 may reverse direction of rotation as soon the elements 52 have become untwisted to an extent that the spring 57 has pivoted the plate a certain distance in the direction opposite R 3 . Reference is now made to FIGS. 17 a - 17 b . where a motor 51 is attached to both opposed ends of an elongate, flexible element such as a string or filament 52 by means of a rotational body 53 that may or may not function as a fly wheel. The element 52 forms a loop 60 within which are located two bodies 61 and 62 . The body 61 is displaceable along a groove 63 in which a pin 64 of the body is slideably received. A spring 65 is attached to the displaceable body 61 such that displacement of said body 61 in the direction R 5 takes place against the biasing force exerted by the spring 65 . The other body 62 is fixedly arranged such that when twisting of the element 52 by rotation of the motor 51 takes place the loop 60 is reduced in size as seen in FIG. 17 b and the displaceable body 61 is forced towards the fixed body 62 along the groove 63 and against the spring force of the spring 65 . When the rotational direction of the motor is reversed so that it rotates in the direction R 7 , the element 52 will be untwisted, the loop 60 will enlarge and the spring 65 will displace the body in the direction R 6 . Although the groove is shown extending substantially linearly, it may obviously be curved and extend at different angles to the axis of the motor. The body 61 may be attached to a multitude of different driving or transmission mechanisms, for example the ratchet and pawl mechanisms shown in FIGS. 1-9 . A displaceable body should be taken to mean any body that can change position either by linear motion, curved motion, rotative motion, etc. and any combination thereof under the influence of a force applied to a point on or in said body. Displacement should likewise be taken to mean any change in position resulting from linear motion, curved motion, rotative motion, etc. and any combination thereof.
Some embodiments of a wearable, disposable medicine dispensing device may include a piston rod that is advanced to dispense medicine from the device. A rotational motor may be coupled to a drive mechanism so as to carry out a certain number of revolutions and thereby displace the piston rod by a desired distance. Such a device can be used in a method of dispensing liquid medicine.
0
FIELD OF THE INVENTION The present invention relates to a motor-operated brake system including an electric motor for producing amplified braking force. DESCRIPTION OF THE RELEVANT ART As disclosed in Japanese Patent Publication No. 48-26711, for example, a conventional automobile brake system includes a push rod coupled to a brake pedal and pushed by a thrust force applied from the brake pedal as it is depressed by the driver, a cylinder unit for converting the thrust force applied to the push rod to hydraulic pressure, a pressure transmitting device for transmitting the hydraulic pressure from the cylinder to drum- or disc-type braking mechanisms associated with respective wheels, and a servomechanism for amplifying the thrust force from the push rod with intake vacuum of the engine and applying the amplified force to the piston of the cylinder unit in order to obtain a strong braking force with a small depressing force imposed on the brake pedal. Therefore, the braking force can be increased by generating increased hydraulic pressure from the cylinder unit even when the depressing force on the brake pedal is small. Since the servomechanism is actuated by the intake vacuum of the engine, the outside diameter of the diaphragm of the servomechanism should be increased in order to produce increased force. With the increased outside diameter of the servomechanism diaphragm, however, the servomechanism is of a large size and requires a large installation space, imposing limitations on the layout thereof within an engine compartment. Dependent on the arrangement of the engine in the engine compartment, the vacuum pipe from an intake manifold may not appropriately be installed for connection to the servomechanism. Another problem is that when the engine is not in operation, the servomechanism is not actuated and hence no sufficient braking force can be generated by depressing the brake pedal deeply. SUMMARY OF THE INVENTION It is an object of the present invention to provide a motor-operated brake system which can produce sufficient braking force reliably even when the engine is shut off, requires no vacuum pipe from the engine, can generate sufficient braking force with an electric motor of a relatively small capacity, and is small in size. According to the present invention, there is provided a motor-operated brake system including an input rod coupled to a brake pedal and displaceable with an axial thrust force commensurate with the depressing force on the brake pedal, cylinder means having at least one piston operable by the thrust force applied to the input rod for producing hydraulic pressure, the cylinder means having a piston, hydraulic pressure transmitting means for transmitting the hydraulic pressure generated by the cylinder means to braking mechanisms associated respectively with wheels, servo means including an electric motor for producing rotational motion and a converting mechanism for converting the rotational motion from the electric motor to linear motion and transmitting the linear motion to the piston of the cylinder means, the servo means being arranged to apply an amplified force to the piston of the cylinder means, thrust detecting means for detecting the magnitude of the thrust force applied to the input rod, and control means responsive to a signal from the thrust detecting means for generating a motor control signal to control operation of the electric motor. The above and further objects, details and advantages of the present invention will become apparent from the following detailed description of a preferred embodiment thereof, when read in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a longitudinal cross-sectional view of a motor-operated brake system according to an embodiment of the present invention; FIG. is a block diagram of a control device in the motor-operated brake system; FIG. 3 is a flowchart of a control sequence executed by the control device; FIG. 4 is a graph showing a thrust force signal; FIG. 5 is a graph showing a motor control signal; and FIG. 6 is a graph showing the relationship between a push rod thrust force and a piston thrust force. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT As illustrated in FIG. 1, a ball screw mechanism 2 includes a nut member 3 disposed in a casing 1 and having a helical groove 3a defined in its inner peripheral surface, the nut member 3 having its opposite ends rotatably supported in the casing 1 by bearings 7, 8, a tubular shaft 4 extending axially through the nut member 3 and having a helical groove 4a defined in its outer peripheral surface in radial registry with the helical groove 3a of the nut member 3, and a plurality of balls 5 rollingly riding in the helical grooves 3a, 4a and movable through a circulatory path (not shown) defined in the nut member 3 as the nut member 3 rotates. The tubular shaft 4 has an open end and a closed end which are axially spaced from each other. The tubular shaft 4 also has an output rod 4b integral with the closed end. A push rod 9 is inserted in and parallel to the tubular shaft 4, and has a yoke 9a on its outer end and a spherical ember 9b on its inner end. The yoke 9a is coupled to a brake pedal (not shown), so that when the brake pedal is depressed, a thrust force is axially applied to the push rod 9. The push rod 9 is supported at its outer portion near the yoke 9a on the casing 1 by means of an elastomeric boot 10. The spherical member 9b is supported in a spherical bearing 11. The spherical bearing 11 is disposed in the tubular shaft 4 and is slightly movable axially therein. The spherical bearing 11 has one end engageable by a radially inward ridge 4c of the tubular shaft 4 which limits axial movement of the spherical bearing 11 to a certain range. Between the closed end of the tubular shaft 4 and the spherical bearing 11, there is disposed a thrust detector 12 in the form of a bridge circuit comprising four strain gages 12A, 12B, 12C, 12D (FIG. 2) with their electric resistances variable by an applied pressure or strain. The strain gages 12A, 12C on a pair of opposite arms of the bridge circuit are located between the closed end of the tubular shaft 4 and the spherical bearing 11 for detecting the thrust force of the push rod 9. The strain gages 12B, 12D on the other pair of opposite arms are positioned in a recess 4d defined in the closed end of the tubular shaft 4 for effecting temperature compensation. The bridge circuit of these strain gages produce at its output terminals output signals S 01 , S 02 that are temperature-compensated, as shown in FIG. 4, which are applied to a control device 40, as described later on. An electric motor 14 comprises magnets 15 fixed to an inner surface of the casing 1, a disc-shaped rotor 16, and a brush 18. The rotor 16 is fixed to the nut member 3 of the ball screw mechanism 2 substantially perpendicularly to the axis of the push rod 9 for rotation therewith. The electric motor 14 also includes an armature winding and a commutator (not shown) which are formed on the rotor 16 as printed circuits. The brush 18 which is housed in a brush holder 17 mounted on the casing 1 is pressed in contact with the commutator on the rotor 16 under the resiliency of a spring 19 acting on the brush 18. Operation of the electric motor 14 is controlled by the control device 40. When the electric motor 14 is energized, the nut member 3 rotates with the rotor 16 to axially displace the tubular shaft 4 (to the left in FIG. 1) for thereby amplifying the thrust force of the push rod 9. A master cylinder 20 comprises a cylinder body 21 having a cylinder 21a and a reservoir tank 22 mounted on the cylinder body 21. The cylinder body 21 is fixed to an end of the casing 1 by means of bolts 23 such that the cylinder 21a is substantially coaxial with the push rod 9. The cylinder 21a accommodates therein a first piston 24 and a second piston 25, and has two ports 26A, 26B near the first piston 24 and two ports 26C, 26D near the second piston 25, the ports 26A, 26B, 26C, 26D communicating with the reservoir tank 22. The first piston 24 has a hole 24a defined in its rear end portion and in which the output rod 4b is fitted. The rear end of the first piston 24 is held against the closed end of the tubular shaft 4. Thus, the first pison 24 is axially movable (to the left in FIG. 1) when pushed by the tubular shaft 4. An oil seal 27 is disposed between the rear end portion of the first piston 24 and the cylinder 21a. The first and second pistons 24, 25 define a first pressure chamber 28 therebetween, with a spring 29 disposed under compression between the first and second pistons 24, 25. A connecting rod 30 is attached axially to the front end of the first piston 24. When the first piston 24 returns (to the right in FIG. 1), the connecting rod 30 engages an engaging member 31 fixed to the rear end of the second piston 25, so that the second piston 25 moves with the first piston 24 upon returning travel. A second pressure chamber 32 is defined between the front end of the second piston 25 and the cylinder body 21, with a spring 33 held under compression therebetween. The pressure chambers 28, 32 are sealed by cup-shaped seal members 34, 35, 36, and connected to respective braking mechanisms through separate pipes and wheel cylinders (not shown) for applying a braking force to wheels under hydraulic pressure. When the first piston 24 is pushed by the tubular shaft 4 to produce a thrust force, the second piston 25 is pushed under the resiliency of the spring 29, and the ports 26A, 26C are closed by the respective seal members 34, 36, whereupon a hydraulic pressure is developed in the pressure chambers 28, 32. The hydraulic pressure is transmitted via the pipes to the braking mechanisms associated with the respective wheels. As the push rod 9 is released, the first and second pistons 24, 25 are moved to the right under the hydraulic pressure in the pipes and the bias of the springs 29, 33 for thereby allowing the braking fluid to return from the pipes into the pressure chambers 28, 32. At this time, a braking fluid is also allowed to flow through holes 26E, 26F defined in the pistons 24, 25 into the pressure chambers 28, 32. The control device 40 and its associated components will be described with reference to FIG. 2. The junction between the strain gages 12B, 12C is connected to the negative terminal of a power supply 46 which may be an automobile-mounted battery. The junction between the strain gages 12A, 12D is connected to an A power source of a constant-voltage circuit 50. Between the strain gages 12C, 12D, there is coupled a variable resistor 12E for zero adjustment. The output signals S 01 , S 02 are supplied from the junction between the strain gages 12A, 12B and a movable contact 12e of the variable resistor 12E. The output signals S 01 , S 02 applied to the control device 40 are amplified by an amplifier 41 and impressed as detected signals S 1 , S 2 on a microcomputer circuit (MCU) 43 through an A/D converter 42. The MCU 43 comprises a CPU, a clock pulse generator, a ROM, a RAM, and an I/O port, and is operated by control software, described later. The output port of the MCU 43 is connected to a relay circuit 51 and a driver circuit 44. The control device 40 is energized by a power supply circuit including the power supply 46 which is connected through a fuse circuit 47 and an ignition key switch circuit 48 to a fuse circuit 49 in the control device 40. The output terminal of the fuse circuit 49 is coupled to the constant-voltage circuit 50 which supplies a constant voltage to the control device 40 and the relay circuit 51 which is turned selectively on and off by a command signal O L from the MCU 43. The MCU 43 is also connected to the constant-voltage circuit 50. When the power supply is switched on, the MCU 43 receives a reset signal from the constant-voltage circuit 50 and enables a timer in the MCU 43 to check whether the CPU operates normally or not. The output terminal of the relay circuit 51 is connected to a resistor 52 for detecting an armature current, the electric motor 14, and an FET 45 in series. The FET 45 has a drain terminal connected to the electric motor 14, a source terminal connected to the negative terminal of the power supply, and a gate terminal connected to the output terminal of the driver circuit 44. The voltage developed across the resistor 52 is applied via an amplifier circuit 54 as a detected current signal S 3 to the A/D converter 42. A diode 53 is connected in a reverse direction across the series-connected resistor 52 and electric motor 14. Operation of the control device 40 will be described with reference to the control software shown in FIG. 3. When the switch circuit 48 is turned on, a reset signal is applied from the constant-voltage circuit 50 to the MCU 43 which starts its operation in a step P 0 . Then, data in the register in the CPU and the RAM are cleared, and the I/O port is initilized in a step P 1 . A step P 2 reads in a detected current signal S 3 and ascertains whether it is zero or not. If zero, then a relay signal O L is issued to turn on the relay circuit 51, and if not, then the relay circuit 51 is de-energized, and an initial failure diagnosis is effected. A step P 3 reads in detected thrust signals S 1 , S 2 from the thrust detector 12. Then, a step P 4 carries out the caculation: (S 1 +S 2 )/2 and checks if this value falls within a prescribed range. If not in the prescribed range, then it is determined that the thrust detector 12 is out of order, and the relay circuit 51 is turned off to stop the operation of the electric motor 14. If in the prescribed range, then control goes to a step P 5 to calcuate the thrust force S=S 1 -S 2 , followed by a step P 6 which fetches stored data addressed by the thrust force S from a look-up table. The look-up table stores control signals (control duty ratios) D for the electric motor 14 in relation to thrust forces S. In a step P 7 , a fetched control signal D is applied to the driver circuit 44 which coverts the control signal D to a PWM signal to control the duty ratio of the FET 45 for thereby controlling the operation of the electric motor 14. The signal S 3 indicative of the armature current of the electric motor 14 at this time is read in a step P 8 . A next step P 9 ascertains whether the read signal S 3 is of a normal value or not. If the signal S 3 is normal in the step P 9 , then control returns to the step P 3 to repeat the above process. If not normal, then the relay circuit 51 is turned off to shut off the electric motor 14. When the brake pedal is depressed to produce a thrust force li (FIG. 6) on the push rod 9, therefore, a rotational force corresponding to the thrust force li and based on the look-up table is generated by the electric motor 14. The rotational force of the electric motor 14 is then converted by the ball screw mechanism 2 to an axial displacement of the push rod 9, which is then imparted to the first piston 24. The thrust force (output force) of the first piston 24, as indicated by lo in FIG. 6, enables the master cylinder 20 to produce a hydraulic pressure commensurate with the thrust force on the push rod 9. With the present invention, as described above, the electric motor is employed, rather than an engine intake vacuum, to produce a power source for the servo mechanism. Therefore, even when the engine is not in operation, a sufficient braking force can be generated by the brake system. The braking force can be controlled in smaller increments as the detected signal representing the thrust force on the push rod is processed. Since sufficient braking forces can be obtained by the small-capacity electric motor, the entire brake system may be small in size, requires a small installation space, and can be arranged with greater freedom in an engine compartment. Inasmuch as no engine intake vacuum is relied upon, difficulty in the layout of vacuum pipes is not encountered. Although there has been described what is at present considered to be the preferred embodiment of the present invention, it will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiment is therefore to be considered in all aspects as illustrative, and not restrictive. The scope of the invention is indicated by the appended claims rather than by the foregoing description.
A motor-operated brake system includes an input rod coupled to a brake pedal and displaceable with an axial thrust force commensurate with the depressing force on the brake pedal, a cylinder having at least one piston operable by the thrust force applied to the input rod for producing hydraulic pressure, the cylinder having a piston, a hydraulic pressure transmitting device for transmitting the hydraulic pressure generated by the cylinder to braking mechanisms associated respectively with wheels, a servo mechanism including an electric motor for producing rotational motion and a converting mechanism for converting the rotational motion from the electric motor to linear motion and transmitting the linear motion to the piston of the cylinder, the servo mechanism being arranged to apply an amplified force to the piston of the cylinder, a thrust detector for detecting the magnitude of the thrust force applied to the input rod, and a control device responsive to a signal from the thrust detector for generating a motor control signal to control operation of the electric motor.
1
REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. application Ser. No. 523,466, filed Aug. 16, 1983, now abandoned, which was a continuation-in-part of commonly assigned U.S. application Ser. Nos. 341,363, filed Jan. 21, 1982 now U.S. Pat. No. 4,405,652 and 445,064 filed Nov. 29, 1982, now U.S. Pat. No. 4,570,534. BACKGROUND OF THE INVENTION There is a continuing consumer demand for low calorie foods and beverages. Market growth and penetration of low calorie soft drinks and light beers have risen dramatically. The wine industry has recently introduced several low calorie wines which appear to be gaining consumer appeal. In keeping with this trend, several alcohol free wines have been introduced but with questionable and varying degrees of acceptance because of quality. However, of far greater importance is the ever increasing requirement for an alcohol free beverage for those who elect not to partake in alcohol for diverse reasons and for those who may have a drinking problem. Thus, there remains a need for a consumer acceptable alcohol free wine of improved quality. In the past, efforts have been made to produce non-alcohol wine using methodology of distillation and/or evaporation. Reports on such efforts, generally indicate poor quality. These processes involved either high temperatures or long holding time due to the nature of the equipment involved. As would be expected, a large reduction of the original water and consequent concentration of non-volatile acids would take place. SUMMARY OF THE INVENTION A principal object of the invention is to provide an alcohol free wine that responds to the identified consumer requirement and/or need that is not filled by any other wine now sold in the United States or abroad, namely, a wine with substantially fewer calories, appealing taste and, above all, substantially no alcohol. Another object is an alcohol free wine production process that may be installed and deployed year round without limitation to times of harvest or seasons of the year. Still another object is to utilize a finished table wine and convert it into a low calorie, alcohol free wine. A further object is to provide an improved process for converting a finished table wine to an alcohol free wine in which essentially all of the feed wine without the alcohol and highly volatile ingredients appears in the finished product. A still further object is to produce a high proof vapor by-product from the alcohol free wine production process that is a superior quality brandy alcohol. The term "alcohol-free" as used herein is a wine derived beverage having less than 0.5% alcohol content considered by the Bureau of Alcohol, Tobacco Products and Firearms Division of the U.S. Treasury Department as not being a wine for tax purposes. It should be understood that if this limit varies it is intended that the term "alcohol-free" as used herein will vary accordingly. BRIEF DESCRIPTION OF THE DRAWINGS The FIGURE is a schematic view of the flow diagram of the alcohol free wine production process incorporating the teachings of the present invention. DETAILED DESCRIPTION In the Figure, an embodiment of the invention is illustrated on which a wine preblend is processed and converted into an alcohol free wine and a superior brandy alcohol by-product. Thus, an original finished table feed wine from tank 10 normally having 11-12% alcohol content and demineralized and/or distilled water from tank 12 are fed into a mixing tank 14 within which a wine preblend is formed. Any type of mixing system may be employed including pump or mechanical agitator. A ratio of approximately 58% feed wine to 42% water will produce a workable preblend. In any event, the preblend will have an alcohol content of 6-7% and according to a successful embodiment of the invention possess an alcohol content of approximately 6.8%. As will be apparent shortly, the addition of water protects and preserves the essential character and oganoleptic properties of the original table wine without degradation or scorching during the subsequent processing steps. Enough water is added to the feed wine for the preblend to arrive at an alcohol reduced base wine that will permit final cutting by water of alcohol to below 0.5% and to keep the original feed wine content about 50% in the final product (whether final water content is derived from this feed wine or added water). The wine preblend is then fed into centrifugal film evaporator 16 which operates in reducing the preblend into a liquid phase which is an alcohol reduced base wine fed therefrom into receiver 18 and a vapor phase which is condensed. The centrifugal film evaporator 16 is disclosed in detail in the above referenced patent applications. Towards this end, the evaporator 16 may be obtained commercially from Alfa-Laval AB, Lund, Sweden under its tradenames CMF6 and CMF 9. Unlike those specific applications the feed rate of the preblend is reduced enough to obtain a base wine having less an 1% alcohol. In some instances, the rate is reduced to one-third to assure contact of the liquid as a thin film on the steamheated cones of the evaporator. Moreover, operation of the process of this invention is at very high vacuum conditions. The contact time of the preblend with the heat transfer surfaces of the evaporator is very short and less than a second; and, therefore, no molecular decomposition or transformation takes place due to chemical reaction. The alcohol reduced base wine leaving the evaporator 16 will range in alcohol content from 0.5% to 1% and in accordance with successful applications of this invention will normally be approximately 0.70-0.8% and preferably 0.75% alcohol. In addition, the yield has ranged from 60-65% of the feed wine. Referring now to the vapor phase system, the vapor phase from the evaporator 16 may be processed according to application Ser. No. 341,363 or may be exposed to a rectifying action within the column 20 which may be of the type disclosed in application Ser. No. 445,064. Similarly, the higher proof vapor product is condensed and cooled within condenser 22, fed into receiver 23 and then transferred to a storage tank 24 by pump 26 through back pressure control valve 28. A vacuum for system is provided by vacuum pump 29 which is connected to the receiver 18 as shown. A reflux return line 30 having rotometer 32 feeds the higher proof by-product back to the top of the column 20 through the reflux control valve 33 to facilitate and enhance the distillation process. Pump 34 draws the alcohol reduced base wine from evaporator 16 into the receiver 18. This base wine is then cooled by heat exchange 36 and then fed into storage tank 37. The essential character and organoleptic properties of the original feed wine including the ph level is retained by the alcohol free base wine in tank 37. However, some of the original bouquet is lost with the removal of the higher alcohols by the evaporator 16. Accordingly, the present invention contemplates adding grape juice concentrate to restore flavor and bouquet. The concentrate is produced in the Alfa-Laval evaporator and therefore such a concentrate has no molecular decomposition or transformation due to chemical reaction. This addition may be done directly into tank 37 from juice concentrate tank 38 or perhaps at some other location in the process if desired or found more practical. This mixture will normally have approximately 0.6% alcohol and may be filtered at this time by filter 39 which may be of the millipore type. The remaining processing steps may be performed shortly thereafter or at a later period of time at the same plant, wine making facility or at a removed bottling plant. Towards this end, if the bottling plant is at a different location, the alcohol base wine and grape juice concentrate mixture will be appropriately transferred to tank 40. Further demineralized water from tank 41 will be added together with citric acid from source 42 as well as further grape juice concentrate from source 43. The citric acid contributes to mouth feel and desired level of tartness. The added grape juice concentrate finally adjusts the organoleptic level of taste. The alcohol content of the mixture is now lowered to a level below 0.5%. Thereafter, the mixture is filtered at station 44 by a millipore filter. Carbonization (CO 2 ) is then introduced at station 48. Normally, 350-400 grams/100/ml will be sufficient for such purposes to attain a prescribed level of effervescence for improvement of tactual properties. Then the mixture may have sulphur dioxide (SO 2 ) added as a preservative. At bottling station 52, the mixture is discharged into bottles by means of a conventional counter pressure filler and thereafter capped. In order to complete the preservation of the bottled mixture, a pasteurization step 54 is employed if desired or necessary. Suitable grape juice concentrate usable with the present invention for producing an alcohol free white wine using a chablis feed wine are the Muscat and blends thereof, with the main volume being Thompson or French Columbard seedless grape juice in the proportion of about 20%-10% to 80% to 90%, In blending an alcohol free rose wine, a Malvasia Bianco or Muscat concentrate would be substituted for the Muscat in the same proportions. In addition, Red Concord grape juice concentrate for coloring could be added to the alcohol free white wine beverage along with enough Muscat to impart a rose character. Similarly, in producing an alcohol free red wine, enough Red Concord grape juice concentrate may be added to the alcohol free white wine beverage for obtaining the desired red wine color. It is also contemplated that the alcohol free drinkable white wine beverage may be utilized to manufacture a champagne. In this connection, a yeast-type of character is sought; and either an additive may be introduced for such purpose or the beverage may be subjected to further fermentation which would have the same effect. In view of adding sulphur dioxide as a preservative or in conjunction therewith, the finished and bottled alcohol free wine beverage may be pasteurized according to conventional techniques to eliminate any possible bacteria, yeast or other organism and/or spores. In addition, the CMF equipment could be deployed for flash pasteurization by exposing the thin film of base wine with demineralized water from tank 37 to cone temperatures of about 170% F. with no vaporization vacuum applied. The following examples describe the manner and process of making and using the invention and sets forth the best mode contemplated by the inventor of carrying out the invention but are not to be construed as limiting. In carrying out these and other examples the chemical analysis results reported were determined by gas chromatograph. EXAMPLE 1 Employing the apparatus and system described above and depicted in the Figure, a matured California white chablis feed wine at 11.2% alcohol was processed as follows utilizing an Alfa-Laval CMF6 and the following parameters. First a preblend was produced in mixing tank 14 having an alcohol content of 6.35% by mixing 1166 gallons of the feed wine with 870 gallons of demineralized water. ______________________________________Preblend Feed Rate 284 g.p.h.CMF Vacuum 27.5" hgCMF Steam Temperature 58° C.CMF Steam Controller -.88 BarCMF Vapor Temperature 40° C.______________________________________The mixture balance was as follows:Entering CMF Pre- -2036 w.g. at 6.35% = 129.29 absoluteblend Feed gallons alcoholLeaving CMF Wine -1297 w.g. at 0.75% = 9.7 absoluteBase gallons alcoholLeaving CMF Vapor -717 w.g. at 15.9% = 114.0 absoluteCondensator gallons alcoholTotal Recovery 2014 w.g. = 123.7 absolute gallons alcohol______________________________________ ##STR1## ##STR2##______________________________________ The base wine thus produced was blended with about 185 gallons white grape juice concentrate (at 62° Brix) in tank 37. After transfer to tank 40, final blending was performed utilizing the mixture of 64% base wine (with concentrate), 9.5% white grape juice concentrate (at 62° Brix) and 26.5% demineralized water. About 3.5 lbs of citric acid were added and thereafter the mixture was filtered. In addition 1/2 lb of SO 2 /1000 gal of liquid was added as a preservative. The beverage was carbonated by introducing 370±20 milligram/100 ml of CO 2 . The finished product was bottled possessing the desirable character of the original chablis feed wine as an alcohol free white wine beverage with an alcohol content of 0.45%. EXAMPLE 2 Employing the apparatus and system described and depicted in the Figure, 966 gallons of a matured California Rose feed wine was blended with 574 gallons of demineralized water to produce a preblend having an alcohol content of 7.42%. The parameters of the system were set as follows: ______________________________________Preblend Feed Rate 310 gphCMF Vacuum 27.5" hgCMF Steam Temperature 59° C.CMF Steam Controller -.85 BarCMF Vapor Temperature 40° C.______________________________________Entering CMF Preblend 1540 gals at 7.42% = 114 gallonsFeed absolute alcoholLeaving CMF Wine 990 gals at 0.93% = 9.2 gallonsBase absolute alcoholLeaving CMF Vapor 539 gals at 18% = 97 gallonsCondensate absolute alcoholTotal Recovery 1529 gals 106.2______________________________________Recovery based on diluted wine feed = 64.3%Recovery based on original wine process = 103%______________________________________ The base wine thus produced was blended with about 185 gallons of white grape juice concentrate in tank 37. After transfer to tank 40, final blending was performed utilizing 64% base wine (with concentrate), 1.5% red grape juice concentrate for color, 8% white grape juice concentrate and 26.5% gallons of demineralized water. About 31/2 lbs/1000 gal. of citric acid/1000 gallons of liquid were added and the mixture was then filtered. In addition, 1/2 lb of SO 2 /1000 gal of liquid was added as a preservative. The beverage was carbonated by introducing 370±20 milligram/100 ml of CO 2 . The finished product was bottled possessing the desirable character of the original rose feed wine as an alcohol free rose wine beverage having 0.43% alcohol content. EXAMPLE 3 The procedure of employing the apparatus of the Figure and Example 1, a California white chablis feed wine was treated in arriving at an alcohol free wine beverage. Chemical analysis of the original chablis feed wine, the preblend, the alcohol free wine base, the base with concentrate in tank 37, and finished bottled alcohol free white wine beverage is given in Table 1 below. TABLE 1__________________________________________________________________________ Alcohol Preblend Alcohol Free White Plus Free Base Beverage Feedwine Water Wine Plus Finished and (Chablis) Feedwine Base Concentrate Bottled__________________________________________________________________________Hydroxymethyl 0.01 -- -- 0.03 0.02FurfuralFurfural 0.14 0.06 0.11 0.15 0.05Tannin, mg/liter 398 160 285 420 228__________________________________________________________________________ EXAMPLE 4 Employing the apparatus of the Figure and the procedure of Example 2, a California rose feed wine was treated in arriving at an alcohol free wine beverage. Chemical analysis of the finished bottled alcohol free rose wine beverage is given in Table 2 below: TABLE 2______________________________________ Alcohol Free Rose Beverage Finished Bottle______________________________________Hydroxymethyl furfural 0.09Furfural 0.06Tannin, mg/liter 338______________________________________ Of particular significance in obtaining an acceptable alcohol free wine beverage by the present invention having desirable organoleptic properties while possessing the desirable character of the original matured feed wine are the following results based on chemical data and analysis comparable to the foregoing tables: i. the hydroxymethyl furfural level is reduced to a level below 1/10 gram/100 liters. This ingredient contributes to a cooked character. ii. the furfural level is reduced by approximately 1/3 to 1/2. iii. The tannins are reduced by about 1/2. Tannins provide an astringent character. Bottled alcohol free white, rose and red wines of this invention possessed the following ingredients: ______________________________________Dealcoholized wine 57.0%Reconstituted grape juice concentrate 42.6%(concentrate and water)Carbon dioxide (370 mg/100 ml) 0.37%Citric acid (3.5 lbs/1000 gal) 0.042%Sulfur Dioxide (170 ppm total) 0.017%______________________________________ Thus the several aforenoted objects and advantages are most effectively attained. Although several somewhat preferred embodiments have been disclosed and described in detail herein, it should be understood that this inventionis in no sense limited thereby and its scope is to be determined by that of the appended claims.
An alcohol free wine beverage is produced by diluting a table wine with demineralized water and feeding the diluted wine to a centrifugal film evaporator where alcohol is stripped from the wine to produce an alcohol free wine base. The wine base is then mixed with grape juice concentrate to produce a finished alcohol free wine. Other ingredients may be added to the wine base such as carbon dioxide, citrus juice and preservatives, and additional demineralized water may be added to further lower the alcohol content prior to bottling.
0
CROSS-REFERENCE TO RELATED APPLICATION Not applicable. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT Not applicable. FIELD OF THE INVENTION The invention relates to a method of leveling a mobile trailer that contains medical imaging or other clinical equipment. BACKGROUND OF THE INVENTION In the area of recreational vehicles such as travel trailers and motor homes, and other general transportable vehicles, there is a need for leveling when these vehicles are parked for use. Recreational vehicles and campers are usually parked in campsites where the parking area is not always level. Various systems are found in the prior art relating to leveling such vehicles. These systems comprise at least a lift mechanism and a level sensing device. Generally, the designs use mechanical, electromechanical, or hydraulic jacks and level sensors for leveling the vehicles. The devices are strategically mounted to the underbody or chassis of the vehicle to achieve the leveling quickly and efficiently. The number of jacks and level sensors used in each application are dependent on the size of the vehicle and the weight of the vehicle being supported, among other things. In one example, a recreational vehicle is equipped with four jacks in the form of hydraulic cylinders mounted to the vehicle frame. Two jacks are located adjacent to the rear of the vehicle and two jacks are located adjacent to the front of the vehicle. In another example, a vehicle leveling system has three jacks, two of which are located at the rearward end of the vehicle and one of which is located at the forward end of the vehicle. The use of a single front jack reduces twisting of the vehicle frame, however, it makes the system less stable because two corners of the vehicle are left unsupported. There is a need for transportable medical equipment in our society today. In areas where medical facilities are not readily accessible, or in areas that experienced disaster and the infrastructure is in a state of disrepair, a mobile medical facility is essential. Manufacturers are sensitive to this need and are providing equipment to meet this demand. Transportable medical equipment trailers are known in the prior art. The need for leveling of these equipment trailers is greater than for the recreational vehicles and campers because of the sophistication and the sensitivity of the medical equipment. Types of equipment used in a transportable medical trailer include, PET/CT scan machines, MRI machines, and CT machines The medical equipment transported in a mobile unit can include at least two machines mounted together such as PET/CT machine. These machines need to be aligned prior to operation. Any deviation from the recommended alignment of the machines in the trailer could result in parallax errors, and possibly, error in diagnosis. These trailers are typically towed behind a semi-tractor and dropped off at a clinical location. The front jacks will be used to lift and support the front of the trailer when it is detached from the tow vehicle and the driver will initially level the trailer, and then leave. Through the course of the day, as environmental conditions change, the level of the trailer may change and need to be re-leveled. It is important that medical clinical personnel be able to perform this function as conditions change, or else use of the machines in the trailer may have to be suspended until the trailer can be re-leveled. The current invention addresses the shortcomings of the prior art. SUMMARY OF THE INVENTION The invention provides a high accuracy medical trailer leveling system capable of detecting at least three level orientations including level along a longitudinal direction, level along a lateral direction at the front of the trailer and level along a lateral direction at the rear of the trailer. The system may have sensors that detect a level orientation in the longitudinal direction at the front of the trailer and a level orientation in the longitudinal direction at the rear of the trailer, in addition to the functions of those sensors detecting lateral level at the front and rear. A touch pad of the system preferably has buttons for controlling the system and a display screen, the display screen being capable of displaying a level condition in a particular location of the trailer and direction. The display screen can display the level orientation of side to side, front; side to side, rear; and front to back, and can also display the angle of inclination. In another preferred aspect, one set of lights on the control pad indicates which jacks to actuate to level the vehicle, and another set of lights indicates which jacks are being actuated. These particular objects and advantages may apply to only some embodiments falling within the claims and thus do not define the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a trailer used in conjunction with the present invention; FIG. 2 is a diagram of a controller and level sensors according to the present invention; FIG. 3 is a plan view of the medical trailer leveling touch-pad of FIG. 2 ; FIG. 3A is a detail view of the directional keypad portion of the touchpad of FIG. 3 ; and FIG. 4 is a plan view of the lift mechanism of FIG. 1 . Like reference symbols in the various drawings indicate like elements. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. 1 , a representation of a medical equipment trailer 10 useful for the present invention is shown. Also shown in FIG. 1 is a lift mechanism 26 located at the front right side of medical equipment trailer 10 . Lift mechanism 26 is one of a plurality of lift mechanisms that are employed in this system. The present invention employs at least four lift mechanisms, including mechanisms 24 , 26 , 28 , and 30 , ( FIG. 2 ). The operation of the lift mechanisms will be discussed in more detail with reference to FIGS. 2 and 4 . Included in the medical equipment trailer 10 is a chassis structure 20 (not shown) that will also be discussed in more detail with reference to FIG. 2 . Chassis structure 20 represents the structural frame of medical equipment trailer 10 , on which the equipment inside the trailer is supported and to which the walls, wheels and lift mechanisms are mounted. Referring to FIG. 2 , a depiction of trailer chassis structure 20 is shown. Chassis structure 20 contains lift mechanisms 24 , 26 , 28 , and 30 that are used in part to level medical equipment trailer 10 . Lift mechanisms 24 and 26 are located at the front end of medical equipment trailer 10 and serve as landing gear. Landing gear should be understood to be the front lift mechanisms that are extended prior to detaching trailer 10 from the truck. Lift mechanism 26 is located at the right hand side and lift mechanism 24 on the left hand side. Lift mechanisms 28 and 30 are located at the rear end of medical equipment trailer 10 with lift mechanism 28 located on the left hand side and lift mechanism 30 on the right hand side. Activation of lift mechanisms 24 , 26 , 28 , and 30 are initiated from touchpad 40 . The lift mechanisms can be activated individually or in pairs. More details on the operation of touchpad 40 are given with reference to FIGS. 3-3A . Still referring to FIG. 2 , the present invention uses two bidirectional level sensors 34 and 36 , located at the front and rear of medical equipment trailer 10 . The level sensors used in this invention are known in the art and can include bubble level sensors, accelerometers, or any other type that detects a level mismatch. Each sensor senses longitudinal (front-rear) level and also senses lateral (side to side) level, so each sensor is oriented in the trailer to have one of its axes lined up with the longitudinal axis of the trailer and the other axis of the sensor lined up with a lateral axis of the trailer. Preferably, the sensors are on or close to the lateral center of the trailer. Alternatively, if unidirectional sensors were used, four sensors could be used, one longitudinally oriented and one laterally oriented at each end of the trailer. With bi-direction sensors, level sensor 36 is located at the front end of medical equipment trailer 10 and is used in conjunction with lift mechanisms 24 and 26 to make level adjustments to the front end of medical equipment trailer 10 for proper functioning of the equipment housed in medical equipment trailer 10 . Conversely, level sensor 34 is located at the rear end of medical equipment trailer 10 and is used in conjunction with lift mechanisms 28 and 30 to attain the recommended leveling. Both level sensor 34 and level sensor 36 are used to ensure that medical equipment trailer 10 is level relative to a horizontal plane as determined by gravity. Level sensors 34 and 36 are configured for accuracy levels of 0.1° front to rear, 0.05° side to side (left to right) in the front, and 0.05° side to side (left to right) in the rear of medical equipment trailer 10 . These accuracy limits are relative to the horizontal plane. Also shown in FIG. 2 is a controller 38 remotely attached to level sensors 34 and 36 . Controller 38 is used in conjunction with lift mechanisms 24 , 26 , 28 , and 30 to process level information from sensor 34 and sensor 36 to screen 52 , as well as receive input commands from keypad 40 and provide outputs thereto. Controller 38 may be positioned inside a compartment that is accessible from outside of the trailer, and another controller 38 (not shown) could be provided inside the trailer. Medical equipment trailer 10 will generally weigh in excess of 50,000 lbs., with the bulk of the weight concentrated toward the rear end. The front of medical equipment trailer 10 is reserved for such things as a waiting area, prep area, and computer equipment. Because of the weight of medical equipment, trailer 10 and the installed machines and its distribution, it is inherently difficult to achieve the system level within tolerance limits which permit proper functioning of the installed machines. Advantageously using two bidirectional level sensors 34 and 36 , and strategically placing level sensor 36 at the front end and level sensor 34 at the rear end of medical equipment trailer 10 , helps to substantially reduce twist, and compensate for it during leveling. Twist is regarded as the deformation of chassis 20 as a result of overly extending any one corner relative to the diagonally opposite corner. Level sensor 36 is used in conjunction with both lift mechanism 24 and lift mechanism 26 to achieve and maintain the recommended level position for the front end of medical equipment trailer 10 . Likewise, level sensor 34 is used in conjunction with both lift mechanism 28 and lift mechanism 30 to achieve the recommended level states for the rear end of medical equipment trailer 10 . Twist is minimized by maintaining a zero level between level sensor 36 and level sensor 34 . Zero level should be understood to mean that the two sensors are equal elevation above the ground and the sides of each sensor are equal elevation above the ground. Referring to FIG. 3 a touchpad 40 for use in the leveling operation of medical equipment trailer 10 is shown. Touchpad 40 is enclosed in an accessory panel that is mounted on the side of medical equipment trailer 10 . The accessory panel (not shown) is accessible from outside of medical equipment trailer 10 . Touchpad 40 is activated by pressing power button 42 . Amber LED 44 , when illuminated, indicates that power is on and touchpad 40 is ready for operation. Screen 52 displays the leveling states of the trailer. Select button 46 is used for scrolling through the displayed information on touchpad screen 52 . Green LED 48 , when illuminated, indicates that medical equipment trailer 10 is level. Red LED 50 , when illuminated, indicates that medical equipment trailer 10 is not level. If Red LED 50 is illuminated, error messages will be shown on screen 52 , including, low voltage, end of stroke, pump time out, etc. Select button 46 is additionally used to cycle through three defined states of leveling. The three states of level are side to side front, side to side rear, and front to rear. Still referring to FIG. 3 , auto button 56 is used to initiate the automatic level cycle for medical equipment trailer 10 . Amber LED 66 , when illuminated, indicates that auto button 56 is activated. In certain examples, automatic leveling is the first option used once medical equipment trailer 10 is parked in its working location. Lift mechanisms 24 and 26 are extended by activating manual button 54 in conjunction with extend button 58 . It is recommended that lift mechanisms 24 and 26 be extended prior to removing from the truck. Lift mechanisms 24 and 26 serve as landing gear. With lift mechanisms 24 and 26 extended, the automatic leveling cycle can be initiated by pressing auto button 56 . The leveling states information is transmitted from level sensor 36 in conjunction with lift mechanisms 24 and 26 through controller 38 and displayed on touchpad screen 52 . Level state is annunciated by the illumination of green LED 80 and message “Platform Level”. Green LED 80 remains illuminated as long as the trailer 10 is level. Referring again to FIG. 3 , manual button 54 is used to initiate the manual leveling of medical equipment trailer 10 . Manual leveling is required when auto leveling does not attain the required accuracy level for proper functioning of medical equipment trailer 10 . For example, if the front jacks need to be extended extraordinarily to detach the tow vehicle, it may be necessary to manually lower the front of the trailer before attempting automatic leveling of the trailer. Activation of manual button 54 is confirmed by the illumination of amber LED 62 . In manual mode, extend button 58 and retract button 60 can be pressed to extend or retract, respectively, individual pairs of lift mechanisms 24 and 26 , or 28 and 30 . Extend button 58 facilitates the manual extension of lift mechanisms 24 , 26 , 28 , and 30 in pairs. For example, front button 72 extends jacks 24 and 26 , left button 78 extends jacks 24 and 28 , right button 74 extends jacks 26 and 30 and rear button 76 extends jacks 28 and 30 . The jacks may also be extended individually, if for example the front and right buttons pressed simultaneously and held down result in only jack 26 extending. Activation of extend button 58 is confirmed by the illumination of amber LED 68 . Retract button 60 is used to retract lift mechanism 24 , 26 , 28 , and 30 in manual mode, indicated by LED 62 and LED 64 . When manual button 54 and retract button 60 are actuated as indicated by the two LEDs 62 and 64 , the directional keypad 70 works similarly to the way it works in manual extension mode, described above, to retract the jacks in pairs or individually. Referring to FIG. 3A , keypad 70 contains directional buttons front 72 , right 74 , rear 76 , and left 78 , which are momentary contact switches. Keypad 70 also shows status LEDs 80 , 82 , 84 , 86 , and 88 used in conjunction with the directional buttons in both auto and manual leveling of medical equipment trailer 10 . Keypad 70 , used in conjunction with touchpad screen 52 , is used to attain the desired accuracy level for medical equipment trailer 10 . Directional buttons and LEDs on keypad 70 can be used to ‘fine tune’ the level states. In one example, screen 52 displays that the side to side rear is not level. Pressing left button 78 along with rear button 76 simultaneously engages lift mechanism 28 resulting in side to side rear achieving the desired accuracy level. LED 80 lights when the system indicates level in all three orientations—front side to side, rear side to side and front to back. LEDs 82 , 84 , 86 and 88 light up when the jack they correspond to is being actuated. Their position on the keypad also indicates which corner of the trailer they are positioned at. Thus, LED 82 is between the front 72 and right 74 buttons and actuates the jack 26 which is at the front right corner of the trailer. Pressing buttons 72 and 74 lights up only LED 82 and actuates only jack 28 . This is the same for each of the jacks 24 , 26 , 28 and 30 , and the corresponding LEDs 88 , 82 , 86 and 84 . LEDs 90 , 92 , 94 and 96 light up in the shape of arrows to indicate to the user which button to press to bring the trailer into level state in the manual mode. Thus, if the rear is lower than the front, LED 94 will light and user will press rear button 76 until LED 94 goes out. Referring to FIG. 4 , lift mechanism 24 of FIGS. 1-2 is shown. FIG. 4 is discussed here as a single lift mechanism 24 ; however, the discussion applies equally to lift mechanisms 26 , 28 , and 30 as the devices and components are the same. Lift mechanism 24 can be any type of electromechanical jack, hydraulic jack, pneumatic jack or screw type jack. In one embodiment, lift mechanism 24 is a hydraulic jack comprising a support base or foot 102 , an extending member or ram 104 , a housing 106 , a mounting support member 108 , an extend tube 110 , and a retract tube 112 . Support base 102 is used in the extend position of hydraulic jack 24 and is generally wider than the extending member 104 to reduce pressure applied to the ground. In the retracted position, support base 102 is lifted off the ground and positioned at a safe height for transportation. The ground clearance for each jack is 8 inches in the preferred embodiment. In the extended position, jack 24 , in conjunction with jacks 26 , 28 , and 30 are used to support the weight of medical equipment trailer 10 and elevate it far enough to achieve all three level states discussed above: front lateral level, rear lateral level and longitudinal level. Also shown in FIG. 4 is housing 106 which contains a grease port 114 . Attached to housing 106 is supporting bracket 108 containing a plurality of mounting holes for fixedly attaching jack 24 to the frame of medical equipment 10 . Extend tube 112 is used to communicate pressurized hydraulic fluid to and from the bore side of cylinder housing 106 to facilitate jack extension. Retract tube 110 is used to communicate pressurized hydraulic fluid to and from the rod side of cylinder housing 106 to facilitate jack retraction. A heavy duty motor with a 50% duty cycle may be used to drive a pump to move hydraulic fluid between a reservoir and the jacks 24 , 26 , 28 and 30 . The pump in this example has a flow rate of 0.25-0.40 gal/min at an operating pressure of 100 psi (no load) and a flow rate of 0.17-0.30 gal/min at an operating pressure of 2000 psi (typical load). These are small flow rates in comparison to other vehicle leveling systems because the accuracy of leveling required in this system is relatively high. As it takes time from the time that a level sensor detects a level or out of level orientation until an electrical valve controlled by the controller can be turned on or off, using a lower flow rate reduces the error introduced by the amount of time it takes. Accordingly, it is desirable to use a relatively low flow rate in practicing the present invention. The lift mechanism is not limited to the description given here. Other suitable embodiments will be apparent to anyone having ordinary skill in the art given the benefit of this disclosure. A drawback to using a low flow rate pump for actuating hydraulic lift mechanisms 24 , 26 , 28 and 30 in the present invention is the amount of time it takes to move the jacks between the fully retracted and the touch-down positions, when there is no significant load on the jacks. One solution to this problem is using a two stage pump, that has a higher flow rate at low pressures, e.g., below 500 psi, and a lower flow rate at higher pressures, e.g., above 500 psi. The pump can incorporate a check valve so that it automatically shifts to the low flow, rate, high pressure mode when the load pressure exceeds the preset value, e.g. 500 psi. Any suitable hydraulic circuit may be used for controlling the actuators 24 , 26 , 28 and 30 . Such circuits usually include one or two solenoid valves per jack, a pump, a reservoir and other valves, orifices or devices to assure operation of the system. Such systems are well known in the art, as are controllers for controlling such systems, and the programming of such controllers. It is specifically intended that the present invention not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.
A high accuracy medical trailer leveling system capable of detecting at least three level orientations including level along a longitudinal direction, level along a lateral direction at the front of the trailer, and level along a lateral direction at the rear of the trailer. The system also includes sensors that detect a level orientation in the longitudinal direction at the front of the trailer and a level orientation in the longitudinal direction at the rear of the trailer. A touch pad has buttons for controlling the system and a display screen, the display screen being capable of displaying a level condition in a particular location of the trailer and direction. The display screen can display the level orientation of side to side, front; side to side, rear; and front to back, and can also display the angle of inclination. One set of lights on the control pad indicates which jacks to actuate to level the vehicle, and another set of lights indicates which jacks are being actuated.
1
FIELD OF TECHNOLOGY [0001] This disclosure relates generally to a composition of a polymerized toner and a method of preparing the same using miniemulsion polymerization (MEP) technology. Further, the disclosure also relates to a composition of a polymer/carbon black composite particle as a polymerized toner and a method of preparing the same using MEP technology. BACKGROUND [0002] Nearly 40 years ago a special kind of emulsion polymerization was firstly reported: the miniemulsion polymerization (Ugelstad,et al, 1974). In this technique a co-stabilizer, sometimes also called hydrophobe, is used to retard the diffusion of monomer molecules from smaller droplets to larger ones (Ostwald ripening effect). Kinetically stable small monomer droplets are formed in the presence of co-stabilizer and the polymerization process can run in these droplets. Using this method it is possible to polymerize water insoluble monomers because there is no need to diffuse from the monomer droplets to the micelles like in emulsion polymerization. In most of MEP a droplet nucleation dominates. That means, the polymerization takes place inside the monomer droplets like in a suspension polymerization. [0003] Beside the commonly used hydrophobic hexadecane (HD) as co-stabilizer in MEP a large variety of substances was used as co-stabilizer in MEP. However, there is still a lack of co-stabilizers in the process of MEP that can provide enhanced stability and low volatile organic content (VOC) to the polymer to be used in toner applications. SUMMARY [0004] The present disclosure relates to a composition of a polymer/carbon black (CB) composite particle and a method of preparing the same. Further, the present disclosure relates to a composition of a polstyrene (PSt)/CB composite particle and a method of preparing the same by MEP technology. [0005] In one embodiment, the present disclosure relates to a composition, comprising: a monomer, a reactive co-stabilizer, a CB, a surfactant and a filler, wherein the composition is used to prepare a polymer/CB composite particle. In another embodiment, the polymer/CB composite particle is prepared by MEP technology. [0006] In one embodiment, the monomer as disclosed is styrene forming a polystyrene. In another embodiment, the polymer is a polystyrene or a polystyrene dominated copolymer. [0007] In one embodiment, the reactive co-stabilizer is a methacrylate derivative whereas in another derivative, the reactive co-stabilizer is a methacrylate derivative containing a long alkyl chain R, with R consisting of 6-22 C atoms and being branched or linear, saturated and/or unsaturated such as a stearyl methacrylate (SteaMA). [0008] In one embodiment, the polymer/CB composite particle as prepared is used as a basic resin. In another embodiment, the composite particle as prepared is used as a basic resin in a material used further for a toner application. [0009] In one embodiment, the size of the composite particle is in the range of 20 nm to 1000 nm. In another embodiment, the size of the composite particle is less than 20 nm. In yet another embodiment, the size of the composite particle is in the range of 50 nm to 300 nm, wherein the reactive co-stabilizer is added in 0.5 to 15 mol %, preferably 2-7 mol %. [0010] In one embodiment, the composite particle are prepared in the presence of a charge control agent (CCA). In another embodiment, the CCA is a bi-salicylate of aluminium (Al) or zirconium (Zr). [0011] Thus, in one embodiment, the present disclosure relates to a method of preparing a polymer/CB composite particle by MEP technique using a fatty acid methacrylate as a co-stabilizer and in the presence of CCA whereas in another embodiment, a method of preparing a PSt/CB composite particle by MEP using a fatty acid methacrylate as a reactive co-stabilizer in the presence of bi-salicylate of Al or Zr is disclosed. [0012] In one embodiment, the composite particle is obtained in the presence of 0.1 and 10 mol % of CCA with regard to St. In another embodiment, the composite particle is obtained in the presence of 1-5 mol % of CCA with regard to St. [0013] In one embodiment, the composite particle as prepared has an enhanced stability, wherein the stability results from a covalent binding of co-stabilizer into the polymer matrix through co-polymerization. In another embodiment, the composite particle as prepared has a low VOC. Enhanced stability is because of the fact that there are no volatile substances like the usually used hexadecane as hydrophobe in the composite. The advantage of using reactive hydrophobes is, that the hydrophobe is coupled to the polymer chain after the polymerization. The “classical” hydrophobe hexadecane can evaporate from the composite at higher temperatures. This evaporation can be avoided by the use of a reactive hydrophobe which can form a copolymer with the matrix polymer like poly(styrene) (PSt). [0014] In most embodiments, the polymer is used in the polymer/CB composite particle preparation is a polystyrene or a polystyrene dominated copolymer. [0015] The above mentioned summary presents a simplified version of one or more embodiments in order to provide a basic understanding of such embodiments. This summary is not an extensive overview of all contemplated embodiments, and is intended to neither identify key or critical elements of all embodiments nor delineate the scope of any or all embodiments. Its sole purpose is to present some concepts of one or more embodiments in a simplified form as a prelude to the more detailed description that is presented later. Other features will be apparent from the accompanying drawings and from the detailed description that follows. BRIEF DESCRIPTION OF DRAWINGS [0016] Example embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, in which like references indicate similar elements and in which: [0017] FIG. 1 shows a SEM picture of PSt/CB composite (5 wt % CB) using SteaMA as co-stabilizer. [0018] FIG. 2 shows a SEM picture of PSt/CB composite (8 wt % CB) using SteaMA as co-stabilizer. [0019] Other features of the present embodiments will be apparent from the accompanying drawings and from the detailed description that follows. DETAILED DESCRIPTION [0020] Although the present embodiments have been described with reference to specific example embodiments, it will be evident that various modifications and changes may be made to these embodiments without departing from the broader spirit and scope of the various embodiments. [0021] The present disclosure describes a composition of a polymer/CB composite particle and a method of preparing the same by MEP in the presence of a methacrylate derivative containing a long alkyl chain R, with R consisting of 6-22 C atoms and being branched or linear, saturated and/or unsaturated (Formula 1) such as SteaMA (Formula 2). [0000] [0022] Formula 1 showing general structure of a reactive co-stabilizer. [0000] [0023] Formula 2 showing structure of stearyl methacrylate. [0024] In a classical MEP, the HD is often used as co-stabilizer, having a relatively high boiling point and is found to evaporate at higher temperatures. This can be a drawback when using the co-stabilizer in preparing such polymer/CB composite particle, preferably PSt/CB or polystyrene copolymer/CB composite particles to be used in toner applications specially during the fixation process of polymer particles using high temperatures. Beside the commonly used HD as co-stabilizer in MEP a large variety of substances was used as co-stabilizer in MEP. The paper by Landfester (Landfester, 2003) gives an overview about the use of different co-stabilizers. [0025] Further, Chem and Chan (Chern and Chan, 2007), reported the use of long chain alkyl methacrylates as co-stabilizer together with different ionic (SDS) or non-ionic surfactants (ethoxylated fatty alcohols or ethoxylated alkyl phenols) in MEP of St (Chern and Chan, 2007). It was found, that SteaMA was more efficient than dodecyl methacrylate (DMA) because of the differences in the water solubility of the monomer. A further advantage is the incorporation of the hydrophobic substance into the polymer chain. It was also reported, that the use of DMA resulted in dispersions with a broader particle size distribution then SteaMA. Beside SDS also nonionic surfactants based on ethoxylated fatty alcohols were investigated. SteaMA was also used for the miniemulsion polymerization of MMA instead that of St. So far, SteaMA was only used as hydrophobe for MEP of different monomers. But it was not described, that St can be also used for the preparation of composites of Carbon Black (CB) by MEP. [0026] Bechthold (Bechthold, 2000) investigated other hydrophobic substances (cyclic siloxanes or olive oil) than HD as a co-stabilizer. Bunker (Bunker et al, 2003) reported the MEP of acrylated methyl oleates for pressure sensitive adhesives. [0027] As shown by way of various examples in the present disclosure, a big advantage of using SteaMA as a co-stabilizer is the formation of copolymers with the monomer like St during MEP. At the end of the polymerization, the co-stabilizer is completely covalently bound in the copolymers. Consequently, a reduction of the VOC can be realized by the use of SteaMA instead of HD. A further advantage of the used SteaMA is the influence of the incorporated SteaMA units on the T g of the polymer matrix of the final composite particles. The T g of a PSt prepared by MEP in the presence of HD is usually in the range between 95 and 105° C., depending on the content of low molecular weight substances. Preparation of CB Composite Using MEP Technique [0028] A number of studies have shown the preparation of CB composites by MEP technique. One such technique is by Landfester (Landfester et al, 2000) as also used in the present application. Co-stabilizer play an important role for the encapsulation process as they not only suppress the Ostwald ripening but also cover the surface of CB to prevent the formation of larger aggregates. The CB was sonicated together with the organic phase in the first step. Later, water and SDS were added and the sonication was repeated. Particles of 100-150 nm size were formed. The CB could be only detected by TEM after the melting of the particles. After the aging the particles at 120° C. aggregates of CB in the size of between 30 and100 nm were detected. The latexes were analyzed by ultracentrifugation in a density gradient which was realized by different sucrose solutions. Unmodified CB could not be observed in any experiments. But it could be shown that the CB was not homogeneously distributed within the PSt. Furthermore, often pure PSt was also observed. The nature of the used co-stabilizer showed a crucial influence on the encapsulation result. Up to max. 8 wt % CB could be encapsulated with this method. [0029] Landfester (Landfester, 2001) reported the encapsulation of relatively large amount of CB using a further developed two step miniemulsion technique (Tiarks et al, 2001). Up to 80 wt % of CB can be encapsulated using this technique. It was described to prepare a stable dispersion of CB in water using surfactants like SDS (e.g. 15 wt % based on CB) first. The resulting particle size of the CB was about 90-140 nm. In a second part, a normal MEP recipe for the polymerization of St was used to prepare a miniemulsion containing St, and SDS. A custom-made polyurethane was preferentially used as co-stabilizer in these experiments. This special co-stabilizer showed good interactions with the CB surface and was closely adsorbed at the CB surface. Finally, the formed miniemulsion of St and the (stable) CB dispersion were mixed together in the appropriate amount and sonicated. After polymerization particles with a size 70 and 90 nm were obtained. This is in the range of the covalently linked CB clusters. Non-spherical particles were formed with a top layer of PSt (TEM). The application of this encapsulation technique was limited to only relatively high amounts of CB in the mixture. [0030] Han (Han et al, 2010) also described an encapsulation process of CB by polystyrene using the miniemulsion approach. First, a surface modification of CB was performed by an oxidation process with KMn 04 . Then the formed OH groups were converted into esters by the reaction with oleic acid. The so modified CB was used in encapsulation processes by the miniemulsion technique. A stable dispersion of the modified CB was realized by sonication process in the presence of water/SDS/HD. The success of the encapsulation process was enhanced by increasing the ration of CB:St from 1:1 up to 5:1. The samples with the high amounts of styrene showed that the excess of St formed pure PSt without any CB. The drawback from a practical point of view was the preparative effort of the surface modification of CB, especially the esterification of the OH groups with oleic acid and the extraction of unreacted oleic acid as purification step. [0031] The commonly used low molecular weight co-stabilizers like HD or hydrophobic oils further have a drawback that they retain only physically bound in the products after the polymerization reaction. Finally, polymeric nanoparticles were obtained which still contain volatile substances. Despite the boiling point of HD is relatively high with about 287° C., the thermogravimetric analysis of pure HD showed evaporation at temperatures up to 200° C. with a T onset of 89° C. and T 10 % of 133° C. (TGA under N2 , 10 K/min). The liberation of volatile substances cannot be excluded in applications like printers where higher temperatures are not unusual. In order to reduce the VOC reactive co-stabilizers replace the “volatile” HD. The reactive co-stabilizer is incorporated by covalent bonds into the polymer chain after the polymerization. Furthermore, the formation of copolymers resulted in products with lower T g like the original PSt. A lowering of T g up to 62° C. was observed by modulated DSC for products with the highest content of SteaMA. [0032] In toner applications so called CCA play an important role. Therefore, the formation of PSt/CB composites was studied in the presence of CCA. The investigated CCA were bi-salicylates of Al or Zr. The use of HD for the formation of composites particles did not give positive results in those formulations. Significant amount of unmodified CB was observed by SEM. But the replacement of HD by SteaMA showed an improvement of the quality of the formed composites. No unmodified CB was found by SEM investigations for both CCA types (examples 13 and 14 in Table 3; the compositions for example 13 and 14 are shown in Table 1). In all of the experiment a conversion of monomer >93% was obtained. Thus, the use of a reactive co-stabilizer like SteaMA instead of HD as the co-stabilizer in MEP of polymer/CB is of advantage especially for obtaining PSt composite particles with CB content relevant for toner application and in the presence of CCA. [0033] Furthermore, St/CB composite formation with CB content up to 10 wt % is possible and the composite particles can be prepared in the presence of CCA. In that case, MEP of higher stability was obtained given further advantage for the preparation of technically relevant polymer particle composition for toner application. [0034] The content of CB was varied between 5 and 10 mass %. In all cases, and using various types of CB, stable composite particles were obtained with a particle size of >90 nm with often bimodal size distribution. High monomer conversions >95% were obtained and the resulting polymers showed high molar masses with Mn>100,000 g/mol (Table 3, FIG. 1 and FIG. 2 ). Experimental [0035] The following samples describe the preparation of PSt/CB composites by MEP using fatty acid methacrylate, such as SteaMA, as a reactive co-stabilizer. Reagents and Materials [0036] StMA was purchased from ABCR. Styrene, CTAB, Sodium styrene sulfonate, SDS (>99% Fluka), HD, 2,2′-Azobis(2-methylpropionitrile) (AIBN), Phosphorous pentoxide, calcium hydride, tetrahydrofurane, hexane, chloroform, sodium chloride, and hydroquinone were purchased. Hydroxyaluminium salicylate derivative (MEC-88) and Zirconium salicylate derivative (MEC-105) were purchased from Korean Material technology. Methanol was purchased from ACROS. Carbon blacks such as NIPex® 35 and NIPex® 150 were purchased from Evonik. MEP of St Using SteaMA as Co-Stabilizer (Examples 1-2) [0037] The details of the performed experiments and the results of the analytical investigations are summarized in Table 1. [0038] 4.27 g of purified St, 0.929 g SteaMA (98%), and 0.146 g AIBN were weighted. After mixing by shaking the organic phase the required amounts of surfactant SDS (0.056 g) and water (41.6 g) were added. Then the mixture was slowly stirred with ca. 150 rpm under N 2 (the needle for purging with N 2 was not in the mixture, very small stream of N 2 , less than 1 bubble/second) for 15 min. During this time the SDS was dissolved in water. A formation of pre-emulsion was not observed because of the slow stirring. Then the mixture was stirred under N 2 at 800 min −1 for 30 min to prepare the pre-emulsion using a glass stirrer. The distance between top side fastener stirrer and lower side of the fastener motor was measured and used in further experiments. So the stirring conditions were comparable. After 30 min the mixture was transferred to the sonifier. During this a moderate stream of N 2 was applied. The miniemulsion was prepared by sonication of the pre-emulsion for 600 s (level 7, pulse, duty cycle 50%) with an ultrasonic disintegrator Branson 450 W using a ½″ minitip. The connection between vessel and tip was realized by a special Teflon adapter. Due to the adapter a tight connection between minitip and vessel could be realized. [0039] During all operations the vessel was purged with a slight stream of nitrogen. A cooling of the reaction vessel by ice water was performed during the sonication in order to avoid a heating of the mixture. The reaction vessel with the formed miniemulsion was transferred to the preheated thermostat (66° C.). The reaction was performed at 400 min −1 for 3 h. Then the mixture was cooled to room temperature within 5 min using ice-water. Before the storage of the dispersion, ca. 200 mg of a 1 wt % solution of HQ in water was added and the mixture was shaken. Removal of Coagulum [0040] After the polymerization, the formed dispersion was poured through a mesh (pore size 20 μm×20 μm) and then used for the analytical investigations. Finally, the rest in the mesh and the rests from the stirrer and the vessel were transferred into a frit using water. The coagulum was washed with water and dried in vacuum at room temperature in order to determine the quantity of coagulum. Determination of Conversion [0041] Three samples of 2 g of the formed dispersion were weighted in a petri dish and kept overnight at room temperature. The air dried products were dried in vacuum at room temperature until the weight was constant. P 4 O 10 was used as drying agent in the vacuum oven. Size Exclusion Chromatography (SEC) [0042] SEC measurements were performed with an apparatus of the Agilent Series 1100 (RI detection, 1PL_MIXED-B-LS-column [7.5×300 mm] and 10 μm PSt gel Agilent column, Chloroform 1.0 mL/min). Polystyrene was used as standard. This was the standard method for all of the samples. The samples containing CB were filtrated to remove the CB before the analysis. The error of the method is about 10%. Results are shown in Tables 2 and 3. Particle Size Measurements [0043] The particle size measurements were performed with a Zetasizer NANO S (Malvern) at a fixed scattering angle of 173°. The given values are the z ave (intensity based). The error of the measurements is about 5%. Higher values of PDI mean that the particle size distribution becomes broader as shown in Table 2. Preparation of Samples for the DLS Measurements: [0044] The measurements were performed in 0.01 N NaCl solutions according to the Malvern recommendation for the measurements of latex standards. For the experiments with 20 wt % solid content ca. 250 mg of the dispersion was weighted and ca. 20g of 0.01 N NaCl solution was added. For the samples with lower solid content (10 or 15 wt %) the amount of NaCl solution was proportionally reduced to keep the concentration of the thinned dispersions nearly constant. The particle sizes of 3 samples were estimated, every of them was consecutively measured twice. In few cases the application of sodium chlosirde (NaCl) solution led to a precipitation of the dispersion. Therefore, the dispersion was thinned only with pure Millipore water. Scanning Electron Microscopy (SEM) [0045] The SEM investigations were performed with an Ultra 55 plus (Zeiss). The thinned dispersions from the DLS measurements were used to prepare the samples. One drop was placed on a C-pad or a wafer. After air drying the samples were sputtered with 3 nm Pt. Preparation of PSt/CB Composite Particle Using SteaMA and Different Surfactants [0046] Two different CB types NIPex®35 and NIPex®150 (Evonik) were selected for the preparation of PSt/CB composites. But the invention is not limited to these CB types. NIPex®35 is a non-oxidized, low structure furnace black with a mean primary particle size of about 31 nm and a pH value of about 9 (according to DIN ISO 787/9). NIPex®150 is a high structure oxidized gas black with a mean primary particle size of about 25 nm and a pH value of about 4 (according to DIN ISO 787/9). MEP of St Using SteaMA as Co-Stabilizer (Examples 1-2, Table 1) [0047] The details of the performed experiments and the results of the analytical investigations are summarized in Table 1. 4.27 g of purified St, 0.929 g SteaMA (98%), and 0.146 g AIBN were weighted. After mixing by shaking the organic phase the required amounts of surfactant SDS (0.056 g) and water (41.6 g) were added. Then the mixture was slowly stirred with ca. 150 rpm under N 2 (the needle for purging with N 2 was not in the mixture, very small stream of N 2 ) for 15 min. During this time the SDS was dissolved in water. A formation of pre-emulsion was not observed because of the slow stirring. Then the mixture was stirred under N 2 at 800 min −1 for 30 mm to prepare the pre-emulsion using a glass stirrer. The distance between top side fastener stirrer and lower side of the fastener motor was measured and used in further experiments. So the stirring conditions were comparable. After 30 min the mixture was transferred to the sonifier. During this a moderate stream of N 2 was applied. The miniemulsion was prepared by sonication of the pre-emulsion for 600 s (level 7, pulse, duty cycle 50%) with an ultrasonic disintegrator Branson 450 W using a ½″ minitip. The connection between vessel and tip was realized by a special Teflon adapter. Due to the adapter a tight connection between minitip and vessel could be realized. During all operations the vessel was purged with a slight stream of nitrogen. A cooling of the reaction vessel by ice water was performed during the sonication in order to avoid a heating of the mixture. The reaction vessel with the formed miniemulsion was transferred to the preheated thermostat (66° C.). The reaction was performed at 400 min −1 for 3 h. Then the mixture was cooled to room temperature within 5 min using ice-water. Before the storage of the dispersion, ca. 200 mg of a 1 wt % solution of HQ in water was added and the mixture was shaken. Example 0 was prepared in a similar manner. [0048] Preparation of PSt/CB Composite Particle Ising SteaMA and Different Surfactants [0049] Two different CB types NIPex®35 and NIPex®150 (Evonik) were selected for the preparation of PSt/CB composites. But the invention is not limited to these CB types. NIPex®135 is a non-oxidized, low structure furnace black with a mean primary particle size of about 31 nm and a pH value of about 9 (according to DIN ISO 787/9). NIPex®150 is a high structure oxidized gas black with a mean primary particle size of about 25 nm and a pH value of about 4 (according to DIN ISO 787/9).The procedure described in above paragraph was repeated using the recipe described in the 2 nd part of Table 1 (from example 3). The CB was added to the organic phase at the beginning and the organic phase was shaken. Then water and the surfactant were added to the mixture which was processed as described above. [0050] Table 1 shows recipes for the MEP of Styrene using SteaMA as co-stabilizer [0000] Water Styrene Surfactant Co-stabilizer AIBN Filler CCA Sample [g] [g] Type [mg] Type [mg] [mg] Type [mg] wt % # Type [mg] 0 37.7 8.6 SDS 103 HD 359 269 Without 0 without 0 (Reference) 1 41.6 4.3 SDS 56 SteaMA 929 146 Without 0 without 0 (Reference) 2 41.6 4.3 SDS 52 SteaMA 955 140 without 0 without 0 (Reference)  3* 28.09 6.4 SDS 76 HD 264 199 CB150 344 5.4 without 0 (Reference) 4 41.6 4.3 SDS 52 SteaMA 979 133 CB150 214 5.0 without 0 5 41.6 4.3 SDS 52 SteaMA 959 134 CB150 344 8.0 without 0 6 41.6 4.3 SDS 53 SteaMA 927 135 CB150 345 10.0 without 0 8 41.6 4.3 SDS 53 SteaMA 934 136 CB150 429 5.0 without 0 9 41.6 4.3 SDS 52 SteaMA 935 134 CB35 214 5.0 without 0 10  41.6 4.3 SDS 54 SteaMA 932 137 CB90 215 5.0 without 0 11  37.7 8.6 SDS 103 HD 356 268 CB150 428 5.0 MEC-88 86 12  37.7 8.6 SDS 103 HD 357 268 CB150 428 5.0 MEC-105 86 13  41.6 4.3 SDS 51 SteaMA 926 134 CB150 214 5.0 MEC-88 467 14  41.6 4.3 SDS 52 SteaMA 926 134 CB150 214 5.0 MEC-105 429 *sonication 20 min at 90% duty, polymerization for 6 h # based on styrene [0051] Table 1 shows results for the MEP of St in the presence of SteaMA [0000] Particle size Con- DLS SEC ver- Coag- z-ave M n M w M w / sion ulum Example [nm] PDI [g/mol] [g/mol] M n [%] [%] 0 78 0.06 149000 693000 4.7 94 0.3 (Reference) 1 72 0.06 121000 1370000 11.3 96 0.2 (Reference) 2 73 0.05 105000 889000 8.5 97 0.2 (Reference) 3 98 0.18 105000 571000 5.4 95 1.0 (Reference) 4 92 — 96000 1375000 14.3 96 0.2 6 100 — 169000 1820000 10.8 94 1.6 8 103 — 157000 1690000 10.8 93 1.6 9 96 — 178000 1870000 10.5 96 0.7 10  90 — 148000 1675000 11.3 93 2.1 [0052] Table 2 shows results obtained for PSt/CB composites using HD or SteaMA as co-stabilizer in the presence of CCA. [0000] Particle size Con- DLS SEC ver- Coag- z-ave M n M w M w / sion ulum Sample [nm] PDI [g/mol] [g/mol] M n [%] [wt %] 11 109 a — 115000 517000 4.5 96 2.4 12 103 a — 115000 473000 4.1 96 0.6 13  94 b — 145000 1633000 11.3 104 0.7 14 118 b — 109000 1677000 15.4 97 0.1 a Unmodified CB and larger agglomerates could be observed by SEM b Unmodified, non-encapsulated CB could not be identified by SEM. Few agglomerates in of about 200 nm were observed.
The present disclosure relates to a composition, comprising a monomer; a reactive co-stabilizer; a carbon black; a surfactant; and a filler, wherein the composition is used to prepare a polymer/carbon black composite particle by MEP technology along with a method for same. The reactive co-stabilizer as disclosed is methacrylate derivative containing a long alkyl chain R, with R consisting of 6-22 C atoms and being branched or linear, saturated and/or unsaturated such as stearyl methacrylate (SteaMA). The polymer/carbon black composite particle as prepared has an enhanced stability and low VOC as compared to a pure polymer prepared by MEP. Further, the prepared polymer can be used as basic resins in materials for toner applications.
2
TECHNICAL FIELD [0001] The present invention is related to the discovery of a new coefficient called “Radicular Spectral attenuation Coefficient-RSAC” applicable in electronic foraminal locators to measure the root canal length and to locate the apical foramen, during the dental endodontic treatment. STATE OF ART [0002] One of the preliminaries procedures in the endodontic treatment is to determine the root canal length (RCL) and the exact location of the apical foramen (LAF). The RCL is related to the deepest point the endodontic file may reach within the tooth root canal. The debridement and the canal filling cannot be performed unless the LAF is correctly determined and the canal completed cleaned. [0003] FIG. 1 presents an illustration of a tooth ( 1 . 14 ) with its radicular ( 1 . 15 ) canal opened. Within the radicular canal ( 1 . 15 ) it is inserted the endodontic file ( 1 . 1 ) used during the treatment of the tooth canal ( 1 . 14 ). Two are the aims of a foraminal locator: determine the distance between the tip of the endodontic file ( 1 . 2 ) and the apical foramen ( 1 . 3 ); and to inform the dentist the exact point when the tip of the file has reached the foramen ( 1 . 3 ). The canal foramen ( 1 . 3 ) is the deepest anatomic point within the tooth canal that the endodontic file may reach during the treatment, that is, the LAF is extremely important for the success of the endodontic treatment. Therefore, the aim of our Radicular Spectral Attenuation Coefficient (RSAC) is to determine the root canal length and inform the dentist the exact point when the tip of the endodontic file reaches the apical foramen. [0004] Up to recently the RCL and the LAF was determined only by radiographic image. The main disadvantage of using radiographic images is that it produces a two-dimension image of an object that has three-dimensions. Thus, the accurate determination of the RCL and the LAF is not always possible by radiography. Another drawback is the ionized radiation applied to the patient. [0005] Electronic apex locators have been subject of many US patents, such as: U.S. Pat. Nos. 5,759,159; 5,211,556; 5,096,419; 6,059,569. All these patens claim different physical principles to perform the task of locating the apical foramen of the tooth canal. Also, all these patents have in common the use of two electrodes: one electrode is inserted into the tooth root canal, in general this electrode is the endodontic file ( 1 . 1 ), and the other electrode is attached to the patient's lip ( 1 . 4 ). The aim is to determine the physical distance in millimeter between the tip of the endodontic file ( 1 . 2 ) and the apical foramen of the tooth canal ( 1 . 3 ). [0006] The U.S. Pat. No. 5,759,159, Jun. 2, 1998, claims the use of a measurement signal with several different components of frequency. This signal is applied to the previously described electrodes. The complex impedance of the tooth canal is measured by the electronic system. For this, the system measures the amplitude in voltage between the electrodes (potential difference) and phases introduced in each frequency component. The amplitudes and phases are then mathematically combined and related with the distance between the tip of the endodontic file and the radicular foramen. At this point we must state that our RSAC, which is the aim of our patent, does not perform any phase measurement or combine amplitudes with phases to determine the RCL or the LAF. [0007] The U.S. Pat. No. 5,211,556, May 18, 1993, claims a methodology of relating the decreasing in the root canal resistance, as the tip of the measuring electrodes approaches the apical foramen, with the physical distance in millimeters between the tip of the inserted electrode (endodontic file) and the apical foramen. The resistance is measured through a measurement signal applied to the electrodes. A methodology to compensate the non-linearity of the measured resistance values, for different electrode position within the canal, is described. At this point we must state that our RSAC, which is the aim of our patent, does not measure resistance or impedances values to determine the RCL or the LAF. [0008] The U.S. Pat. No. 5,096,419, Mar. 17, 1992, claims an apparatus to detect the apical position. In this patent a measurement signal with different frequencies is applied to the previously described electrodes. The ratio of the tooth canal impedance measured with different frequencies is calculated. The apical position is detected by monitoring the changes in the ratio value as the tip of the file gets near the apical foramen. According to the patent there is a significant change in this ratio when the tip of the endodontic file reaches the apical position. At this point we must state that our RSAC, which is the aim of our patent, does not calculate any ratio of impedances measured within the tooth canal with different frequencies. [0009] The U.S. Pat. No. 6,059,569, May 9, 2000, describes an apical locator where two signals of alternated current with different frequencies are applied in the electrodes previously described. These two signals provide two current measurements that are logarithmically combined to indicate the foramen position. At this point we must state that our RSAC, which is the aim of our patent, does not measure electrical current that goes through the tooth root canal. DESCRIPTION OF THE INVENTION [0010] The origin of the idea for the new coefficient RSAC to measure the tooth canal length and to localize the apical foramen is based on the technique used to measure the ultrasound attenuation within the human tissue. [0011] The technique for the ultrasound attenuation coefficient is called “Broadband Ultrasound Attenuation” or BUA. As the ultrasound propagates through the human tissue, its intensity decays exponentially with the distance. The BUA coefficient is determined by analyzing the logarithm of the ultrasound signal spectrum. Detailed explanation is beyond the scope of this patent. The fact is that resistors and capacitors circuits can be used to model the acoustic and electrical impedance of the tissues. Thus, we have visualized that a similar procedure, that is, the BUA measurement, is applicable to determine the tooth canal length and to localize the apical foramen. [0012] Therefore, this patent of invention describes the discovery of a new coefficient called Radicular Spectral Attenuation Coefficient or RSAC. The RSAC is directly related with the distance between the tip of the endodontic file ( 1 . 2 ) and the radicular foramen ( 1 . 3 ). This distance is called Root Canal Length (RCL). Thus, since the RSAC is directly related to the RCL, it also can be used as a reference for the localization of the radicular foramen (LRF). In the following paragraphs it is described the physical principle involved with the RSAC measurement and how this coefficient is converted in the RCL and used as reference for the LRF. [0013] The process of RSAC calculation is divided into three steps: 1) the application of a measurement signal; 2) the measurement of an electrical signal and from this signal the determination of the RSAC and 3) the conversion of the RSAC into the RCL and the LAF. The first two steps make use of the already described measurement electrodes ( 1 . 1 ) and ( 1 . 4 ). [0014] The measurement signal, applied in the first step of the RSAC calculation, is composed by a sum of sine waves trigonometric functions, all them with the same amplitude but different frequencies (or periods) and initial phases. The measurement signal, represented by f(t), is determined by equation 1, [0000] f  ( t ) = A · ∑ i = 1 N  sin  ( 2 · π · f i · t + ϕ i ) ( 1 ) [0000] where A is the sine waves amplitudes, f i is the i th component of frequency, π=3.14151617, φ i is the sine wave phase shift of the i th component of frequency, sin is the trigonometric sine wave function, t represents the time and Σ is the sum of the sine waves with i varying from one to N. N is the number of sine waves used to generate f(t). [0015] The f(t) signal spectrum is represented in FIG. 2 . In FIG. 2 the axes ( 2 . 1 ) and ( 2 . 2 ) are the sine wave amplitude in volts and its frequency in cycles per second, respectively. The vertical arrows ( 2 . 3 ) are the N sine waves functions with frequencies (f 1 ), (f 2 ), (f 3 ), . . . , (f N ) that compose the measurement signal f(t). Note that all frequencies components ( 2 . 3 ) have the same amplitude value (A). [0016] The signal f(t) is used to modulate or control a constant electrical current source. Thus, we have an electrical current signal whose waveform has the same all N components of frequencies given by equation 1. The root mean square (RMS) value of the electrical current generated by the current source is below four micro-amperes and does not represent any risk for the patient or the surgery. The electrical current signal is applied to electrodes ( 1 . 1 ) and ( 1 . 4 ). This current circulates through the canal of the tooth and produces a potential difference between the electrodes ( 1 . 1 ) and ( 1 . 4 ). [0017] The second step in the process of determining the RSAC is the process of measuring the potential difference between the electrodes ( 1 . 1 ) and ( 1 . 4 ). This potential difference has the same components of frequencies of the applied signal f(t). However, due to the electrical characteristics of the tooth canal, the frequency components of the applied signal ( 2 . 3 ) are attenuated differently. The spectrum of frequencies of the measured signal (potential difference between the electrodes ( 1 . 1 ) and ( 1 . 4 )) is shown in figure ( 2 . 6 ). The length of the vertical arrows ( 2 . 6 ) represents the amplitude of each frequency component of the measured signal, indicated by (A 1 ), (A 2 ), (A 3 ), (A 4 ), . . . (A N ). The axis ( 2 . 4 ) and ( 2 . 5 ) are the amplitudes in voltage and the frequency in Hz, respectively. [0018] In a study performed by the inventors of this patent, it has been discovery that the attenuation of the frequency components ( 2 . 6 ) has a behavior very similar to an exponentional mathematical function. Thus, we have noticed that there is an exponentional attenuation ( 2 . 7 ) of the applied frequencies components ( 2 . 3 ). In an in vivo experiment, we notice also that the exponentional decay ( 2 . 7 ) changes as the file is introduced into the tooth canal. [0019] The RSAC is determined by converting the axes scale ( 2 . 4 ) to a logarithm scale using the natural logarithm function. FIG. 2 illustrates the frequency spectrum, in which the axis ( 2 . 8 ) and ( 2 . 9 ) were logarithmized. In the logarithmized scale, the spectrum attenuation is a linear function ( 2 . 10 ). The RSAC is the line inclination, given by equation 2, [0000] R   S   A   C = tan - 1 [ ∑ i = 1 N - 1  (  ln  ( A i ) - ln  ( A i + 1 )   ln  ( f i ) - ln  ( f i + 1 )  ) N - 1 ] ( 2 ) [0000] where A i e A i+1 are the voltage amplitudes, f i and f i+1 are the frequencies, In is the natural logarithm, tan −1 is the arc tangent function, | | is the absolute value, Σ is the sum with i varying from one to N−1 and N is the number of frequency components used to generate f(t). [0020] The third step in the measurement process is to convert the RSAC in the distance value between the tip of the endodontic file ( 1 . 2 ) and the apical foramen ( 1 . 3 ) in millimeter. This process is made through a calibration curve. This calibration curve is obtained from in vivo experiments. [0021] FIG. 1 presents a block diagram of the implemented electronic circuit used to obtain the RSAC for the measurement of the RCL and in the LAF. The instrument makes use of a measuring electrode ( 1 . 1 ) that is inserted into the tooth canal and a clipping electrode ( 1 . 4 ) that is attached to the patient's lip or other oral soft tissue. A control unit ( 1 . 8 ), made with a micro-controller or microprocessor ( 1 . 8 ), executes the firmware (programme) stored in the microprocessor memory ( 1 . 12 ). [0022] The measurement signal is the one previously described and given by equation 1. The measurement signal is then stored into memory ( 1 . 11 ). As the control unit ( 1 . 8 ) performs the memory addressing, the data stored in ( 1 . 11 ) is then sent to the digital-to-analog-D/A ( 1 . 9 ) and converted to voltage. The voltage at the output of the D/A ( 1 . 9 ) is then filtered by a low-pass-filter ( 1 . 10 ) to remove higher component of frequencies generated by the A/D and converted to an electrical current signal by a voltage-current source converter ( 1 . 5 ). The current signal is then applied to the measuring ( 1 . 1 ) and clipping ( 1 . 4 ) electrodes. [0023] A potential difference between the electrodes ( 1 . 1 ) and ( 1 . 4 ) is then measured. This potential difference is amplified and filtered by the Signal Conditioner ( 1 . 6 ). After that, the signal is applied to analog-to-digital-A/D converter ( 1 . 7 ). The digitalized signal is then processed by the control unit ( 1 . 8 ), according to the firmware stored in ( 1 . 12 ). The result of the firmware process is then presented in the display ( 1 . 13 ). Firmware Description [0024] FIG. 3 presents a block diagram of the signal processing used to determine the RSAC, calculate the RCL and the LAF. The programme is divided into three parts: 1) Signal Generator ( 3 . 21 ); 2) Signal Detector ( 3 . 22 ) and 3) Signal Processing ( 3 . 23 ). The Signal Generator ( 3 . 21 ) has the Signal Modulator ( 3 . 1 ) whose signal is determined by equation 1. This signal is converted to electrical current by the Modulated Current Source ( 3 . 2 ). The instrument here described makes use of seven components of frequency (N=7): 500 Hz, 1 kHz, 2 kHz, 4 kHz, 8 kHz, 16 kHz and 32 kHz. Other components of frequency may be used, depending on the hardware capability, that is, faster processors allow the use of higher frequencies. [0025] Next the amplitude of the measured signal is analyzed. This task is performed by the Signal Detector ( 3 . 22 ). The measured electrical signal ( 3 . 3 ), between the electrodes ( 1 . 1 ) and ( 1 . 4 ), must be between the upper ( 3 . 8 ) and lower ( 3 . 11 ) threshold values. If the measured signal is not below the upper threshold ( 3 . 8 ) the Gain Control ( 3 . 9 ) of the amplifier is automatically decremented. This gain is reduced ( 3 . 9 ) until the signal is below the upper threshold ( 3 . 8 ) and than it can be processed, or until the gain is at its minimal value ( 3 . 12 ). If the gain is at its minimal and the signal is still above the upper threshold, it is because the endodontic file is not inserted into the root canal ( 3 . 13 ) and it must be inserted for the measuring process be performed ( 3 . 3 ). [0026] If the measured signal between the electrodes ( 1 . 1 ) and ( 1 . 4 ) is not above the lower threshold ( 3 . 11 ) the Signal Detector ( 3 . 22 ) automatically tries to increment the amplifier gain ( 3 . 10 ). The increase of the gain is performed until the measured signal amplitude is above the lower threshold, so it can be processed. On the other hand, if even with the amplifier set to its maximum gain ( 3 . 7 ) the signal is still below the minimum threshold, it is because the measuring electrodes are short-circuited ( 3 . 6 ). [0027] Once the amplifier gain has been automatically set, the measured signal spectrum (spec) is calculated using a Fast Fourier Transform (FFT) algorithm ( 3 . 14 ). This procedure is repeated 32 times (counter ( 3 . 16 )) for each calculated averaged. The average of 32 spectrum of the measured signal is calculated (( 3 . 15 ), ( 3 . 16 ) and ( 3 . 20 )) to improve the signal to noise ratio (SNR) of the measured signal. It is important to mention that the number of spectrum used to calculate the average may vary. In our studies, performed in vivo the average of 32 acquisitions is enough to obtain a good SNR. Also, if for any reason (lets say, movement of the endodontic file), during the acquisition of the 32 signals used in the averaging process, there is a significant change in the amplifiers gain, the averaged is cancelled ( 3 . 4 ) and ( 3 . 5 ) and new signals are acquired. [0028] Only after the average of 32 spectrum of the measured signal is calculated, the RSAC is computed ( 3 . 19 ) and its value converted in distance ( 3 . 18 ). After that the distance is then displayed ( 3 . 17 ). [0029] Finally, it is important to emphasize that the RSAC is a new measurement coefficient discovered by us from in vivo experiments performed in patients, and it is completely different from any other method found in the literature.
The discovery of a new coefficient named “Radicular Spectral Attenuation Coefficient-RSAC”, applicable in electronic foramen locators is described. The novelty is the use of the spectral attenuation of a multifrequency electrical current signal, applied through the endodontic file into the tooth canal (TC), to determine the root length and the foramen position. FIG. ( 2 ): ( 2.1 ), ( 2.4 ), ( 2.8 ) and ( 2.2 ), ( 2.5 ), ( 2.9 ) are the amplitude and frequency axes, respectively; ( 2.3 ) is the electrical current frequency spectrum applied into the TC; ( 2.6 ) shows the spectrum exponential decay ( 2.7 ) of the signal measured over the TC. In ( 2.10 ) the axes ( 2.4 ) and ( 2.5 ) were logaritmized to linearize the exponential decay. The RSAC is the average inclination of the line ( 2.11 ), which is proportional to the distance between the tip of the endodontic file and the apical foramen. The RSAC changes as the tip of the file gets near the foramen.
0
CROSS REFERENCE TO RELATED APPLICATIONS: [0001] This document claims priority to French Application Number 03 04973, filed Apr. 23, 2003 and U.S. Provisional Application No. 60/470,504, filed May 15, 2003, the entire contents of which are hereby incorporated by reference. FIELD OF THE INVENTION [0002] The present invention relates to an assembly for the packaging and application of a fluid product, and in particular to a device for the packaging and application of a cosmetic, pharmaceutical or dermo-pharmaceutical product. The assembly can be particularly advantageous for use in the packaging and application of a hair product, such as a product to prevent hair loss. BACKGROUND OF THE INVENTION [0003] 1. Discussion of Background [0004] Products intended to prevent hair loss are applied in the form of several doses, which are applied at successive time intervals. Such products may be packaged in breakable vials, for example glass vials. There is, however, a risk of injury when the vial is being broken, as well as during application of the product since the broken end of the vial, which may be sharp, is placed in contact with the scalp. [0005] These products may alternatively be packaged in small bottles, on which a plastic dispenser head is removably fixed. With this arrangement, it is desirable for the head to be capable of being fitted easily on a bottle, then removed from the bottle in order to be fixed on another bottle corresponding to another dose. [0006] In other application fields, packaging and application assemblies are known which are formed by a container, on which an application head is fixed. For example, GB 2 249 078 describes a container containing a fluid product such as paint, onto which an application head is screwed. With this arrangement, the head is screwed onto the container when it is already open. It is therefore necessary to open the container beforehand if it is closed, and then to screw on the head, which makes it necessary to perform two separate operations. [0007] FR 2 811 372, U.S. Pat. No. 5,042,690 and U.S. Pat. No. 4,898,923 describe application devices formed by a container which is closed in a leaktight fashion by a closure element and on which an applicator head is fixed. In these arrangements, the container is opened when installing the head, which perforates the closure element. All these documents, however, describe containers whose opening is closed by a membrane or a heat-sealed or welded film. The manufacturing cost of these containers closed in this way is relatively high. [0008] FR 2 236 748 describes a dispensing head screwed onto the neck of a tube, which is initially closed by a cap formed integrally with the neck of the tube. The head has a cutting element to pierce the cap when the head is being screwed onto the neck of the tube. The head also has a detachable ring at its bottom. This ring bears against the shoulder of the tube and keeps the cutting element away from the cap. Before first use, the ring is torn off from the rest of the head so that the head can continue to be screwed onto the neck until the cutting element reaches the cap, so as to cause the cap to be pierced. In order to dispense the product, it is necessary to press on the walls of the tube so as to squeeze the product into the head and deliver it through dispensing orifices provided on the head. With such a configuration, it can be difficult to control the flow of the product out of the head. [0009] U.S. Pat. No. 3,812,992 describes a baby bottle formed by a container, on top of which there is a teat. The container is initially closed by a metal cap which is crimped onto the neck of the container. In addition, a seal is compressed between the cap and the neck in order to improve the leaktightness. Here again, the manufacturing cost of these containers closed in this way is relatively high. Furthermore, a hollow cutting tip is provided inside the teat in order to pierce the cap, substantially all around its periphery, when the teat is being screwed onto the bottle. Since the tip extends over 360°, significant friction is generated when screwing the teat onto the bottle. In addition, such a device is not suitable or readily adaptable for applying some of the product onto a person's head. [0010] U.S. Pat. No. 5,817,082 describes a container for pharmaceutical products. The container is closed by an elastomeric stopper, on top of which is provided a head having a central tip through which a channel passes. The tip pierces the stopper at a point. The product is then dispensed through the tip by gravity when the container is inverted. Here again, such a device does not make it possible to apply the product while easily or reliably controlling the product flow. SUMMARY OF THE INVENTION [0011] It is therefore one of the objects of the invention to produce a packaging and application assembly which does not have the drawbacks of the prior art. [0012] It is another object of the invention to provide an applicator assembly that can be produced at a low cost. [0013] It is yet another object of the invention to provide a packaging and application assembly which is simple to use. [0014] It is still another object of the invention to provide an assembly in which the head can be used several times in the same way, on a plurality of containers. [0015] It is another object of the invention to provide a packaging and application assembly which makes it possible to apply the product in a precise and straightforward way. [0016] It is yet another object of the invention to provide an assembly which is compact, such that the assembly is suitable for small product doses. [0017] It is a further object of the invention to produce a small assembly having ergonomics suitable for use with one hand. [0018] The invention therefore relates to an assembly for the packaging and application of a fluid product. According to an illustrated example, the assembly includes a container having a free edge defining an opening. A closure element or cover is provided to close the opening in a manner which is leaktight for the product, with the closure element being fixed on the container, for example, by snap-fastening or screwing. The assembly also includes an application head which can be fixed on the container. In a preferred arrangement, the application head includes: i) a dispensing orifice which can communicate with the interior of the container; ii) an opening component intended to break the closure element of the container when the head is being fastened onto the container, in order to establish communication between the dispensing orifice and the interior of the container; and iii) a deformable wall which can deform in response to an external pressure exerted on the head, so as to cause the product to be delivered. [0022] Where the closure element of the container is snap-fastened or screwed on, the assembly can be produced much more straightforwardly or conveniently than when the container is closed by a heat-sealed membrane. [0023] According to one of the advantageous aspects, the user performs only a single operation in order both to fix the head on the container and to open the container, so that the packaging and application assembly is relatively easy to use. [0024] The head can have a screw thread used for fastening the head onto the container. It is therefore easy to fix the head on the container and to remove the head from the container for subsequent use. Alternatively, the head can be fixed on the container by snap-fastening. The deformable wall of the head can be, for example, a convex wall or a bellows. [0025] The head can be formed, for example, by molding from a single piece. It can be obtained by molding from a single piece, particularly in a single material, or alternatively the deformable wall may be produced by over-molding, in particular by bi-injection molding, of an elastomeric material. An assembly can thus obtained which has a small number of parts, and which can therefore be produced at a low cost. In fact, in an illustrated example, the assembly can be formed of only three parts: the container, the closure capsule and the head. [0026] The head can include a nozzle, at the end of which the orifice for dispensing the product is formed. With this arrangement, it is possible to apply the product in a precise way. The nozzle can be off-centered on the head. This arrangement can be advantageous in that it is thereby more convenient to provide space, particularly along the axis of the nozzle, in order to produce a deformable wall large enough to make the product flow. [0027] The closure opening component can be in the form of a blade. The blade can be formed as an axial extension of one wall of the nozzle, so as to avoid increasing the size of the assembly and furthermore to facilitate mould release of the head. A relatively compact assembly is thus obtained. [0028] The closure element can include a weakened region which can break when the opening component is being engaged with the closure element. [0029] The closure element can be made of a single material. Alternatively, the closure element can be made of two materials. The closure element can, for example, have a fastening flange made of a rigid or semi-rigid thermoplastic material and a central part obtained by injection of an elastomeric material. The closure element can also include a fastening flange made of a rigid or semi-rigid thermoplastic material and a central part formed by a film, for example of aluminum, welded onto the fastening flange. [0030] The edge of the container and/or the closure element can include an anti-rotation arrangement intended to limit the rotational movement of the closure element relative to the container. The edge of the container may, for example, have asperities which engage with asperities formed on the closure element. [0031] The container can have a recess or concave base in order to facilitate positioning of the thumb. The ease of the application procedure is thereby improved. [0032] Thus, the invention can provide an assembly for the packaging and application of a fluid product. The arrangement can include a container having a free edge defining an opening, and a closure element intended to close the opening in a manner which is leaktight for the product. The closure element is preferably fixed on the container by snap-fastening or screwing. The arrangement further includes an application head which can be fixed on the container, with the head preferably including: i) a nozzle, at the end of which a dispensing orifice is formed which can communicate with the interior of the container, with the nozzle being off-centered on the head; and ii) an opening component intended to break the closure element of the container when the head is being fastened onto the container, in order to establish communication between the dispensing orifice and the interior of the container. [0035] The assembly according to the invention is particularly advantageous for use in for the packaging and application of a cosmetic product, particularly a hair product, such as a product containing alcohol-based compounds. BRIEF DESCRIPTION OF THE DRAWINGS [0036] The invention will become further apparent from the following detailed description, particularly when considered in conjunction with the drawings in which: [0037] FIG. 1 illustrates a perspective view of a packaging and application assembly according to the invention; [0038] FIG. 2 represents an exploded view of the assembly of FIG. 1 ; [0039] FIG. 3A represents the packaging and application assembly of FIG. 1 in cross-section, when the application head is being fixed on the container; [0040] FIG. 3B represents the packaging and application assembly of FIG. 1 in cross-section, when the application head is mounted on the container; [0041] FIG. 4 illustrates the packaging and application assembly of FIG. 1 during use; [0042] FIG. 5 illustrates a second embodiment of a packaging and application assembly according to the invention; [0043] FIG. 6 illustrates a variant of the capsule or cover of the bottle; [0044] FIG. 7 illustrates an example of a component for opening the capsule; and [0045] FIG. 8 illustrates a variant of the component for opening the capsule. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0046] Referring to FIGS. 1 to 4 , an example is illustrated of an assembly 10 according to the invention for the packaging and application of a liquid product. The invention is particularly advantageous for liquids used to prevent hair loss. The assembly 10 includes a container 20 , on top of which is disposed on an applicator head 30 . [0047] By way of example, the container 20 is in the form of a rigid bottle made of a thermoplastic material, for example PET. Alternatively, a bottle made of glass may be used. The bottle has, for example, a capacity of 6 ml. The bottle has a longitudinal axis X and includes an axisymmetric side wall 21 , one end of which is closed by a base 22 . The base 22 is, for example, a concave or recessed wall intended to facilitate positioning of the thumb or another finger. The second end of the bottle ends in a free edge 23 , which defines an opening 24 . [0048] In order to fasten the applicator head 30 onto the bottle, the bottle has a screw thread 25 on its outer surface, close to the free edge 23 , which is intended to interact with a complementary screw thread provided on the inner surface of the applicator head. [0049] Between the screw thread 25 and the free edge 23 , the outer surface of the bottle in the illustrated example has striations 26 , the function of which will be explained below, and which extend parallel to the axis X. The striations 26 may extend over only a part of the periphery of the bottle, for example over two diametrically opposite annular portions on the bottle. Alternatively, the bottle may have striations over its entire periphery. [0050] The bottle also has an annular groove 27 , which is formed between the striations 26 and the screw thread 25 and which, as discussed further below, makes it possible to fasten a capsule 40 onto the bottle. [0051] The applicator head 30 is arranged to be screwed onto the neck of the bottle. To that end, the head has a fastening flange 31 provided with a screw thread 32 on its inner periphery, which interacts with the screw thread 25 of the bottle. Alternate arrangements can be provided for fastening or coupling the head to the bottle. For example, the head can be fixed on the neck of the bottle by snap-fastening. [0052] The upper part of the flange 31 has a radial shoulder 33 provided with a sealing ring 34 intended to bear on the capsule 40 in a leaktight fashion, as shown in FIG. 3B . [0053] Beyond this shoulder, the fastening flange is extended by a nozzle 35 delimiting an internal channel 35 a . The free end of the nozzle opens into an orifice 36 for dispensing the product. The nozzle is formed on one edge of the head, in an off-centered fashion with respect to the axis X. The dimensions of the internal channel 35 a can be selected according to the viscosity of the product, preferably so as to prevent the product from flowing simply under the effect of gravity. [0054] The fastening flange 31 is also closed by a convex wall 37 in its upper part. The convex wall 37 is capable of deforming when a pressure is exerted in a direction parallel to the axis X, so as to be depressed towards the interior of the head. This deformation makes it possible to break the surface tension of the product inside the head, so as to allow the product to flow towards the dispensing orifice 36 . [0055] The head 30 also has an opening component 38 used to break a capsule or cover 40 , described below, which closes the opening 24 in a leaktight fashion before the bottle is used. The opening component is a blade 38 , which in the illustrated embodiment extends parallel to the axis X as far as a free edge 39 towards or into the bottle. The blade 38 is slightly curved so as to follow the contour of the periphery of the fastening flange 31 . In the illustrated arrangement, the blade 38 extends over a portion of a circular arc. As can be seen in FIG. 3A , the free edge 39 of the blade is beveled in order to facilitate its insertion into the capsule 40 . In the illustrated example, the free edge 39 is also inclined with respect to the plane of the capsule to be broken, as can be seen in FIG. 7 , so as to come progressively in contact with or progressively penetrate the capsule. [0056] According to a variant which is illustrated in FIG. 8 , the free edge 39 has two parts inclined with two different slopes. As shown in FIG. 8 , this arrangement includes, a substantially inclined first part 39 a , which is intended to initiate the cutting of the capsule, and a second part 39 b , which is less inclined than the first, for finishing off the cutting. [0057] In order to limit the size of the assembly while producing a sufficiently large de-formable wall, the blade 38 can be at least partially axially aligned or formed as an axial extension of one wall of the nozzle. This arrangement also facilitates mould release of the nozzle. [0058] The screw threads 25 and 32 preferably have a shallow slope in order to further improve the cutting, preferably so that the head requires more than one turn in order to be screwed home when it is being screwed onto the bottle. The capsule or cover is therefore cut gradually, to better ensure the capsule is cut sufficiently in order to free the opening of the bottle. [0059] The head can be advantageously obtained by molding from a single piece. It may be made, for example, of a single thermoplastic material, in particular a polyethylene, a poly-propylene, a polyethylene terephthalate, a polyvinyl chloride, a polyamide. Alternatively, the convex wall 37 may be over-molded onto the rest of the head, with the wall 37 made for example of an elastomeric material, in particular rubber, for example Santoprene®. A head which is washable can be obtained in both cases, so that it can be used several times. [0060] According to a variant which is represented in FIG. 5 , the convex wall 37 may be replaced by a bellows 137 . For example, such a bellows can be formed by a pleated flexible arrangement. [0061] Before the applicator head 30 is fixed on the bottle, the bottle is closed by a capsule 40 made for example of a thermoplastic material, for example PET. In the illustrated example, the capsule is snap-fastened onto the neck of the bottle. Alternatively, the capsule 40 could be screwed onto or into the bottle. [0062] In the illustrated arrangement, the capsule 40 is formed by a circular wall 41 , which includes a weakened region 42 intended to be cut. The weakened region 42 extends along a circle which, preferably, lies close to the periphery of the capsule so that almost the entire opening 24 of the bottle can be freed. The weakened region 42 can be formed by a circular portion of the wall 41 which has a smaller thickness than the rest of the wall. Instead of having a smaller thickness all along the circle, the weakened region may have a variable thickness, for example which varies in a crenellated fashion. The thickness may vary repetitively between two values along the circle: a first value corresponding to the thickness of the wall 41 and a smaller thickness second value. [0063] Beyond the portion 42 with a lower thickness, the circular wall 41 is extended by a fastening flange 43 which extends axially and, on its inner surface, has an annular bead 44 intended to be accommodated in a groove 27 of the bottle. The fastening flange 43 also has striations (not shown in the figures) on its inner surface, which are intended to engage with the striations 26 of the bottle. This arrangement provides an example of anti-rotation means which make it possible to limit the rotational movement of the capsule on the bottle. Other forms of asperity or antirotation coupling other than striations which could fulfill this anti-rotation function can be provided on the capsule and/or on the bottle. By way of example, as an alternative or in addition, the internal diameter of the fastening flange may be selected in relation to the external diameter of the bottle so that the clamping of the capsule 40 on the bottle limits the rotational movement of the capsule with respect to the bottle. [0064] In the illustrated example, a sealing flange 45 , concentric with the fastening flange, is also provided on the capsule. This flange extends axially from the circular wall 41 , between the region 42 of lower thickness and the fastening flange 43 , and to an end lip 46 . The flange bears against the inner surface of the bottle in a leaktight fashion. The lip 46 is slightly inclined in the direction of the center of the flange, so as to facilitate insertion and centering of the sealing flange 45 in the neck of the bottle when the capsule 40 is being fastened onto the bottle. Such a shape can also facilitate distribution of the capsules on a production line, in particular by preventing them from stacking up on one another. The end lip 46 is continuous in the example which is illustrated in FIG. 2 . According to a variant which is illustrated in FIG. 6 , the end lip is formed by tabs 47 which make it possible to obtain a more flexible lip. [0065] By way of example, the capsule 40 can also be formed by molding in a single piece from a thermoplastic material, in particular a polyethylene, a polypropylene, a polyethylene terephthalate, a polyvinyl chloride, a polyamide. The capsule can be made of a single material or, alternatively, the circular wall 41 may be made by bi-injection of an elastomeric material. [0066] According to one variant (not shown), the applicator head 30 need not be screwed directly onto the bottle but instead onto the capsule 40 , which then has a screw thread on its outer wall. As a further alternative, the head 30 may be snap-fastened onto the bottle. [0067] In order to use the device, the user grips a bottle 20 which is closed by a capsule or cover 40 . He fixes the head 30 on the closed bottle, by screwing it onto the neck. While screwing, the capsule remains fixed rotationally with respect to the bottle, for example, due to the presence of the striations on the capsule, which prevent rotational movement of the capsule with respect to the bottle by friction on the striations 26 formed on the bottle. While screwing, the blade 38 engages progressively with the capsule's circular portion 42 having a lower or smaller thickness, as can be seen in FIG. 3A , until this portion is broken. The dispensing orifice is then in communication with the interior of the bottle. When the screwing action is completed, the circular wall 41 of the capsule can be fully detached and fall into the bottle, as has been represented in FIG. 3B . As an alternative, the circular wall 41 may remain connected to the capsule by a small radial portion. [0068] The user can then apply the product by inverting the device and pointing the nozzle towards his scalp. As can be seen in FIG. 4 , for example, the user holds the applicator by positioning his thumb on the base of the container and his index finger on the convex wall. He can then bring about delivery of the product by pressing on the convex wall in order to deliver the product. It is sufficient for him to stop pressing in order to stop the flow. The user therefore has better control over the delivery of the product. The assembly obtained in this way is highly ergonomic, and has a miniature shape or small size that is suitable for being used between two fingers. Such an arrangement is very convenient to use. Since the orifice has a small diameter and lies at the end of the nozzle, the product can flow onto the person's head in a highly localized fashion, which makes it possible to apply the product with a great deal of control. [0069] After having applied the contents of the bottle, the user may unscrew the head 30 from the empty bottle with a view to using it again later. Indeed, the head can be re-used in another bottle under the same conditions as during its first use, preferably after having been washed. [0070] Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
An assembly for the packaging and application of a fluid product in a container. A closure element closes an opening in the container in a manner which is leaktight for the product, with the closure element being fixed on the container by snap-fastening or screwing. An application head can be fixed on the container, and includes; i) an orifice for dispensing the product, which can communicate with the interior of the container; ii) an opening component intended to break the closure element of the container when the head is being fastened onto the container, in order to establish communication between the dispensing orifice and the interior of the container, and iii) a deformable wall which can deform in response to an external pressure exerted on the head, so as to cause the product to be dispensed.
1
FIELD OF THE INVENTION [0001] The invention relates to compositions and methods for prevention or treatment of negative effects of consuming ethyl alcohol in the form of alcoholic beverages. The composition can be used in the form of a nutritional supplement and the treatment may be administered prior to, during, or after the consumption of ethyl alcohol. BACKGROUND OF THE INVENTION [0002] The consumption of ethyl alcohol may be followed by a syndrome known as hangover. Symptoms of a hangover include headache, dehydration, nausea, nerve and muscle pain, lethargy, congestion, chills, tremor, diarrhea and fever. These symptoms may be particularly severe, especially after heavy consumption of alcoholic drinks. While not life-threatening, these symptoms are unpleasant and may interfere with job performance or home life. Additionally, the condition of alcohol induced hangover may cause a person to suffer a social stigma associated with the condition. [0003] Ethyl alcohol, or ethanol, is typically consumed by ingesting a liquid containing ethyl alcohol is typically produced by yeast in a fermentation process which converts sugars to alcohol and is then consumed, as is, in the case of beer or wine, for example. The fermented alcohol may be distilled to form spirits and then consumed, as is, in the case of vodka, for example. Additional sweeteners, water and other ingredients may be added. Once consumed, the ethyl alcohol in the beverage is absorbed by the stomach or small intestine and transferred to the liver through blood vessels. Metabolism of the alcohol takes place in a two-step enzymatic reaction. First, the alcohol is oxidized to acetaldehyde by alcohol dehydrogenases. Second, the acetaldehyde is oxidized to acetic acid by acetaldehyde dehydrogenases. The acetic acid is transported to the muscles and adipose tissue where it will be further broken down into carbon dioxide and water. The rate at which alcohol is metabolized depends upon the level of presence and activity of these enzymes. The rate at which alcohol is metabolized and eliminated from the body varies greatly among individuals. [0004] The negative effects of consumption of ethanol are due mainly to the toxic effects of acetaldehyde. Acetaldehyde provokes disturbances in bodily processes by, for example, forming adducts with hemoglobin and proteins of plasma of the brain and other organs; and inhibiting the transfer of reducing agents along the mitochondrial respiratory chain. Acetaldehyde also accumulates in the cerebellum causing headache by contracting cerebral blood vessels thereby decreasing blood flow resulting in pain. [0005] The symptoms of hangover have been treated with painkillers, such as aspirin or non-steroid anti-inflammatory drugs (“NSAIDs”) or antacids. However, painkillers may cause additional stomach upset and do not, alone, treat other symptoms of hangover. Acetaminophen, which is neither aspirin nor an NSAID, has been used to treat headaches and pains associated with hangover, but acetaminophen in combination with ethanol can result in extensive liver damage. The diuretic effect of alcohol results in dehydration and is generally treated with the consumption of large amounts of water after drinking ethanol. The consumption of water after drinking alcohol, however, does not alleviate the problems associated with the build up of acetaldehyde in the liver. [0006] Other means for treating hangover symptoms include “hair-of-the-dog” type treatments involving additional ethyl alcohol consumption for its analgesic properties. Such remedies ultimately prolong the effects of overindulgence, are dangerous and may lead to alcohol addiction. [0007] Herbal remedies have been used to alleviate or prevent symptoms of hangover. Examples of herbal remedies include teas made from the extracts of leaves, stems or roots of alder or mountain ash. This tea is rich in tannin that is said to provide protection to the stomach mucosa. Extracts of fruits of other plants may be added to the teas for their Vitamin C, amino acids and beta-carotene content. The beta-carotene is effective at clearing up cough and phlegm. [0008] Ginkgo biloba extract and taurine are components of another composition that has been used to alleviate hangover symptoms. The taurine is taken for liver protection and the Ginkgo biloba for its antioxidant effects against ethanol-derived oxidation and also facilitates circulation in the brain. [0009] Several methods of preventing alcohol absorption or allaying drunkenness are known. Abstinence, charcoal ingestion and charcoal ingestion in combination with Vitamin B-6 and Ephedra are examples. By abstaining from the consumption of alcoholic beverages a person avoids absorption of any ethanol and subsequent build up of acetaldehyde in the liver. However, the abstainer also will not enjoy the intoxicating effects of alcohol consumption. Charcoal ingestion is intended to absorb the alcohol in the stomach or small intestines resulting in a lower blood alcohol level. Charcoal ingestion therefore will decrease the socially desired effects associated with the consumption of ethanol. The Ephedra in the combination of Ephedra, charcoal and Vitamin B-6, acts as a vasoconstrictor of blood vessels, a stimulant, and a bronchiodialator. Galenic compositions have also been used to decrease the amount of blood alcohol. Another method of allaying drunkenness has been to ingest a combination of succinic acid, an L-glutamate compound, a fumaric acid compound, ascorbic acid, an energizer and a sugar. This method is also intended to dampen the intoxicating effects of alcohol consumption as well as treat the negative symptoms. [0010] There is a need for compositions and preventative treatments for ethanol induced hangover symptoms that are effective at treating the various symptoms of hangover without aggravating the symptoms further. Further, there is a need for the compositions and treatments for hangover symptoms to allow the user to enjoy the desired social effects of ethanol consumption while treating the cause of the negative effects of alcohol consumption. [0011] The invention provides a composition and method for preventing or treating ethanol induced hangover symptoms while avoiding the worsening of symptoms. These compositions and methods also allow for the enjoyment of the desired social effects of ethanol while preventing or treating the negative effects of ethanol consumption. BRIEF SUMMARY OF THE INVENTION [0012] One embodiment of the invention is a composition comprising silymarin, salicin, at least one B vitamin, magnesium, molybdenum and manganese. In one form of the composition, the at least one B vitamin is a combination of folic acid, Vitamin B12 and Vitamin B6. [0013] In one embodiment, the silymarin is soluble and in another embodiment the silymarin is a methylglucamine salt of silymarin. [0014] Another embodiment is a beverage comprising the composition of silymarin, salicin, at least one B vitamin, magnesium, molybdenum, manganese and a sweetener. In other embodiment, the beverage comprises the composition of silymarin, salicin, at least one B vitamin, magnesium, molybdenum, manganese and natural or artificial flavors. [0015] In yet a further embodiment of the invention, a method is provided for decreasing the negative effects of ethyl alcohol consumption comprising the step of administering to a person an amount of the composition sufficient to decrease the effects of acetaldehyde build up. [0016] Further, alternate embodiments include practicing the method prior to, simultaneously with or subsequent to the ingestion of ethyl alcohol. DETAILED DESCRIPTION OF THE INVENTION [0017] The composition of the present invention comprises essentially silimarin, salicin, B vitamins, magnesium, molybdenum and manganese. The composition may be administered before, during or after the consumption of ethanol to prevent or treat the negative effects of ethanol consumption while allowing the consumer of ethanol to enjoy the pleasant social effects of the alcohol. [0018] The terms “ethyl alcohol” and “ethanol” as used herein refer to any ethyl alcohol containing, or alcoholic, beverage including beer, wine, spirits and the like. [0019] Silymarin is a compound contained in a plant named Milk thistle ( Silybum marianum ) and is commonly known as St. Mary's thistle and Our Lady's thistle. Silymarin consists of various forms of hepatoprotectant flavonolignins. Silymarins protect the liver against a variety of toxins. The active components in silymarin include silybin, silychristin and silydianin. Silymarin repair mechanisms include increased synthesis of cellular proteins, increased rate of hepatocellular repair and anti-oxidant activity. Silymarin contributes to the regenerative activity of the liver by stimulating RNA polymerase and increasing synthesis of ribosomes. [0020] Silybins are only partially soluble in aqueous environments such as the body. Aqueous solutions of the compositions described herein are preferred for their increased bioavailability of silybins. The solubility of silybins is increased by forming salts of the compound or by chelation forming salt like compounds. Salts of silymarin extract have greater aqueous solubility and therefore greater bioavailability. One such salt of silymarin is an esterified hemisuccinate salt of silymarin. In particular, methylglucamine salt of silymarin is preferred for increased aqueous solubility and bioavailability. Chelation between methylglucamine and silymarin forms a salt. The methylglucamine salt of silymarin is available from Infinity Industries, Inc. (Ronkonkoma, N.Y.), as are all ingredients of the compositions described herein. [0021] The bioavailability of silymarin may also be increased by preparing a fluid mixture of Milk thistle dry extract in polyethylene glycol as described in EP 1 021 198 B 1. [0022] Concentrations or methylglucamine salt of silymarin in the range of from about 1.3 to about 27 percent by weight are used in the composition to alleviate hangover symptoms. A preferred concentration is about 3.6% by weight. [0023] Salicin is a compound contained in a plant known as Willow Bark or White Willow Bark. The extract of Willow Bark contains salicinium which reduces headache pain. The pain-relieving effects of salicin are similar to those of aspirin without side effects such as stomach upset. Salicin is converted to aspirin in vivo and provides a delayed pain relieving affect after the ingestion of the compositions disclosed herein. Therefore, stomach upset is delayed or may not be perceived due to the pain relieving effects of the alcohol ingested. Salicin's inhibitory effect on prostaglandin synthesis in nerve cells is the mechanism by which salicin relieves pain. White willow bark extract or pure salicin in the concentration range of from about 1.5 to about 21 percent by weight are used in the compositions described herein to provide relief from hangover symptoms. A concentration of about 4.5% is preferred. [0024] B vitamins combat the depressive effects of ethanol consumption, particularly vitamins B12 and folic acid. Vitamin B6, in addition to combating depression, also assists in the transmission of chemicals in the nervous system. B vitamins are lost during the consumption of ethanol due to the diuretic effects of such consumption. It is preferred to use vitamins B6, B12 and folic acid in combination as these vitamins in combination increase levels of tetrahydropterin, a coenzyme necessary for the production of serotonin (and thus melatonin), dopamine, epinephrine and norepinephrine. A concentration of vitamin B6 in the range of from about 0.12 to about 2.05 percent by weight is used in the composition and a concentration of about 0.36% by weight is preferred. Concentrations of folic acid of from about 0.05 to about 0.8 percent by weight are used and a concentration of about 0.14% by weight is preferred. Concentrations of vitamin B12 of from about 0.06 to about 1.03 are used and a preferred concentration is about 0.18% by weight. [0025] Magnesium is a component of red blood cells and plays role in controlling blood pressure. Maintaining control of blood pressure is a factor in controlling the severity of a headache. Magnesium may be included in the compositions disclosed herein the forms of magnesium citrate in concentrations of from about 55% to about 97.45% by weight and preferably about 90% by weight. [0026] Molybdenum acts as a co-factor of aldehyde dehydrogenase in the oxidation process that results in the conversion of alcohol to acetic acid. Specifically, molybdenum assists the enzyme aldehyde oxidase or aldehyde dehydrogenase in acetaldehyde to acetic acid. Molybdenum also alleviates the allergenic effects of aldehydes or ketones in persons sensitive to these compounds. Molybdenum may be added to the compositions disclosed herein in the form of chelated molybdenum in concentrations that from about 0.03% to about 1.03% by weight and preferably about 0.18% by weight. [0027] Manganese directly oxidizes acetaldehyde to acetic acid and therefore quickens the alleviation of negative symptoms caused by acetaldehyde build up after the consumption of ethanol. Aldehyde dehydrogenase enzyme may use manganese as a cofactor instead of molybdenum. Preferred manganese compounds exhibit the lowest oxidation state (+2). The Manganese may be added to the compositions disclosed herein in the form of manganese sulfate in concentrations that range from about 0.3% to about 5% by weight and preferably about 0.9% by weight. [0028] The formulations described herein may be administered by any appropriate means. The preferred means of administration is by oral route. The formulation may be ingested in pill, tablet, capsule or liquid form. The liquid form is preferred for its higher bioavailibity of silymarin. Effective amounts of the compositions may be administered before or after the consumption of an alcoholic beverage, preferably before the consumption of alcohol so that the active components are available when acetaldehyde levels begin to build. The compositions may be administered during the consumption of alcohol alone or in combination with a specific ethanol as a drink mixer. [0029] The compositions may be self-administered and the amount required to be taken is dependent upon several factors regarding the person ingesting the ethanol. The amount, type and strength of the alcoholic beverage the person intends to consume, knowledge of ethanol tolerance of the person and the need for alertness and/or focus for activities that will follow consumption of such beverages are factors considered when determining dose. [0030] Subjective tests were conducted by asking individuals who used the compositions described herein before during and after the consumption of alcoholic beverages how they felt after consuming several alcoholic drinks. The following compositions offered noticeable relief to the negative effects to alcohol consumption: [0031] 20-150 mg of silymarin methylglucamine (1.23-35.81 wt %); [0032] 10-75 mg salicin (0.59-21.17 wt %); [0033] 2-6 mg of Vitamin B6 (0.11-2.05 wt %); [0034] 0.8-2.4 mg folic acid (0.03-0.83 wt %); [0035] 1-3 mg Vitamin B12 (0.05-1.03 wt %); [0036] 250-1500 mg of magnesium citrate (49.56-97.45 wt %); [0037] 0.5-3 mg of chelated molybdenum (0.03-1.03 wt %); and [0038] 5-15 mg of manganese sulfate (0.29-5.01 wt %) [0039] Preferred ranges of the individual components of the composition are: [0040] 20-60 mg of silymarin methylglucamine (1.23-10.09 wt %); [0041] 25-75 mg salicin (1.55-21.17 wt %); [0042] 2-6 mg of Vitamin B6 (0.11-2.05 wt %); [0043] 0.8-2.4 mg folic acid (0.05-0.83 wt %); [0044] 1-3 mg Vitamin B12 (0.06-1.03 wt %); [0045] 500-1500 mg of magnesium citrate 75.26-97.45 wt %); [0046] 1-3 mg of chelated molybdenum (0.06-1.03 wt %); and [0047] 5-15 mg of manganese sulfate (0.29-5.01 wt %) [0048] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein. [0049] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention. [0050] While some potential advantages and objects have been expressly identified herein, it should be understood that some embodiments of the invention may not provide all, or any, of the expressly identified advantages and objects. [0051] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations of those preferred embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. [0052] The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope. [0053] Example 1 includes the following formulation (values are in wt %): silymarin methylglucamine 9.94 salicin 16.75 Thiamine HCL 1.23 Riboflavin 1.68 Niacinamide 1.68 pantothenic acid 0.84 Vitamin B6 0.17 folic acid 0.03 Vitamin B12 0.05 Chelated molybdenum 0.03 magnesium citrate 67.15 manganese sulfate 0.45
Described is a composition for the prevention and treatment of symptoms associated with ethyl alcohol consumption. The composition comprises silymarin, salicin, at least one B vitamin, magnesium, molybdenum and manganese. Treatment of symptoms associated with the consumption of ethyl alcohol involves ingesting the described composition prior to, during, or after the consumption of the alcohol.
0
FIELD OF THE INVENTION [0001] The field relates to mobilization equipment for shelving. BACKGROUND [0002] Within the context of this specification, gondola, gondola run, gondolas and gondola islands all refer to store shelving known in the field. Gondolas, such as the one depicted in FIGS. 13A-13C , are known with or without a central support column and with one or two sides having shelving attached. Warehouse pallet racking is also known, such as pallet racking used in home centers and warehouses. Unless otherwise expressly indicated, the term gondolas refer to both a single gondola or a gondola run having a plurality of gondolas or both. [0003] Lifting systems are known that use a plurality of caster wheels to mobilize empty gondolas or gondolas that have at least a portion of the racked products removed from the gondolas. U.S. Patent Publication 2007/0194546, published Aug. 23, 2007, and U.S. Patent Publication 2007/0059138, published Mar. 15, 2007 illustrate systems with a screw or hydraulic jack for lifting gondolas, the description and drawings of which are hereby incorporated for background herein. Two devices are disposed on opposite sides of the gondolas at each upright support, which may be accessible behind a kick plate. Each upright support is raised using the lifting apparatus and the gondola, even if quite long, is movable using the lifting system as a hand truck, with each of the hand trucks being moved at the same time. [0004] However, deep gondolas and gondolas with products racked on the gondolas cannot be moved using these known devices. An upright support in the middle of a gondola, between two opposite sides of the gondola, bows excessively, causing damage to the gondola support structure and tumbling of the products. Thus, a time consuming unracking and reracking of at least a significant portion of the products on the gondolas is required in order to mobilize the gondolas. [0005] U.S. patent application Ser. No. 12/364,177, the disclosure of which is incorporated herein, teaches a system for mobilization of stocked gondolas that allows for mobilization without removing shelving and without removing the products from the shelving of the gondolas or pallet racking. The system described a lifting mechanism attachable an H-support or other upright support of pallet racking, such as for use in mobilization of the pallet racking, but only from an exposed front or side of the H-support. Using the system for mobilizing a gondola permits even very deep and very wide gondolas to be mobilized, without unracking and/or disassembly of the gondolas and/or removal of product from the shelves, when a pair of opposing members are positioned such that the members extend along the depth of the gondola from one side to an opposite side. Each pair of opposing members is positioned such that the pair of members is disposed on opposite sides of a gondola support. A slidable middle lift bracket on each of the pair of opposing members is positioned at the middle, upright support of the gondola, and may have additional lift brackets disposed at other upright support members of the gondola. An interlinking tongue and loop system may be used to slide under the supports and to engage one lift bracket to its opposite lift bracket. Thus, the pair of opposing members may provide rigid support to the gondola, when the pair of opposing members are lifted, allowing for mobilization of the gondola. In this system, a modified jack engaged each end of each of the opposing members, such as a screw or hydraulic mechanism coupled with a pair of forks capable of engaging the pair of opposing members, such that the forks raise and lower the pair of opposing members together, at the same time. The forks are fixed in position and are not capable of displacement to make positioning of the jack in narrow inaccessible spaces. [0006] In one example, a hand crank, such as a hand crank and screw similar to that of a boat trailer hitch apparatus, is used to lift a pair of forks inserted into the opposing members. A screw and handcrank is capable of replacing a heavier, more expensive and harder to maintain hydraulic jack, for example, when a plurality of such lift mechanisms are coupled to opposite ends of a plurality of the support apparatuses spaced at intervals along a gondola run. No single lift mechanism is required to exceed its rated lifting potential. The lack of any significant sagging from one side of the gondola reduces the height that the lift must raise the gondola to mobilize it, because the support bar is capable of supporting the supporting structure of the gondola a plurality of support points, such as three or more support points. In some of the examples, three support points are disclosed, but additional support points may be added in other applications requiring support of larger spans, for example. [0007] Single sided gondolas and islands may be raised and lowered similarly to the double-sided gondolas provided in the examples. In single sided gondolas, a support bar may be supported on only one side by a lift mechanism or on both sides. If supported on only one side by a lift mechanism, then other end of the support bar may be unsupported, requiring a counterbalance on the lift mechanism, or may be provided with a low-profile caster wheel that provides a fulcrum at an opposite end of the support bar assembly for lifting of the gondola during raising of the end of the support bar assembly attached to the lift mechanism, for example. In this way, a gondola having one side against a wall may be mobilized, for example, using a plurality of lift mechanisms along the side of the gondola facing away from the wall, only, while the low-profile casters inserted into or onto the support bar assemblies allow the support bar assemblies to be inserted and aligned under the gondolas. [0008] Instead of forks, other structures are suggested to mount the lifting apparatus to the support structures used in lifting of the gondolas or to the gondolas, themselves. These other structures may be grabs, bolts or fingers, for example. Grabs are L-shaped extensions from a surface of the lift mechanism that are capable of engaging slots in a coupling mechanism or a gondola. For example, forks may be attached to an attachment member having slots that engage the grabs, allowing the forks to be positioned in the ends of the gondola support bars prior to engaging the lift apparatus to the forks. Then, the lift apparatus may be positioned such that the grabs engage the slots in the attachment member of the forks, and the lift apparatus may be raised until the grabs firmly engage in the slots prior to raising the gondolas. Bolts are fasteners extending from the lift mechanisms that are coupled with nuts or plates having a threaded or other coupling mechanism for attachment to the bolts when inserted through a hole or slot in the gondolas or the attachment member of the forks, for example. Fingers are projections, shaped or straight that matingly engage the gondola or the attachment member of the forks, for example. Thus, when properly engaged to the supports or the gondolas, the lift mechanism provides for a positive displacement upward and downward. However, these other structures did not suggest the use of any structures capable of moving, pivotally, while remaining engaged to the lift mechanism. [0009] Shelving used in warehouses, superstores, consumer retail clubs and home improvement stores cannot be moved using a lifting bar mechanism. Furthermore, these types of shelves are usually positioned back-to-back to form aisles with little space between the shelves, making it difficult to insert any known lifting mechanism between the shelves. Instead, only the sides of the shelving are accessible for coupling to the jacks described in a Mobilization System for Lifting and Mobilization of Gondolas. SUMMARY [0010] A lifting device includes a jack and a pivotably positionable attachment mechanism, pivotally coupled to the jack, such that the attachment mechanism is capable of being initially displaced in the plane of the jack mechanism during insertion of the lifting device in a narrowly accessible space adjacent to shelving. Then, the attachment mechanism is capable of being pivoted to extend outwardly from the plane of the surface of a jack facing the shelving, such that the shelving may be attached to the attachment mechanism extending on one or both sides of a shelving support. [0011] For example, the shelving support may be an upright element of H-shelving that has holes provided in the upright element, and the attachment mechanism may comprise one or more holes extending through a plate pivotally coupled to the jack by a hinge. When pivoted into position for attaching to the shelving, a pair of plates may sandwich the upright element. By adjusting the height of the plates, such as by raising or lowering the jack with a ratchet mechanism, one or more pins may be inserted through the holes in the holes in the plates and the holes in the upright element of the shelving, securing the lifting mechanism to the upright element. By raising the raising the lifting mechanism using the jack, the lifting element, in conjunction with a set of lifting mechanisms likewise attached to other upright elements of the shelving, supports the weight of the shelving, with or without unstocking the shelving. [0012] The pivotably displaceable attachment mechanism makes insertion of the lifting device possible in a narrow space provided between back-to-back rows of stocked shelving, which would otherwise be immovable using known jacks and mobilization gear. [0013] In addition, the pins used with the attachment mechanism to secure the upright element of shelving to the attachment mechanism may, themselves, be secured to the jacks by a tether, at all times. In combination with the pivotally coupled plates of the attachment mechanism, for example, the tethered pins insure that everything necessary to align and attach a lifting device to shelving is present at all times. BRIEF DESCRIPTION OF THE DRAWINGS [0014] FIGS. 1A-1C illustrate views of one example of a support bar assembly of a mobilization system for lifting and mobilization of gondolas. [0015] FIG. 1B illustrates a top plan view of the example in FIG. 1A . [0016] FIGS. 2A and 2B illustrate views of a tube having a channel. [0017] FIGS. 3A-3B illustrate (A) a partial cross sectional view of an example of a caster wheel insert 300 for single-sided gondola mobilization, and (B) an end portion 302 for coupling with an end of a support bar assembly. [0018] FIG. 4A illustrates a side view of an extendable member for insertion telescopically into a receiving extendable member of the example illustrated in FIGS. 1A-1C . [0019] FIG. 4B illustrates an end plan view of the extendable member of FIG. 4A . [0020] FIG. 5A sketches an example of a system for mobilization of stocked gondolas mounted on two different types of manual lift trucks. [0021] FIG. 5B sketches a push pull rod. [0022] FIG. 6A illustrates a perspective view of an extendable tube for use in fabricating an extendable member of the system of FIG. 1A and FIG. 1B . [0023] FIG. 6B illustrates a side view of the extendable tube of FIG. 6A . [0024] FIG. 6C illustrates a top view of the extendable tube of FIG. 6A . [0025] FIG. 6D illustrates an end view of the extendable tube of FIG. 6A . [0026] FIGS. 7A-7C illustrate views of a receiving member. [0027] FIG. 7B illustrates a side plan view of the receiving member of FIG. 5A . [0028] FIGS. 8A-8C illustrate views a tongue. [0029] FIG. 9A-9C illustrate views of a tube fabricated from two L-shaped members. [0030] FIGS. 10A-10C illustrate views a retaining member. [0031] FIGS. 11A and 11B illustrate a mating portion of a lifting apparatus for use with examples of a mobilization system for use with gondolas. [0032] FIGS. 12A-12C illustrate views of a slide bracket. [0033] FIG. 12B illustrates an end plan view of the assembly of FIG. 12A . [0034] FIGS. 13A-13C illustrate a known gondola with (A) an assembled gondola run, (B) an exploded view of a gondola section, and (C) an end cap for terminating one end of the gondola run. [0035] FIG. 14 illustrates a sketch of an example of a portion of a lifting apparatus for mobilization of stocked gondolas assembled and installed on one end of a gondola having products displayed on the shelving of the gondola. [0036] FIGS. 15A-15E illustrate sketches of an example of a lifting mechanism. [0037] FIGS. 16A-19B illustrate views of examples of a lifting device insertable in a gap between two back-to-back rows of warehouse shelving, for example. [0038] FIG. 20 illustrates an exploded view of one example of a lifting device. [0039] FIG. 21 illustrates a detailed, perspective view of an example of a plate used in an attachment mechanism. [0040] FIG. 22 illustrates a support plate used in a support for an attachment mechanism. [0041] FIG. 23 illustrates a known ratchet wrench. [0042] FIG. 24 illustrates a plurality of lifting devices supporting shelving. DETAILED DESCRIPTION [0043] Many variations and combinations of the component parts illustrated in the drawings and disclosed in the examples are included within the scope of the invention. FIGS. 1A-1C and 5 A illustrate an example of a support bar assembly 1000 of a mobilization system for stocked gondolas 1 . A system comprises two opposing, complementary assemblies 1000 that have brackets 50 , 120 and one or more extendable members 60 , 160 —with tongues 32 , 124 , 82 that fit into receiving members 70 , 122 of one assembly 1000 opposite from the other assembly 1000 . The tongues 32 , 124 , 82 and receiving members 70 , 122 interlock and support a plurality of support points of a gondola, such as the middle support B and outer supports A, C of gondola 1 , as illustrated in the example of FIG. 14 . The gondola 1 may be stocked with items 3 on the shelves during mobilization of the gondola 1 . [0044] Components may be fabricated, such as by welding and assembly, to provide a pair of complementary, opposing support bar assemblies 1000 , such as illustrated schematically in the sketch of FIG. 5A . FIG. 2A shows a side plan view of a tube used in fabricating components of the examples. The tube 200 may be made of a rigid material having a sufficient stiffness and other mechanical properties to safely raise and move gondolas together with items stocked on the gondolas. The dimensions of the tube 200 are selected to provide sufficient stiffness and to mate with other components of the assemblies 1000 . For example, components may be coupled telescopically, as illustrated in FIG. 1A-1C . The height H of a support component, such as the extendable member 60 , must be able to fit under the bottom shelf of a gondola, if a solid kick plate is removed or if an open-faced kick plate is present or otherwise. The length of a support component L, such as an extendable member 60 , may be selected to allow the assembly 1000 to extend from one side of a gondola to the other, when coupled telescopically with other components of the assembly 1000 . A plurality of opposing assemblies 1000 may be coupled at a plurality of supports along the length of a gondola or gondola run, such as a gondola run running the length of an aisle in a store. By installing a plurality of the assemblies 1000 along the length of the gondolas, the entire aisle of gondolas may be lifted and mobilized, together with stockage, for example. [0045] On one end of an assembly 1000 , an end bracket 50 may be attached to an extendable member 160 , which may be telescopically mated with another extendable member 60 , for example. An end bracket 50 may be coupled to an extendable member 60 , 160 by any means, such as by welding, fastening, bonding or the like. In one example, an extendable member 60 has an integrated end bracket with a slot 65 for holding a pin, as illustrated in detail in FIGS. 6B and 11B , and a retaining member 70 and tongue 82 welded to a bottom portion of the extendable member 60 . The slot may have a length q greater than its width p, and may be distance from the top of the member 60 and at a distance c from the end of the member 60 . The distances a, c may be selected to align the slot 65 with a recess 25 in one of the forks 20 , as illustrated in FIG. 11A , for example. [0046] In one example of an extendable member 60 , fourteen through holes 63 or recesses may be provided at a height h and starting at a distance 1 from one end of the extendable member 60 as illustrated in more detail in FIG. 6A-6C . The holes may be disposed at a distance b one from the other, for example, such that telescopically inserted second extendable member 160 may be coupled with a retainer in one or more of the holes 63 of the first extendable member 60 having the holes 63 , as illustrated in FIGS. 1A and 1B , which show the second extendable member 160 extending into the first extendable member 60 , by making the first extendable member 60 transparent or using hidden lines. The holes 63 may be provided for convenience and flexibility in adjusting the length of a support bar 1000 during installing and disassembly of the system, for example. [0047] FIG. 2B shows a perspective view of a tube 200 having a channel 229 extending along the length of a tube 200 . The example of a tube 200 , as illustrated in FIGS. 2A and 2B may be used to fabricate components of the support bar assembly 1000 , for example. The channel 229 may have another tube inserted along the channel, providing for a telescopic fit of one tube inside of the other or a sliding fit of a bracket made from the tube on another tube. Thus, the tube 200 may cooperatively engage another tube or a solid member for extending along the axis of the tube 200 . In this way, the system may be adjusted in length to accommodate a variety of gondolas with varying lengths, depths, widths and configurations. For example, a middle slide bracket 120 may be fabricated from such a tube 200 and may be slidably disposed on the extendable member 60 , as illustrated in FIG. 1C . The slide bracket 120 is moveable in either direction Q along the extendable member 60 , allowing the slide bracket 120 to be aligned with a central support B of a gondola 1 , for example, as illustrated in FIG. 14 . A middle slide bracket 120 , as illustrated in the example of FIGS. 9A-9C , may be fabricated by tube forming or by welding or otherwise binding together of two L-shaped members 121 , 123 to form the tube 200 . FIGS. 12A-12C illustrate a detail view of such a slide bracket 1200 having a tongue 82 and a retainer 122 welded to the bottom of one of the L-shaped members 121 , 123 that form the tube 200 , for example. Dimensions shown are provided as an example, only. [0048] A tongue 82 may have a tapered end 84 , such as illustrated in FIGS. 8A-8C , for example. In one example, the tongue 82 has material removed, such as by machining or grinding, to form the tapered end 84 . In another example, the tapered end 84 of the tongue 82 is forged into shape. The tapered end 84 is insertable to provide support under a gondola 1 support A, B, C and extends through a retaining member 122 of an opposite positioned assembly 1000 , for example. [0049] FIGS. 3A-3B illustrate (A) a partial cross sectional view of an example of a caster wheel assembly 300 for single-sided gondola mobilization, and (B) an end portion 302 for insertably coupling with an end of a support bar assembly. Other end portions may be used to couple with the support bar assembly. A caster wheel 304 multi-directionally couples a wheel 305 to a coupling member 306 , such as by a threaded lug 307 . The wheel 305 pivots freely about a rotational axis that may be aligned with the axis of the lug 307 , for example. A cavity is formed by the coupling member 306 that permits free pivoting of the wheel 305 within the cavity during mobilization of the gondolas. The wheel 305 extends below the end portion 302 used for coupling with the support bar assembly. By extending slightly below the support bar assembly, the wheel 305 may acts as a fulcrum point for raising a gondola, when support bar assemblies having the caster wheel assembly 300 coupled at one end are raised at an opposite end by a lift mechanism. In one example, the end portion 302 is coupled to the support bar assembly by inserting the end portion 302 into the support bar assembly in the same manner as one of the forks of a lift mechanism would be inserted into the support bar assembly. A slot or hole 309 may be provided for insertion of a pin to retain the end portion 302 within the support bar assembly, for example. [0050] One-sided gondolas and islands may be raised and lowered similarly to the double-sided gondolas provided in the example of FIG. 14 . In single sided gondolas, a support bar may be supported on only one side by a lift mechanism or on both sides. If supported on only one side by a lift mechanism, then other end of the support bar may be unsupported, requiring a counterbalance on the lift mechanism, or may be provided with a low-profile caster wheel assembly 300 , such as illustrated in FIGS. 3A and 3B , for example. In this way, a gondola having one side against a wall may be mobilized, for example, using a plurality of lift mechanisms along the side of the gondola facing away from the wall, without the use of any other special equipment than the caster wheel assemblies 300 . Thus, a system for mobilization of double-sided gondolas 1 may be used for single-sided gondolas positioned against a wall, without much modification to the method or equipment. A push/pull rod or other device may be coupled to a mounting bracket 301 , which may be coupled to the caster wheel assembly 300 , for example, to assist in the pushing or pulling of gondolas 1 . In another example, a pair of caster wheel assemblies 300 may be used for one or more of the pair of opposing support bar assemblies 1000 in mobilization of double sided gondolas 1 or gondola islands. [0051] FIGS. 4A and 4B show an extendable member 400 for insertion into a receiving extendable member 60 . A detent ball 405 provides for retaining of the member in the receiving member, for example. Alternatively or additionally, a pin may be inserted through a hole 406 in the member. [0052] FIG. 5 provides a sketch of an assembled example of pair of support assemblies 1000 of a system for mobilization of stocked gondolas mounted on two different types of manual lift trucks 1400 , 1401 . One of the trucks 1401 uses a lift mechanism similar to a boat trailer jack. A boat trailer jack uses a hand crank to raise and lower the boat and to give the trailer mobility, in some instances, when the jack has one or more caster wheels. A rack and pinion gear mechanism may be used to translate rotational motion of a hand crank to translational motion of the jack raising and lowering the gondolas, for example. The other truck 1400 uses a hydraulic jack, for example. Any jack with sufficient force to lift the gondolas may be used with a hand truck of the type known in the art to lift and mobilize the gondolas. The hydraulic truck 1400 has an hydraulic jack 1559 mounted between a base and a height adjustable lifting mechanism 1557 , which may have one or more grabs 1510 for coupling to a mounting fixture, such as a plate 1593 or slats 1594 , 1596 . A handle 1553 is provided for positioning and coupling the hydraulic lift 1400 to the support assembly 500 . As illustrated in FIG. 5B , a push-pull rod 1580 may be coupled by a hook to an eyebolt 1526 or a U-shaped attachment point 1525 on a truck 1400 , 1403 , as illustrated in FIGS. 5A and 15A , respectively. [0053] FIG. 6A shows a perspective view of an example of an extendable member 60 that has a channel 61 for mating with a fork-like extension, for example. The member 60 may itself be inserted into a channel 42 , 52 of another tube 40 , 41 . As sketched in the example of FIG. 5A , a support assembly 500 may comprise a pair of opposing support bar assemblies 1000 , as illustrated in detailed views of FIGS. 1A-1C , for example. In the detailed views of FIGS. 1A-1C , one end 50 slips telescopically over a first end of an intermediate member 160 , and an elongated member 40 slips telescopically over an opposite end of the intermediate member 60 . The elongated member 40 in this example has a plurality of holes 63 extending through the thickness of at least one outer wall of the tubular member 40 , such that a pin or detent ball or both may be used to couple the elongated member 40 and the intermediate member 160 preventing relative movement of the two members 40 , 160 during mobilization of a gondola or a pallet racking. In FIG. 5A , a partial exploded view illustrates the alignment and positioning of two examples of trucks 1400 , 1401 with one using a hand crank 145 for raising and lowering the system and the other using a hydraulic jack handle 1555 to raise and lower a hydraulic jack 1559 that raises and lowers the system. One end 41 may be coupled to the other tube 40 , 60 , 160 by an intermediate member 54 , as illustrated in the example of FIG. 11B , for example. Regardless of the type of coupling of one member of a support bar to another, tongues 32 , 34 and retainers 70 are aligned between the right-hand and left-hand support bars to provide an interlocking fit, for example. [0054] As illustrated in the drawings of the system, a receiving member 70 is attached to opposing members and are disposed to receive the tongue of the opposing member. A receiving member 70 has a first end 73 and a second end 71 that are attachable to a portion of the system and a body 72 connecting the first end 73 and the second end 71 , as illustrated in the views of FIGS. 7A-7C , for example. [0055] FIGS. 8A and 8B illustrate a tongue 82 having a tapered end 84 . A tongue 82 and a receiving member may be assembled for a bracket. A receiving member 70 , 122 may be used, as illustrated in FIGS. 7A-7C and FIGS. 10A-10C , for example. The bracket 1200 in FIGS. 12A-12C is assembled using the tube 200 of FIGS. 2A and 2B with the receiving member 122 of FIGS. 10A-10C , such as by welding, for use as a slidable, middle bracket for engaging the gondolas at a middle shelf support B. This middle bracket 1200 allows very heavy gondolas and very deep gondolas to be moved without unstocking the shelves, for example. The tongue 82 may be welded to the tube 200 and the receiving member 122 , as illustrated in FIGS. 12A-12C , for example. The assembly provides for an interlocking of the tongues 82 , 124 , 125 of opposing assemblies 1000 . [0056] FIGS. 11A and 11B show a portion of a manual truck having forked extensions 10 , 20 , extending fork-like, that mate with tubes 40 , 41 . The extensions 10 , 20 fit into the channels 42 , 52 of their respective tubes 40 , 41 , as illustrated in FIG. 11B , for example. One of the ends may have a pin 45 inserted through a slot 49 formed in the end of the member 40 , and the pin 45 may be disposed such that it engages a recess 25 formed in the end of at least one of the forks 20 . When the pin 45 engages the recess 25 , the fork 20 is latched in the end of the member 40 . Then, when the system is raised, the lifting system, which has wheels, such as caster wheels, may be pulled or pushed to mobilize the gondola and the fork 20 remains latched in the channel formed by the end of the member 40 . By lifting the pin 45 free of the recess 25 formed in the at least one fork 20 , the fork 20 may be withdrawn from the channel 42 , after the gondola is moved and the pair of opposing members are lowered to rest the gondola on the ground, for example. The pin 45 may be retained by a flange, such as a head 47 and/or threaded nuts 43 , and/or a cotter pin or the like. Preferably, the pin may be easily raised to release the pin 45 from the recess 25 . [0057] FIG. 11B illustrates the interlocking relationship between two tongues 32 , 34 , at one end of a pair of support members, for example. When the opposing members 40 , 41 are aligned on opposite sides of the gondolas supports and are mated, the tongues 32 , 34 are retained by the receiving members 70 in the opposing member opposite of the tongues 32 , 34 . [0058] FIG. 14 illustrates an example of a system for mobilization of stocked gondolas 1 assembled and installed on one end of gondolas 1 having products 3 displayed on the gondolas 1 , for example. A tongue 182 from an opposite half of a lift assembly 500 matingly engages a receiving member of the half of the lift assembly 500 shown on an end of the gondolas 1 . In a method of moving gondolas 1 a plurality of lift assemblies 500 are positioned along the length of the gondolas 1 such that the entire length of the gondolas 1 may be raised by the lift mechanisms of the trucks 148 . When raised, the gondolas 1 may be moved on the caster wheels 149 of the trucks 148 by pulling or pushing the trucks 148 , such as by the push-pull handle 1580 illustrated in FIG. 5B , for example. In one example, a hand crank 145 with a rack and pinion gear mechanism 142 is used to raise and lower the fork-like extensions 10 , 20 attached to the truck 1401 , as illustrated in the example of FIG. 5A , for example. In another example, a hydraulically activated truck 1400 is used to raise and lower fork-like extensions 10 , 20 attached to the truck 1400 . Either mechanism, or other lift mechanisms, may be capable of raising and lowering gondolas 1 , when the lift assembly 500 is aligned on opposite sides of gondola supports A, B, C and is matingly assembled by inserting the tongues 32 , 34 , 82 , 124 , 125 , 126 into the receiving members 70 , 122 . In a preferred example, each tongue fits into its respective receiver provider an interlocking fit between each pair of support bar assemblies 500 . [0059] If the opposite halves of the support assembly 500 are properly aligned and matingly engaged, then the extensions 10 , 20 of the trucks 147 , 148 are aligned and engaged in tubular channels 42 , 52 in the ends of tubular members 40 , 41 , 50 , as illustrated in FIG. 5 , FIG. 11A , FIG. 11B , and FIG. 14 , for example. A bracket 120 is capable of being aligned with a middle support B, for example, by slidably engaging a continuous tubular member 40 on each of two opposite halves of the support assembly 500 , as illustrated in FIG. 14 , for example. [0060] In the example of FIG. 14 , the length of the two halves of the support assembly 500 is adjusted using extension member 60 and intermediate member 54 for aligning the ends of the tubular supports 40 , 60 having tongues 82 with one outer support A of the gondolas 1 and the tongues 32 , 34 , 182 of a tubular member 50 with an opposite outer support C of the gondolas 1 . The extendable member 60 and intermediate member 54 may telescopically engage to provide for adjusting of the length of the support assembly 500 from one meter to several meters, for example. Since the gondola 1 is fully supported by the middle and outer supports A, B, C, items 3 do not have to be removed from the gondola 1 , even for very wide gondolas 1 , which otherwise requires labor intensive removal and restocking. Thus, the support assembly 500 provides for a method that saves substantial time and money compared to prior art methods of gondolas mobilization that could not be used to move wide gondolas. In prior art systems, lifts and wheels were only positioned on the outer supports A, C and could not provide support at all of the supports A, B, C. Another system is known that only provides support at a middle support B but not at all of the supports A, B, C. [0061] In the example of FIGS. 15A-15E , views of an example of a preferred lifting mechanism 1403 are illustrated or sketched that comprise a hand crank 1530 (detailed view in FIG. 15C ), a screw mechanism contained in a column 1550 , such as a rack and pinion gear, for raising and lowering a coupling mechanism 1500 (detailed views in FIGS. 15D and 15E ) attached to the column 1550 by one or more pins 1502 . A pin 1502 may be biased into a hole 1556 in the column 1550 by a biasing mechanism 1503 , adjustably. A pull knob 1501 may be used to release the pin 1502 from the hole 1556 , as illustrated in FIGS. 15A and 15B , for example. The coupling mechanism 1500 may include one or more grabs 1510 , 1511 , which are capable of being mounted in slots on a plate or other mounting device. As illustrated in the example of FIGS. 15D and 15E , the grabs 1510 , 1511 are both L-shaped members welded to a flared portion 1509 of the coupling mechanism 1500 , for example. A shaft 1507 fits slidably around the column 1550 of the lifting mechanism 1403 , for example. In an alternative embodiment, the coupling mechanism 1500 may be fixed to the column 1550 such as by welding. [0062] A base 1560 includes a pair of casters 1558 and a mounting surface for mounting to a bracket 1562 of the column 1550 . The coupling mechanism 1500 may include one or more stabilizers 1520 capable of extending to the ground to provide a point of contact to the ground in addition to the casters 1558 for keeping the lifting mechanism 1403 balanced in an upright position, as illustrated in the views of FIGS. 15A and 15E , for example. Alternatively, the coupling mechanism 1500 may include grabs, fasteners or another coupler for coupling directly or indirectly with a gondola. The coupling mechanism, as illustrated in FIGS. 15D and 15E , are provided with L-shaped grabs that are capable of mating with slots formed a gondola structure or in a mounting plate that may be attached to a mechanism for coupling to a gondola or support assemblies, such as the fork extensions 10 , 20 of FIG. 11A and as illustrated in FIG. 5A , for example. In FIG. 5A , a plate 1593 and a pair of lateral members 1594 , 1596 are shown for mounting the forks 10 , 20 to an example of a rack and pinion lift mechanism 1401 or a hydraulic lift mechanism 1400 , for example. [0063] A handle 1530 , such as illustrated in detail in FIG. 15C may include a rotatable grip 1532 and a ratchet coupling 1535 for removably attaching the handle to a ratchet mechanism in the head of the screw mechanism, such as by the biased detent ball 1537 engaging a groove in the ratchet mechanism 1545 . A ratchet mechanism 1545 in the head 1540 attached to column 1550 is surprisingly useful, allowing precise simultaneous raising of a plurality of lift mechanisms by a plurality of users of a plurality of lifting mechanisms, even if one or more of the lifting mechanism are in areas having insufficient room to rotate the handle 1530 by 360 degrees. In addition, an unexpected advantage of having a removably coupled handle 1530 is that storage requirements for a mobilization system are greatly reduced compared to a system with a fixed handle. A U-shaped handle 1525 on the lifting mechanism 1403 provides for coupling to a pull bar (not shown). A pull bar may have a hook on one end of an elongated member for coupling to the U-shaped handle 1525 and may have a handle on the opposite end of the elongated member. The pull bar may be used to pull or push the lifting mechanism 1403 during mobilization of a gondola 1 , for example. [0064] FIGS. 18A-22 illustrate views of a swing support mobilization lifting device. In this example, a lifting device 5000 is provided for insertion in otherwise inaccessible locations for attachment to support structures of shelving. Holes H in the support structure P of the shelving are aligned with holes, slots, slits or the like in an attachment mechanism 5010 , 5040 . The attachment mechanism may comprise one or more swing arms 5010 , 5040 capable of pivotally rotating about a hinge 5017 coupling the swing arm 5010 , 5040 to a jack capable of raising and lowering the swing arm. The jack may be any jack, mechanical, electric, hydraulic or pneumatic; however a mechanical jack, such as used for a boat trailer is preferred for ease of maintenance and small size. The attachment mechanism in the example is comprised of two plates 5010 , 5040 (or plate-like members), but may be comprised of a one or more members of any type capable of pivoting out of the way during placement and being pivoted into a support position capable of engaging a portion of the shelving to be supported. In the example of FIG. 21 , holes or slots, 5013 , 5015 are provided in an end of a plate 5010 opposite of the hinge 5017 . A locking tab 5011 may extend from a bottom surface to engagingly fit into slots 5032 , 5034 of a support plate 5030 , as illustrated in FIG. 22 , providing locking of the plate in one of two positions. A spring 5012 may bias the plate downwardly, locking the tab 5011 in a slot 5032 , 5034 of the support plate 5030 . Thus, the attachment mechanism is displaceable from a stowed position to a support position, for example, by lifting the plate 5010 , allowing the lifting device to fit into an otherwise inaccessible location in the stowed position, such as illustrated in FIG. 19A , and to support the shelving when pivoted to the supporting position, such as illustrated in FIG. 19B . [0065] In FIG. 16A , one of pins 5056 is shown in a stowed position, tethered to the lifting device. The pin 5056 is removed from the stowed position prior to inserting the pin through one of the holes in the pair of plates 5040 , 5010 comprising the attachment mechanism as illustrated in FIG. 16B . Each of the plates are pivotally connectable as illustrated in FIGS. 17A and 17B , to connect the lifting device 5000 to a support structure 5030 . The jack 5016 of the lifting device 5000 , raises and lowers the support structure 5030 and the pair of plates 5040 , 5010 . Each of the pair of plates 5040 , 5010 in the example illustrated in FIGS. 16A-19B are biased downwards by a spring 5012 , which functions with a detent 5011 or other structure of each plate to keep it in its stowed position until a user raises the plates when pivoting the plates 5010 , 5040 into a support position, as illustrated in FIG. 19B , for example. In the example, additional support tabs 5042 , 5044 are welded in place on one plate 5040 to increase the area in contact with the each pin 5056 . [0066] The support structure 5030 is comprised of a pair of identical plates, for example, mounted to the jack 5016 on opposite sides of the attachment mechanism plates 5040 , 5010 . A bolt passing through the identical plates of the support structure 5030 provides a hinge for the plates 5040 , 5010 of the attachment mechanism. Each of the plates 5040 , 5010 includes a sleeve through which the bolt passes, coupling the plates to the support structure 5030 . The spring 5012 biases the plates 5040 , 5010 downward, keeping a tab on the bottom of the plates engaged with a slot in the plates of the support structure 5030 . By applying a force upward on the plates 5040 , 5010 of the attachment mechanism, the plates are pivotable to a support position on opposite sides of a shelving support structure, as illustrated in FIG. 19B . [0067] The lifting device includes caster wheels 5054 for mobilization of shelving once the jack 5016 raises the shelving off the floor. A ratchet mechanism 5014 is provided that allows the jack 5016 to be raised and lowered using a socket wrench. A tab 5011 integrally formed on a bottom surface of a plate 5010 in FIG. 21 is capable of engaging each of a plurality of slots 5034 , 5032 of a support plate 5030 , as illustrated in FIG. 22 , when the plate 5010 is in the stowed and support positions, respectively. The plurality of slots may be arranged to position the attachment mechanism in one or more stowed and/or support positions. A hinge bolt extends through the hole 5036 in each of the identical support plates 5030 and the sleeve 5017 of the plate 5010 of the attachment mechanism, pivotally coupling the plate 5010 of the attachment mechanism to the pair of identical support plates 5030 , which may be welded to the jack of the lifting device for raising and lowering of stocked shelving. [0068] A handle 5020 is provided on the lifting device 5000 for ease in lifting, holding and positioning the lifting device. [0069] Use of the lifting device illustrated in the examples is accomplished by positioning the attachment mechanism tabs in the stowed position, prior to inserting the lifting device in an otherwise inaccessible space. Then, the attachment mechanism plates 5010 , 5040 are raised to disengage the tabs 5011 , allowing the plates to pivotally rotate about the axis of the hinge bolt 5033 to a support position as illustrated in FIG. 19B . In one example, in FIG. 19 , tabs T 1 , T 2 are included to prevent rotation of the plates 5010 , 5040 beyond the tabs T 1 , T 2 . The holes 5013 , 5015 in the plates 5010 , 5040 of the attachment mechanism may be aligned by adjusting the height of the jack 5016 , and the pins 5056 are inserted through holes H in the shelving supports P and the holes 5013 , 5015 of the plates of the attachment mechanism when aligned with those holes, by removing the tethered pins 5056 from their stowed location and inserting the pins 5056 through the aligned holes 5013 , 5015 , H. The jack 5016 may then be raised using a socket wrench 2301 attached to the ratchet extension 5014 . When used to raise a row of shelving, a plurality of lifting devices 5000 are attached to a plurality of shelving supports P. Then, all of the lifting devices are raised to raise the entire row of shelving. In one example, the shelving remains stocked, as illustrated in FIG. 24 , during the raising and mobilization of the shelving. The process achieves a very surprising and unexpected rate for the mobilization of shelving compared to any known system of mobilization. [0070] Any jack could be used to raise and lower the shelving; however, a jack 5016 using a rack and pinion gear is surprisingly versatile in tight spaces and provides adequate lifting capability when used as a system having a plurality of lifting devices. For example, a boat trailer type jacket mechanism has the advantage of having an acceptably narrow width while providing for a displacement that positively locks the position of the shelving in its raised position without slipping or lowering or need of a separate locking mechanism. Other combinations and variations of the features in the examples, obvious to those knowledgeable in the art, may be included and are contemplated as being within the scope of the claims that eventually issue.
A swing support mobilization lift includes a jack and a pivotably positionable swing arms, pivotally coupled to the jack, such that the attachment mechanism is capable of being initially displaced in the plane of the jack mechanism during insertion of the lifting device in a narrowly accessible space adjacent to shelving. Then, the swing arms are capable of being pivoted to extend outwardly from the plane of the surface of a jack facing the shelving, such that the shelving may be attached to the swing arms, such as by pins tethered to the jack. In one example, a pair of swing arms disposed on opposite sides of a portion of the shelving sandwich the portion of the shelving and support opposite ends of the pins coupling the swing arms to the shelving.
1
BACKGROUND AND SUMMARY Pesticide concentrates and other highly toxic liquid concentrates are commonly shipped to farmers and other users in metal containers of five gallons or more capacity. The users then mix such concentrates with relatively large quantities of water (dilutions of 1000 to 1 or more are common) for application as required. It is in the opening and handling of such containers in connection with the diluting procedure that risks are especially great. Splashing of the concentrate during an opening or pouring procedure, spilling of the contents during handling of an opened container, and contacting residual concentrate in or upon the surface of a discarded container, present serious risks not only for users but also for others who might touch such containers (e.g., children, trash collectors, pets, wildlife, etc.). While experienced users generally wear protective clothing while opening and handling such containers, the use of such clothing is often inconvenient and uncomfortable and presents additional risks because direct contact with concentrate clinging to such garments may readily occur as the clothing is put on or taken off, or otherwise handled as, for example, in laundering operations. Even where extreme precautions are taken to avoid skin contact with the highly toxic liquid concentrates, significant dangers may still exist in the form of vapors which escape after the containers are opened and especially when their contents are poured into tanks containing water for dilution. Finally, it is believed that errors in following the directions on such containers and, in particular, in mixing the concentrates to produce the wrong dilutions, present additional risks, especially if the final solutions are of excessive strength. Accordingly, it is an object of this invention to provide an apparatus which allows a liquid pesticide concentrate or other toxic concentrate to be removed from its shipping container and transferred to an applicator tank in such a way that the user and others are protected against exposure to such concentrate, including the vapors thereof and the rinse solutions which result when such a container is flushed with water. Another object is to provide an apparatus which may be easily and safely manipulated to pierce the wall of a concentrate container, extract a selected and accurately measured amount of such concentrate for automatic mixing with water and, when the container is empty, flush the inside surfaces of that container as well as surfaces of the apparatus exposed to such concentrate, so that the emptied container may be safely handled and discarded. A still further object is to provide an apparatus which protects the user even if some of the toxic contents of a container should spray or otherwise escape as a discharge opening is formed in the container wall. Briefly, the apparatus takes the form of a supporting frame for a conventional pesticide concentrate container, a top member hingedly connected to the frame for movement between raised and lowered positions, a piercing tube mounted upon the top member for piercing a wall of the pesticide container as the hinged top member is swung into its lowered position, an elongated suction tube telescopingly carried by the piercing tube for movement between a retracted position (wherein its lower end is concealed within the piercing tube) and any of a plurality of extended positions (wherein the lower end of the suction tube is extended into a container to withdraw a desired amount of pesticide concentrate therefrom). The suction tube is provided with indicia means so that a user may easily adjust the position of the suction tube to withdraw a measured amount of concentrate from a pierced container. Thus, the suction tube performs the multiple functions of serving as the concentrate extracting tube, indicating to the user the amount of concentrate that will be withdrawn, and automatically limiting such withdrawal to the indicated amount. An automatically-expandable shroud extends about the lower end portion of the piercing tube so as to contact the wall of a concentrate container just prior to a piercing step, and to remain in contact with such wall throughout the piercing, extracting and flushing operations. The shroud, piercing tube, and suction tube are so dimensioned and interrelated that all surfaces coming in contact with concentrate during such operations, and the interior surfaces of the emptied container, may be thoroughly rinsed with water before the hinged top member is raised to release the container. Other features, objects, and advantages of the apparatus will become apparent from the specification and drawings. DRAWINGS FIG. 1 is a fragmentary perspective view of a trailer equipped with an apparatus embodying the invention. FIG. 2 is a side elevational view, shown partly in section and partly in schematic form, of the apparatus. FIG. 3 is an enlarged vertical sectional view illustrating the hinged top member as it is being swung into its lowered position to pierce the wall of a container. FIG. 4 is a vertical sectional view similar to FIG. 3 but showing the top member in its lowered position and illustrating the suction tube positioned for liquid extraction. DETAILED DESCRIPTION Referring to FIG. 1, the numeral 10 generally designates a liquid concentrate metering apparatus mounted on the bed 11 of a trailer equipped with a large applicator tank 12. While the apparatus may be conveniently mounted upon the trailer or other vehicle which carries the applicator tank and spray equipment, it is to be understood that the apparatus might instead be supported upon its own vehicle or stand to suit the requirements or preferences of users. Alternatively, tank 12 may serve as a fresh water source with the diluted concentrate flowing either to another tank or directly to an applicator (not shown). FIG. 1 is presented simply to show what is believed to be one particularly convenient arrangement, especially for agricultural operations. The structural and functional relationships are best shown in FIG. 2 where it will be seen that the apparatus 10 includes a support frame assembly 13 secured to member 14 of the trailer. The frame assembly includes a base member 15 which rests upon frame member 14 and is secured thereto by U-bolts 16. A leveling platform 17 is also part of the frame assembly and is carried by upstanding threaded studs 18, or by any other conventional leveling means, secured to base member 15. By adjusting supporting nuts 19, the corners of the platform may be raised or lowered until proper leveling is achieved. The frame assembly also includes a standard 20 which is secured at its lower end to platform 17. A top member 21 is connected by hinge 22 to the upper end of the standard and is pivotally movable between the raised position indicated by broken lines and the lowered position represented by solid lines. In its lowered position, the hinged top member is generally horizontal and is disposed directly above platform 17 and a conventional shipping container 23 supported by the platform. The shipping container is ordinarily (but not necessarily) of generally cylindrical configuration, having a side wall 23a and end walls 23b. Where the container is provided with a handle and/or a bung at one end (not shown), it is often convenient to invert the container so that the upwardly-facing end wall is relatively smooth and, consequently, the container need not be rotated or maneuvered upon the platform to expose a clear zone of the top surface for the piercing, extracting, and flushing operations. Top member 21 is also equipped with a handle assembly 24 which is composed of two elements, namely, a connecting element 25 and a handle lever 26. The connecting element or link is pivotally joined to the free end of top member 21 and, at its opposite end, is pivotally connected to an intermediate portion of handle lever 26. It is believed apparent that in a piercing and locking operation, the handle 24 is swung downwardly from the position depicted in broken lines until a cross pin 27 of the handle lever is received beneath the latch hook 28 projecting from upstanding frame member 29. Further downward pivotal movement of the free end of handle lever 26 exerts a downward force of considerable mechanical advantage upon top member 21 until the handle lever 26 swings past a center point into the self-locking position shown in solid lines (FIG. 2). Since the force-multiplying and self-locking action of such a handle assembly is quite conventional and well known, further description is believed unnecessary herein. Referring to FIGS. 3 and 4, it will be seen that a piercing tube 30 is secured to top member 21 and projects downwardly therefrom when the top member is in its lowered position. The lower end of the piercing tube is beveled to define an angled piercing tip 31. It will be noted that the angle of the bevel is such that the extreme lower end of the piercing tip is located closest to the pivot axis of top member 21, thereby promoting the piercing and infolding action of the tip and lower edge of the tube when the piercing tube engages the end 23b of a container as illustrated in FIGS. 3 and 4. The piercing tube 30 has a pair of spaced annular end walls 32 and 33 which are channeled to support resilient sealing rings 34 and 35. A concentric suction tube 36 extends through the openings of the sealing rings and snugly engages the rings in a manner which not only results in a fluid-tight seal but also serves to hold the rigid, elongated suction tube in any selected position of adjustment relative to the piercing tube 30. In FIG. 3, the suction tube 36 is shown in a fully raised or retracted position with retaining ring 37 (which is secured to the lower end of the tube and serves as a stop element) engaging the underside of end wall 33 of the piercing tube. When the suction tube is so retracted, its lower end is elevated above the beveled edge of tip 31 and is therefore concealed within the lower end portion of the piercing tube. After a container-piercing operation has taken place, the suction tube 36 may be telescopically lowered or extended into any selected position as indicated in FIG. 4. The outer surface of the elongated suction tube is provided with indicia means in the form of calibration marks and numerals 38 which, when aligned with the top edge of the piercing tube 30, indicates the volume of concentrate the suction tube is positioned to withdrawal from a pierced container 23, although it is to be understood that if desired the indicia means on the suction tube may take the form of a pointer and the calibrations may appear on a suitable scale secured to the top member. The upper end of the suction tube is connected by a suitable fitting 39 to a flexible conduit or hose 40 (FIGS. 1 and 2) leading to a valve 41 and a main water supply line 42. Line 42 carries fresh water from any available source 43 of water under pressure. A control valve 44 is interposed along line 42, a suction device in the form of a venturi or flow nozzle 45 is disposed in line 42 adjacent the branch point of suction line 40, and a bypass line 46 equipped with valve 47 may be provided to shunt water about the suction device during certain operations to be described. As illustrated in FIG. 2, line 42 discharges into the applicator tank 12. Looking to FIGS. 3 and 4, it will be seen that the inside diameter of piercing tube 30 is substantially larger than the outside diameter of suction tube 36, with the result that an annular space or chamber 49 is formed therebetween. Such chamber is delimited at its ends by end walls 32 and 33 of the piercing tube and by the sealing rings 34 and 35 carried by those end walls. Near lower end wall 33, the piercing tube is provided with an annular series of circumferentially spaced openings 50. A similar series of circumferentially spaced openings 51 is provided at approximately the longitudinal mid point between the upper and lower end walls 32 and 33. Above openings 51, a rinsing tube 52 communicates with the piercing tube for conducting rinse water to chamber 49 for discharge through openings 50 and 51. Tube 52 connects to hose 53 which is equipped with valve 54 and which connects to the water line 42 at a point upstream of venturi 45 (FIG. 2). Tube 52 is provided with an air-inletting check valve 55 which allows air to enter chamber 49 and container 23 (through ports 50 and 51) to replace concentrate as it is withdrawn from the container. A tubular shroud or sleeve 56 extends about the lower portion of the piercing tube below top member 21 as depicted in FIGS. 3 and 4. The shroud is formed of flexible material (such as synthetic rubber) and has a helical spring 57 embedded therein, causing the tubular shroud or sleeve to expand into a normally fully extended condition in which its lower end is disposed slightly below the extreme end of tip 31. A rigid collar 58, equipped with a resilient annular seal 59 for sealingly engaging the upper surface of the end wall of container 23 in the manner indicated in FIG. 3, is provided at the lower end of the tubular shroud. While depicted as an assembly, elements 56, 57, 58, and 59 might instead be an integral unit. At its upper end, the shroud is securely connected to the piercing tube by annular wall 60. In the operation of the apparatus, a user first places a concentrate container 23 upon platform 17 and then lowers and locks the top member 21 by means of handle assembly 24. As the top member is lowered, the springloaded annular shroud 56 contacts the top wall 23b of the container to provide a seal and to deflect and redirect any concentrate that may be exuded during piercing of the container. As the top member approaches its fully lowered position, and after the shroud has engaged container 23, the tip 31 of the piercing tube punctures end wall 23b of the container in the manner depicted in FIG. 3. Continued downward movement of the top member into its fully locked position results in complete entry of the tip portion of the piercing tube as shown in FIG. 4. With the top member in its lowered and locked position, the user lowers the suction tube 36 into any selected position for the withdrawal of an amount of liquid concentrate represented by the calibration marking 38 aligned with the upper end of the piercing tube. To this point, all of the valves 41, 44, 47, and 54 have remained closed; now valves 44 and 41 are opened to allow water under pressure to flow from source 43 to applicator tank 12 and to aspirate concentrate through the suction line 40. The liquid concentrate continues to be drawn from the container 23 until the level of concentrate has descended to the lower end of suction tube 36, at which time the suction tube is automatically cleared. Such clearing of the tube is audibly signaled by a sudden increase in air flow through the orifice of check valve 55. The user then closes suction valve 41 and opens bypass valve 47 to speed up the filling of mix tank 12 with water. Thereafter, the bypass valve and supply valves 47 and 44 are closed. The diluted chemical in applicator tank 12 is then sprayed or applied in the desired manner until the applicator tank has been emptied. The above steps may then be repeated, each time the suction tube 36 being lowered into a new position in order to draw off an additional measured amount of concentrate for mixing with water in tank 12. In the final withdrawal stage, the suction tube 36 is lowered until its lower end contacts the bottom inside wall of the container. Concentrate is therefore drawn from the container until only a small amount remains as a film on the inside bottom and side walls of the container. When concentrate stops flowing through suction line 40, the user opens rinse valve 54. With bypass valve 47 remaining closed, fresh rinse water flows through line 53 into the chamber 49 of the piercing tube 30, flushing the inside surfaces of that tube and a portion of the outside surface of suction 36. Such rinse water is discharged through openings 50 and 51 to spray and flush the inside surfaces of the shroud 56, the outer surfaces of the piercing tube, the top surface of container 23 within the line of contact defined by shroud seal 59, and the inside surfaces of the container 23, and is then withdrawn from the bottom of the container by suction tube 36 and line 40. The flow of rinse water is continued until the surfaces previously in contact with the concentrate have been thoroughly rinsed. Thereafter, with both the rinse valve 54 and suction valve 41 closed, and with bypass valve 47 opened, the user fills the applicator tank to the desired level. The fully rinsed container is removed from the apparatus by simply lifting the suction tube 36, releasing handle assembly 25, and lifting top member 21. It is to be noted that during the rinsing operation not only are the interior surfaces and certain exterior surfaces of the container flushed by rinse water, but that those elements of the apparatus 10 in direct contact with the pesticide concentrate are also flushed or rinsed. The apparatus therefore provides a relatively safe procedure for opening the containers of toxic liquids, removing selected volumes of such liquids for dilution with water, and finally rinsing the emptied containers with clear water so that such containers may be more safely handled and discarded. While in the foregoing we have disclosed an embodiment of the invention in considerable detail for purposes of illustration, it will be understood by those skilled in the art that many of these details may be varied without departing from the spirit and scope of the invention.
An apparatus is disclosed for removing toxic liquid concentrates from their shipping and/or storage containers, mixing selected amounts of such concentrates with water, and rinsing the containers when they are empty, in a manner that avoids exposure of users to such concentrates.
0
FIELD OF THE INVENTION The present invention relates to a process employing slurry catalyst compositions in the upgrading of heavy oils. These oils are characterized by low hydrogen to carbon ratios and high carbon residues, as well as high asphaltene, nitrogen, sulfur and metal content. BACKGROUND OF THE INVENTION Slurry catalyst compositions used in heavy oil upgrading are generally not recycled, due to the particulate size which tends to range from 1 to 20 microns. The processes that attempt to recycle these catalyst particles tend to require multiple steps in the separation and concentration of the catalyst from the final products. The steps used are well known in the refining art. They include but are not limited to the following steps: solvent deasphalting, centrifugation, filtration, settling, distillation, and drying. Other equipment used in these steps may include and is not limited to use of hydrocyclones, extruders, and wiped film evaporators. These catalyst particles tend to lose catalytic activity during the separation and concentration process steps. This is contrary to the purpose of recycling. This loss of catalytic activity is thought to be due to the precipitation onto the catalysts of polycondensates and coke. Polycondensates and coke are created by temperature and pressure reduction during the steps of catalyst separation and concentration. In slurry catalyst hydroprocessing, the costs of fresh catalyst must be weighed against the costs of catalyst separation, catalyst concentration, and catalyst rejuvenation. U.S. Pat. No. 5,298,152 (which is incorporated by reference) teaches recycling to the hydrogenation zone of an active catalyst made from a catalyst precursor, without regeneration or further processing to enhance activity. While it is being separated from the product, the active catalyst is maintained under conditions substantially the same as the conditions encountered in the hydrogenation zone in order to avoid the precipitation of polycondensates and coke. In this way, the catalyst is not quickly deactivated, as often happens when it is separated from the product. Unlike the instant invention, Kramer teaches that a high pressure separator may act as a high pressure settler. In the instant invention, the catalyst is never permitted to settle. U.S. Pat. No. 5,374,348 teaches a process of hydrocracking of heavy hydrocarbon oils in which the oil is mixed with a fractionated heavy oil recycle stream containing iron sulphate additive particles. The mixture is then passed upwardly through the reactor. Reactor effluent is passed into a hot separator vessel to obtain products and a liquid hydrocarbon stream comprising heavy hydrocarbons and iron sulphate particles. The heavy hydrocarbon stream is further fractionated to obtain a heavy oil boiling above 450° C., which contains the additive particles. This material is recycled back to the hydrocracking reactor. SUMMARY OF THE INVENTION The instant invention is directed to a process for hydroconversion of heavy oils, employing an active slurry catalyst composition. A process for upgrading heavy oils which employs a slurry catalyst composition that is not allowed to settle, comprising the following steps: (a) combining, in an upgrading reactor under hydroprocessing conditions, heavy feed, hydrogen gas, fresh catalyst slurry composition, and recycle slurry composition; (b) passing the effluent of the upgrading reactor to a separation zone wherein products boiling at temperatures up to 900° F. are passed overhead; (c) passing the material remaining in the separation zone from step (b) to a constantly stirred catalyst storage tank; and (d) passing at least a portion of the material in the constantly stirred catalyst storage tank back to the upgrading reactor of step (a). Advantages of the instant invention include: Prevention of catalyst agglomeration (a source of catalyst deactivation) by not permitting catalyst to settle. Removal overhead of middle distillate product from hydrogenation zone (as gas vapor from hot high pressure separator). Catalyst-fee product from the hydrogenation zone (no requirement of settling, filtration, centrifugation, etc.). No significant deactivation of catalyst when there is substantial pressure and/or temperature drop due to the 100% conversion. Production in very low amounts of supercondensates (asphaltenes) and coke that do not significantly affect the activity of the catalyst composition. Concentration of catalyst in the separation step—no further concentration required. BRIEF DESCRIPTION OF THE FIGURE The FIGURE illustrates the process steps of the instant invention. DETAILED DESCRIPTION OF THE INVENTION The instant invention is directed to a process for hydroconversion of heavy oils, employing an active slurry catalyst composition such as those disclosed in co-pending applications T-6344 (Ser. No. 10/938,202) and T-6393 (Ser. No. 10/938,003). These applications are incorporated by reference. Such catalyst compositions comprise a Group VIB metal compound such as molybdenum. A slurry catalyst composition can be recycled, using only a single separation step, without significant catalyst deactivation occurring. The single separation step preferably employs a hot, high pressure separator. The slurry catalyst composition is useful for upgrading carbonaceous feedstocks, which include atmospheric gas oils, vacuum gas oils, deasphalted oils, olefins, oils derived from tar sands or bitumen, oils derived from coal, heavy crude oils, synthetic oils from Fischer-Tropsch processes, and oils derived from recycled oil wastes and polymers. The catalyst composition is useful for but not limited to hydrogenation upgrading processes such as thermal hydrocracking, hydrotreating, hydrodesulphurization, hydrodenitrification, and hydrodemetalization. The catalyst may be used in processes employing both fixed and ebullated beds. The process of the present invention can be operated in either one or two stage modes. The upgrading reactor 10 (see FIGURE) represents only the first stage. The second stage (if present), which may be an integrated hydrotreater, is not shown in the FIGURE. In one-stage operation, the heavy oil feed (line 25 ) is contacted with the active catalyst slurry and a hydrogen-containing gas (line 5 ) at elevated temperatures and pressures in continuously stirred tank reactors or ebullated bed catalytic reactors. The active catalyst slurry is composed of up to 95 wt % recycle material (line 30 ) and 5 wt % fresh catalyst (line 15 ). The feed, catalyst slurry and hydrogen-containing gas are mixed in upgrading reactor 10 at a residence time and temperature sufficient to achieve measurable thermal cracking rates. The effluent from the upgrading reactor 10 passes through line 35 to the hot high pressure separator 40 . The resultant light oil is separated from solid catalyst and unconverted heavy oil in the hot high pressure separator 40 , and passes through line 45 to middle distillate storage. Alternately, the light oil may be sent to the second-stage reactor (not shown). This reactor is typically a fixed bed reactor used for hydrotreating of oil to further remove sulfur and nitrogen, and to improve product qualities. The product is free of catalyst and does not require settling, filtration, centrifugation, etc. In the hot high pressure separator 40 , substantially all of the upgraded products generated from the heavy oil hydroconversion upgrading zone 10 goes overhead as gas-vapor stream 45 . The liquid in the bottom of the hot high pressure separator 40 , composed primarily of unconverted oil and active catalyst, is passed through line 70 to the recycle catalyst storage tank 60 . This tank is constantly stirred, as depicted by Mixer 55 , and a constant reducing atmosphere is maintained by the addition of hydrogen (line 65 ). Excess hydrogen may be removed by bleed stream 50 . The catalyst slurry is recycled back to upgrading reactor 10 as needed (through line 30 ). Recycle makes up can be as high as 95 wt % of the catalyst used in the upgrading reactor. The catalyst activity is maintained by running the upgrading process at 100% conversion, maintaining an at least minimum reducing atmosphere throughout the upgrading, separation and storage, and not allowing the catalyst composition to settle at any time. Following the separation in the hot high pressure separator, there is no need for further separation steps. Throughout the process, substantial temperature and pressure fluctuations are tolerated with only minor precipitate formation of supercondensates and coke. In past processes in which recycle has been employed, the slurry catalyst composition has sustained substantial fouling and deactivation. Process Conditions For the first-stage operation as depicted in upgrading reactor 10 , the temperatures for heavy oil feedstocks are normally above about 700° F., preferably above 750° F., and most preferably above 800° F. in order to achieve high conversion. Hydrogen partial pressures range from 350 to 4500 psi and hydrogen to oil ratio is from 500 to 10,000 SCFB. The concentration of the active slurry catalyst in the heavy oil is normally from about 100 to 20,000 ppm expressed as weight of metal (molybdenum) to weight of heavy oil feedstock. Typically, higher catalyst to oil ratio will give higher conversion for sulfur, nitrogen and metal removal, as well as the higher cracking conversion. The high pressure separator temperature can be as high as 800° F. Near 100% demetalation conversion and 1000° F.+ cracking conversion of the heavy oil can be achieved at appropriate process conditions, while the coke yield can be maintained at less than about 1%. The process conditions for the second-stage (not shown in the FIGURE) are typical of heavy oil hydrotreating conditions. The second-stage reactor may be either a fixed, ebullated or a moving bed reactor. The catalyst used in the second-stage reactor is a hydrotreating catalyst such as those containing a Group VIB and/or a Group VIII metal deposited on a refractory metal oxide. By using this integrated hydrotreating process, the sulfur and nitrogen content in the product oil can be very low, and the product oil qualities are also improved. EXAMPLES Example 1 This example depicts heavy oil upgrading (Athabasca vacuum residuum) in recycle mode. The catalyst is activated by using the method disclosed in co-pending application Ser. No. 10/938,003(T-6393). This catalyst is activated using only a single oil. The catalyst prepared by the method of T-6393 was used for Athabasca vacuum resid (VR) and vacuum gas oil (VGO) feed upgrading in a process unit which employed two continuously stirred tank reactors. Catalyst was recycled with unconverted heavy oil. A feed blend with 97% Athabasca VR and 3% Athabasca VGO was used. The Athabasca VR feed properties are listed in the following table: API gravity at 60/60 3.9 Sulfur (wt %) 5.58 Nitrogen (ppm) 5770 Nickel (ppm) 93 Vanadium (ppm) 243 Carbon (wt %) 83.57 Hydrogen (wt %) 10.04 MCRT (wt %) 17.2 Viscosity @ 212° F. (cSt) 3727 Pentane Asphaltenes (wt %) 13.9 Fraction Boiling above 1050° F. (wt %) 81 The Athabasca VGO feed properties are listed in the following table: API gravity at 60/60 15.6 Sulfur (wt %) 3.28 Nitrogen (ppm) 1177 Carbon (wt %) 85.29 Hydrogen (wt %) 11.01 MCRT (wt %) 0.04 Fraction Boiling above 650° F. (wt %) 85 The process conditions used for the heavy oil upgrading is listed as following: Total pressure (psig) 2500 Fresh Mo/Fresh Oil ratio (%) 0.24 Fresh Mo/Total Mo ratio 0.1 Fresh oil/Total oil ratio 0.75 Total feed LHSV 0.21 Reactor temperature (°F.) 825 H 2 gas rate (SCF/B) 9100 The product yields, properties and conversion are listed in the following table: C4-gas (wt %) 12.1 C5-180° F. (wt %) 7.5 180-350° F. (wt %) 15.5 350-500° F. (wt %) 20.8 500-650° F. (wt %) 22.2 650-800° F. (wt %) 14.8 800-1000° F. (wt %) 3.9 1000° F.+ (wt %) 0.3 HDN conversion (%) 62 HDS conversion (%) 94 HDM conversion (%) 99 Liquid product API gravity 33 Middle distillates compose 58.5 wt % of the product and heteroatom content is drastically reduced. Example 2 This example depicts heavy oil upgrading (Hamaca vacuum residuum) in recycle mode. The catalyst is activated by using the method disclosed in co-pending application Ser. No. 10/938,003 (T-6393). This catalyst is activated using only a single oil. The catalyst by the method of T-6393 was used for Hamaca vacuum resid (VR) and vacuum gas oil (VGO) feed upgrading in a process unit which contains two continuously stirred tank reactors, and a recycle portion which enables recycling catalyst with unconverted heavy oil. A feed blend with 90% Hamaca VR and 10% Hamaca VGO was used. The Hamaca VR feed properties are listed in the following table: API gravity at 60/60 1.7 Sulfur (wt %) 4.56 Nitrogen (ppm) 9222 Nickel (ppm) 168 Vanadium (ppm) 714 Carbon (wt %) 83.85 Hydrogen (wt %) 9.46 Viscosity @ 266° F. (cSt) 19882 Pentane Asphaltenes (wt %) 32 Fraction Boiling above 1050° F. (wt %) 91 The Hamaca VGO feed properties are listed in the following table: API gravity at 60/60 14.2 Sulfur (wt %) 3.53 Nitrogen (ppm) 2296 Carbon (wt %) 84.69 Hydrogen (wt %) 11.58 Fraction Boiling above 650° F. (wt %) 89 The process conditions used for the heavy oil upgrading is listed as following: Total pressure (psig) 2600 Fresh Mo/Fresh Oil ratio (%) 0.55 Fresh Mo/Total Mo ratio 0.25 Fresh oil/Total oil ratio 0.75 Total feed LHSV 0.16 Reactor temperature (°F.) 825 H2 gas rate (SCF/B) 9400 The product yields, properties and conversion are listed in the following table: C4- gas (wt %) 14 C5-180° F. (wt %) 6.6 180-350° F. (wt %) 15.4 350-500° F. (wt %) 21.1 500-650° F. (wt %) 22.4 650-800° F. (wt %) 12.6 800-1000° F. (wt %) 4 1000° F.+ (wt %) 1.5 HDN conversion (%) 63 HDS conversion (%) 96 HDM conversion (%) 99 Liquid product API gravity 33 Middle distillates compose 58.9 wt % of the product and heteroatom content is drastically reduced.
The instant invention is directed to a process employing slurry catalyst compositions in the upgrading of heavy oils. The slurry catalyst composition is not permitted to settle, which would result in possible deactivation. The slurry is recycled to an upgrading reactor for repeated use and products require no further separation procedures for catalyst removal.
2
SUMMARY OF THE INVENTION An assembly of parts which together form a shoe comprise a sole adapted to be attached to the foot by any one of a plurality of pairs of differently colored, styled or textured straps which are adapted to be positioned at the front part of the foot and connected to the sole by releasable means whereby the straps may be changed, for example to match other clothes worn by the wearer. DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a shoe showing one embodiment by the means provided by the invention for releasably attaching the sole to the foot; FIG. 2 is a view similar to FIG. 1 showing a second embodiment of the invention; FIG. 3 is a perspective view of the end of each of the straps shown in FIG. 1. FIG. 4 is a perspective view of the end of each of the straps shown in FIG. 2, and FIG. 5 is a perspective view showing a further embodiment of the invention. DESCRIPTION OF THE INVENTION It is often desirable that shoes which are worn match the color, style, texture or other characteristic of the dress or suit which is also being worn, and in order to permit this it is usually necessary to wear shoes of different colors, textures or styles in order to achieve a matching effect. By the present invention I have provided means whereby a single pair of soles may have associated with it a plurality of pairs of differently colored straps for releasably connecting the soles to the feet, the straps of each pair being of different color, texture or style from those of the other pairs so that by changing and interchanging the straps with a single pair of sides the visual parts of the shoes may be made to match the color, style or texture of the clothing which is being worn. A first embodiment of the invention is disclosed in FIG. 1 of the drawings, in which there is disclosed the sole 2 of a shoe which, as is usual, comprises a heel part 4 and a toe part 6 which are integrally connected to provide a platform underlying the entire foot of a wearer. A supporting heel 8 may be provided under the heel part 4, if desired, and it will also be understood that the means provided by the invention do not require that the sole, as that term is used in the claims, underlie the entire foot. Means are provided for attaching the sole to the foot of the wearer, and this is usually accomplished by means located at the toe and heel parts of the sole. In the embodiment of the invention disclosed in FIG. 1 the means for accomplishing this comprise, first, two anchoring means 10 which are positioned in longitudinally spaced relation on both sides of the toe part of the sole and each of which comprises a generally cylindrical part 12 extending longitudinally of the sole and protruding from its upper side edge and preferably formed integrally with the sole, as by molding, each of these anchoring means being aligned transversely of the sole with a corresponding anchoring means on the other side of the sole. Associated with the sole having these anchoring means there is provided means for releasably connecting the sole to the foot, each of which comprises two elongated straps 20, 22 which are arranged in crossed relation and connected at their center points 24, and each of which is stiffened by one or more internal wires 26 which extend longitudinally of each strap. A plurality of pairs of these crossed straps are provided in accordance with the invention, and each pair provides means for connecting two soles to the feet of a wearer, and the straps of each such pair are colored, textured or styled differently from the straps of other pairs. In the embodiment of the invention being described each of the straps of each pair has at each of its ends an elongated open, generally oval-shaped loop 30 which is held to the end of the strap by passing the end of the strap through the loop and back onto the strap where is may be connected to the main body of the strap by any suitable means such as Velcro attachments 32. Each of the loops is of such size and configuration that it may be passed over the cylindrical part 12 of one of the attaching means 10 where it will be held under the lip of the part 12 of the connecting means, whereby the ends of the two crossed straps will be firmly connected to the sole but may be easily released from the sole in order to substitute straps of one color texture or style for those of another color, texture or style. As illustrated in FIG. 1, one or more straps may be provided at the heel end of the shoe, and connecting means of the described construction and arrangement may be provided for connecting these heels straps to the sole. A second embodiment in the invention is disclosed in FIG. 2 and it will be seen that in this form of the invention two spaced loops 36 are provided at each side edge of the toe end of the sole, each loop comprising an upwardly bowed part which provides an opening for the reception of the looped end of one of the straps 20, 22 of a pair of crossed straps which, in accordance with the invention, may be differently colored, textured or styled and which may have a jewelry ornament 40 positioned at the juncture of the straps and which may form the connection between them. Each strap may be connected to the sole by passing each of its ends through the opening of loop 36 and then folding the end back into the strap for connection by suitable means such as the Velcro connections 32. A still further form which the invention may take, and which is particularly designed and intended for doll's shoes is disclosed in FIG. 5 in which the usual sole is partially shown at 2. The attaching means in this embodiment comprises, first, two permanent magnets 44 which are embedded in the sole in longitudinally spaced relation to each other along each side edge of the sole adjacent its toe end, and a permanent magnet 46 embedded in the end of each strap of a pair of crossed straps 20, 22. In using the means provided by the invention any pair of crossed straps may be selected and used to attach soles to the feet of the wearer to assure match of the colors of the shoe with that of other clothes being worn.
A convertible shoe having a sole and releasable upper strap portions. Anchoring means attached to the sole edge cooperate with ring means at the ends of the strap portions to releasable secure the upper and sole portions.
0
RELATED APPLICATIONS/PRIORITY BENEFIT CLAIM [0001] Not applicable. FIELD [0002] The subject matter of the present application is in the field of batter-dipping pans of the type used in restaurant kitchens. BACKGROUND [0003] Commercial kitchens such as those in restaurants often employ large “flat bottom” fryers for frying foods like battered fish. Flat bottom fryers usually have an angled frying surface, shallower near the front edge and deepening gradually toward the rear of the fryer, with a raised front edge to help contain the oil as it expands during heating. A batter-dipping pan is commonly kept near the fryer, holding for example several quarts or more of batter in which food is dipped before frying. A common type of batter-dipping pan comprises a fairly deep rectangular stainless steel pan with an out-turned flange or lip extending around the upper end of the pan, well known to those skilled in the art. [0004] It is important to keep the batter-dipping pan close to the fryer in order to minimize drips and spills as the battered food is removed from the pan and transferred to the fryer. However, because the fryer contains a significant amount of hot oil, it is also important to keep the dipping pan stable and in a location where the person dipping the food in the batter is protected from splash and heat. [0005] One prior device is a batter-dipping pan holder supported on the front edge of the fryer in cantilever fashion. The prior holder comprised a rectangular frame with a rectangular opening sized to receive the body of the batter dipping pan, the lip of the batter dip pan resting on the outer frame or edge of the holder. While this prior holder was an improvement over earlier arrangements, it suffers some drawbacks, including difficulty in removing the pan for refills and cleaning; a tendency to allow too much heat to be transferred from the oil in the fryer to the holder and pan; and, because the holder juts out in front of the fryer, interference with the cook's ability to easily access utensils stored at the sides of the fryer. BRIEF SUMMARY [0006] I have invented an improved batter-dipping pan holder for mounting at the front of a commercial fryer of the type used in restaurant kitchens. The inventive holder solves the problems of the prior known pan holder, with the following improvements. [0007] The holder comprises a rectangular horizontal frame with an opening configured to receive and hold a batter-dipping pan; a rear hook edge spaced from a rear edge of the frame, and extending downwardly to hook over the raised front edge of a fryer; and generally triangular side brace panels extending downwardly from the sides of the frame to support the weight of the frame and pan against the front of the fryer. [0008] The first improvement comprises frame sides wider than the width of the pan's upper side flanges, with finger holes or depressions formed in the upper side surfaces. [0009] An inner portion of each finger hole extends into an inner pan-supporting portion of the respective upper side surface covered by the pan's flange, and an outer portion of each finger hole remains exposed on an outer free portion of the respective upper side surface. The finger holes allow a pan to be lifted easily and evenly out of the frame, especially important when the pan is full. [0010] The second improvement comprises a utensil holder formed in the triangular side brace of the pan holder, comprising an upwardly bent or curved hook extending outwardly from the side brace. In the preferred form the utensil hook is formed from an outwardly-bent tab partially cut from the side brace, leaving an opening in the side brace underneath the utensil hook, which in the case of a metal pan holder helps keep the utensil hook and any utensils therein cool. [0011] The third improvement comprises a perforated rear hook edge, with holes or slots that reduce heat transfer and promote draining of oil. In the preferred form, the rear hook edge has a discontinuous bottom edge, for example formed by slots or perforations that leave the solid portions of the bottom edge spaced from each other with air between them. [0012] All portions of the inventive pan holder can be formed from a flat metal blank, making it economical and efficient to produce. [0013] These and other features and advantages of the invention will become apparent from the detailed description below, in light of the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0014] FIG. 1 is a perspective view of a known type of commercial fryer, and a batter dipping pan holder according to the invention secured to the fryer's front edge and holding a batter dipping pan. [0015] FIG. 2 is similar to FIG. 1 , but shows a batter-dipping pan exploded from the holder. [0016] FIG. 3 is similar to FIG. 2 , but further shows the holder in exploded assembly view relative to the fryer. [0017] FIG. 4 is a perspective enlarged view of the holder of FIG. 1 . [0018] FIG. 5 is a top plan view of a flat metal blank from which the holder of FIG. 1 is formed. [0019] FIGS. 6 and 7 are top plan views of flat metal blanks from which a holder similar to that of FIG. 1 can be formed, with the modification of a perforated rear hook edge shown in two alternate forms. [0020] FIG. 8 is a rear perspective view of a detail of the pan holder of FIG. 7 where it engages the front edge of the fryer. DETAILED DESCRIPTION [0021] Referring to FIG. 1 , a restaurant or commercial fryer 10 of known type is illustrated schematically. Fryer 10 is a generally shallow fryer used to fry items such as battered fish filets in hot oil. Fryer 10 has a front face 11 , a cooking surface 12 , some or all of which is typically flat, a rear edge 14 , sides 16 , and a raised front edge 18 . Cooking surface 12 is often angled or tapered downwardly from front edge 18 to rear edge 14 , so that the oil is deeper toward the rear of the fryer and shallower toward the front of the fryer. This allows the cook to adjust the cooking depth for different pieces of food. [0022] In some fryers the raised front edge 18 might comprise an oil-redirecting channel at the front edge of cooking surface 12 as shown in FIG. 1A , rather than a raised wall as illustrated in FIG. 1 , and it should be understood that the invention is applicable to both types, since the front of the fryer would still have a raised front edge 18 raised relative to the bottom of any such channel. The thickness of the front edge 18 of the fryer may vary. [0023] A pan holder according to the present invention is generally shown at 20 , configured to hold a batter-dipping pan 120 of known type against the front edge of fryer 10 . Batter-dipping pan 120 is typically formed of stainless steel or similar food-safe metal, has a peripheral lip or flange 121 extending around its upper end, and may hold a quantity of batter on the order of several quarts or more. [0024] Pan holder 20 in the illustrated example is formed from a similar food-safe metal such as stainless steel. As best shown in FIG. 2 , the pan holder 20 includes an opening 23 sized to receive the body of pan 120 therethrough, and a pan-holding frame 22 forming a generally flat horizontal support for the upper flange 121 on pan 120 . Frame 22 includes a rear edge 24 , sides 26 , and a front edge 28 with an optional downturned lip 29 . Frame 22 and opening 23 are illustrated as rectangular in the example, corresponding to the shape of typical batter-dipping pans such as 120 , but it will be understood by those skilled in the art that variations in the shape of the pan and holder are possible. [0025] Pan holder 20 further includes a rear fryer hook edge 30 , comprising a downturned flange of metal spaced from the innermost end 24 a of rear edge 24 of frame 22 and generally at right angles to the horizontal plane of frame 22 . Fryer hook edge 30 generally has a height equal to or less than the front raised edge 18 of the fryer 10 with which it is used, for example on the order of two inches. The spacing of rear hook edge 30 from the rear edge 24 and/or the side bracing panels described below may vary according to the thickness of the front edge 18 of the fryer. [0026] Pan holder 20 further includes side brace panels 40 , in the illustrated example having a generally triangular shape, with longer bases 42 tapering toward a point or shorter front edge 44 to provide clearance for a cook's legs when standing near the fryer. The rear edges of side braces 40 are spaced from the fryer hook edge 30 a distance corresponding approximately to the distance between the raised front edge 18 and the front face 11 of fryer 10 , in order to brace frame 22 as closely as possible to actual horizontal when attached to the fryer. Due to the differences in the dimensions of different fryers, in particular the thickness of front edge 18 , there may be some variation from horizontal in the attached position of the frame 22 , provided that batter does not spill over the sides of the pan 120 in holder 20 . [0027] The upper horizontal sides 26 of frame 22 are provided with finger holes 50 , in the illustrated example openings or depressions cut or stamped from the metal of the frame. Whether finger holes 50 are formed as depressions or actual holes through the upper surface of sides 26 will depend on preference and on the thickness of the metal. Sides 26 have a width greater than the width of the corresponding side portions 121 a of flange 121 on pan 120 , such that each side includes an inner pan-holding portion 26 a shown to the inside of the dotted line P marking the edge of pan flange 121 , and an outer free portion 26 b shown to the outside of dotted line P. Finger holes accordingly 50 have inner ends 52 that extend into the inner pan-holding portions 26 a of frame sides 22 , and outer ends 54 that extend into the outer free portions 26 b of frame sides 22 . Inner ends 52 of the finger holes may be extended to interrupt the inner side of the frame side 22 , although it is preferred that the holes leave a significant width of uninterrupted metal on either side so that the strength of the sides 22 is not compromised. [0028] When pan 120 is held in frame 22 , as best shown in FIG. 1 , the outer ends 54 of finger holes 50 are exposed so that a finger or utensil can be inserted under the flange 121 of the pan. This allows a cook to easily and evenly lift pan 120 from holder 20 , even with gloved or mitted fingers, without having to tilt the pan and possibly spill batter. [0029] It will be understood that while two finger holes 50 are illustrated in the example, one hole on each side of the frame, the number and size of finger holes 50 can vary. [0030] As shown in FIGS. 1-4 , side braces 40 are equipped with utensil holding tabs or hooks 60 , in the illustrated example formed by bending three-sided tabs cut from the sheet metal of the side braces and remaining attached at their base ends 60 b . Hooks 60 are generally upwardly-bent, -angled, or -curved members sized to receive and hold utensils commonly used for frying. The preferred, illustrated construction leaves a large opening 61 in the brace metal directly underneath each hook 60 , and only a relatively small area of connection between the body of hook 60 and side brace 40 , helping the hooks 60 and any utensils therein to stay cool. [0031] Referring to FIGS. 4 and 5 , in the preferred form pan holder 20 is stamped, cut, and/or formed from a flat blank of metal 100 shown in FIG. 5 . [0032] Referring next to FIGS. 6-8 , pan holder 20 is shown with modified fryer hook edges 130 ( FIG. 6 ) and 230 ( FIG. 7 ) at the rear of the pan holder 20 . Fryer hook edge 130 in FIG. 6 has a continuous lower edge 32 , while the body of the hook edge includes a plurality of perforations or holes 34 that do not interrupt lower edge 32 . Fryer hook edge 230 in FIG. 7 is provided with a discontinuous lower edge 32 interrupted by alternating openings 38 between tabs or portions of metal 36 . In the illustrated example, interruptions 38 are formed by generally rectangular open-ended slots removed from the metal of hook edge 230 . The size, spacing, and shape of the interruptions may vary, however, and may include rounded, triangular, and other shapes of varying contour and depth such as waves or scallops, which can all be considered “slots” or removed portions of the metal in between solid portions of metal at the lower edge 32 . Holes 34 and interruptions 38 reduce the surface area of hook edges 130 , 230 exposed to expanding hot oil at the front edge of the fryer, as shown for example in FIG. 8 , and help keep the metal pan holder 20 cooler. For example, the metal surface area of the hook edge 130 , 230 should preferably be significantly reduced by the slots/discontinuous edge/perforations 34 , 38 , for example on the order of 25% or more. Also, the slots and/or perforations should extend over a majority of the height of the hook edge 130 , 230 from its lowermost edge toward the junction with rear holder edge 24 , without weakening the junction. Further, lower edge interruptions 38 help drain oil from hook edge 230 as the hot oil in the fryer cools and contracts, or when the pan holder 20 is lifted from the fryer. Description of Operation [0033] In operation, pan holder 20 is used by attaching it to the front edge 18 of fryer 10 , by securing hook edge 30 over the raised front edge 18 on the fryer, and lowering the rear edges 42 of side braces 40 into contact with the front face 11 of the fryer. Batter-dipping pan 120 can then be placed in frame 22 for convenient access to the batter when frying food. Utensils used for frying can be handily stored on utensil hooks 60 on the sides of holder 20 . When it is desired to replace or refill batter-dipping pan 120 , it is easily removed from holder 20 without tilting by inserting fingers into the outer exposed portions of finger holes 50 in the sides 26 of frame 22 , and evenly lifting the pan from the frame. [0034] It will finally be understood that the disclosed embodiments represent presently preferred examples of how to make and use the invention, but are intended to enable rather than limit the invention. Variations and modifications of the illustrated examples in the foregoing written specification and drawings may be possible without departing from the scope of the invention. It should further be understood that to the extent the term “invention” is used in the written specification, it is not to be construed as a limiting term as to number of claimed or disclosed inventions or discoveries or the scope of any such invention or discovery, but as a term which has long been conveniently and widely used to describe new and useful improvements in science and the useful arts. The scope of the invention should accordingly be construed by what the above disclosure teaches and suggests to those skilled in the art, and by any claims that the above disclosure supports in this application or in any other application claiming priority to this application.
A pan holder for supporting batter-dipping pans from the front edge of a restaurant type fryer, especially a flat bottom type fryer with a raised front edge. The pan holder comprises a frame with an opening for receiving the batter-dipping pan and supporting the upper flange of the pan, a rear hook edge configured to mate with the front raised edge of the fryer, and side brace panels for engaging the front face of the fryer. The holder includes finger holes in both sides of the frame, extending beyond the pan flange so that the pan can be lifted evenly out of the frame; utensil holders formed in the side brace panels; and a perforated and/or discontinuous rear hook edge configured to reduce heat transfer and increase drainage of hot oil.
0
BACKGROUND OF THE INVENTION [0001] For safety and other reasons, it is often desirable to wash a vehicle before it leaves a particular site or location. Such situations can arise from natural disasters, man-made disasters, military activities, and even terrorist attacks. [0002] Asbestos, glass particles and caustic powder are among the many continuing dangers after the collapse of a building. The World Trade Center towers contained 5000 tons of asbestos for insulation, just in the structural steel. This asbestos was part of the dust clouds that rolled through lower Manhattan and settled surrounding the site. [0003] To protect people outside the contaminated zones, persons and vehicles must be cleaned prior to leaving the area. Because of the thin fibers inherent to asbestos, this kind and other contaminated dust must be taken up wet. While individuals can be decontaminated in tent stations, that they must leave the contaminated site through, heavy vehicles such as fire trucks and transport vehicles require a thorough vehicle wash so they do not contaminate outside the hot zone. [0004] Vehicle wash systems capable of washing large trucks are generally massive systems at fixed locations. Trucks drive through spray arches to reach all sides of the vehicle. Water and chemical cleaning solutions are pumped throughout the system and water is collected and recycled or disposed of. [0005] Disasters, military activities and terrorist attacks can occur anywhere in the world and, as such, vehicles need to be washed of contaminants in many different locations with the equipment being provided to these locations quickly and by means of various modes of transportation. [0006] The ability to ship a system over road, rail, ocean and air, along with the ability for it to be lifted by various means, are desirable requirements. [0007] The transportation industry, as well as the Department of Defense, has an ongoing initiative to standardize shipping containers so they may be easily deployed using truck, train, ship or plane. The United States participates in ANSI/ISO under the sponsorship of the American National Standards Institute. ANSI/ISO Technical Committee 104 handles a variety of matters related to freight containers. The Department of Defense and many other organizations have adopted these standards for transport containers. [0008] In view of the foregoing, there exists a need for a vehicle wash platform that can be easily transported and rapidly deployed. BRIEF SUMMARY OF THE INVENTION [0009] The present invention is a portable vehicle wash platform, capable of washing large trucks, that can be broken down and reconfigured such that the reconfigured platform itself forms a standard ANSI/ISO “container” that can be lifted by standard container handling equipment and can be transported by standard modes of container transportation. [0010] A vehicle wash system that can be broken down and reconfigured into a container size that complies with the standards for ANSI/ISO containers could be rapidly deployed to a disaster zone or other location to wash vehicles exiting the site and reduce the risk of contamination in the surrounding areas. BRIEF DESCRIPTION OF THE DRAWINGS [0011] FIG. 1 a is a perspective view of a fully deployed wash station in accordance with the present invention; [0012] FIG. 2 is a side view of the wash station seen in FIG. 1 ; [0013] FIG. 3 a - 3 g illustrate the wash station, seen in FIG. 1 , in successive configurations as it is being reconfigured into a shipping container or containerized platform; [0014] FIG. 4 is a perspective view of a wash station according to a second embodiment of this invention; and [0015] FIG. 5 is a table illustrating various standard methods for lifting containers and the “containerized” wash platform of this invention. DETAILED DESCRIPTION [0016] The following description of the preferred embodiments are merely exemplary in nature, and is in no way intended to limit the scope of the invention or its application or uses. [0017] In the preferred combination, a portable vehicle wash platform 10 capable of washing large vehicles 11 such as trucks, cars, tractor-trailers, gravel or debris handlers, fire-trucks, and military vehicles is provided. The wash platform 10 can be disassembled and reconfigured as a standard sized ANSI/ISO container or containerized platform 12 . The container 12 includes well known fittings 14 on its corners which meet ISO standards and allow lifting of the container 12 onto various means of transportation by different lifting methods. Once the containerized platform 12 is at the deployment site, it may be readily reassembled into its wash platform 10 configuration. This reassembly can be performed by a variety of means including manually, with a crane or by an automatic mechanism, such as hydraulic means, built into the vehicle wash platform 10 . [0018] In one embodiment of the vehicle wash platform 10 , six module portions are provided. These module portions includes an entrance ramp 13 with two entrance ramp modules 14 , 16 for the vehicle 11 to drive onto the platform 10 , an exit ramp 17 with two exit ramp modules 18 , 20 for the vehicle 11 to drive off the platform 10 and two main platform modules for the vehicle to be supported upon while it is being washed. Several views of a vehicle wash platform 10 are shown in various stages of disassembly in FIGS. 1-3 g. [0019] Referring to FIGS. 1 and 2 , a spray arch 26 or multiple spray arches are attached to the main platform modules 22 , 24 of the vehicle wash platform 10 to allow the vehicle 11 to pass therethrough and wash the truck 11 from a variety of angles. The arch 26 may otherwise be per a construction well known in the vehicle wash industry. Plumbing 28 is run through the vehicle wash platform 10 to bring water and/or chemicals to the spray arch 26 , or the plumbing may connect directly to the arches. Various other mechanisms commonly necessary for vehicle washing can be self contained within the main modules and included in the system, as one skilled in the art will appreciate. [0020] The main platform modules 22 , 24 have a grate top surface 30 and built in sloped internal surfaces 32 to divert the dirty water from the vehicle wash to an outlet 34 , which could lead to a settling pit constructed underneath the vehicle platform 10 or an integral pump (not shown) that sends the dirty water to another location for disposal and/or recycling. The entrance and exit ramps 13 , 17 could also be provided with internal surfaces directing the water to collection areas after washing to be disposed of at a later time. The top portions of the various modules, for example in the areas of man-ways 36 , are provided as removable panels for permitting access to the interior of the vehicle wash platform 10 and the various modules. [0021] Provided according to this invention, the vehicle wash platform 10 can be brought to and removed from the contaminated site in its containerized condition 12 , which has the external dimensions and capabilities of a standard ANSI/ISO shipping container. The overall or external dimensions of the containerized platform 12 is therefore 8 ft. (height)×8 ft. (width)×20 ft. (length) or 8 ft.×8 ft.×40 ft. Half heights and other divisions of the container dimensions may also be possible, so long as the end configuration of combined multiples is of a standard size. [0022] FIGS. 3 a - 3 g illustrate one method by which the six individual modules of the vehicle wash platform 10 can be broken down and reconfigured during containerization. As will be apparent from the following discussion, converting the containerized platform 12 into the vehicle wash platform 10 entails the reversal of the steps mentioned below. [0023] Starting from the vehicle wash platform 10 seen in FIG. 3 a , end supports 38 are added to low height ends 40 , 41 , 42 , 43 of the entrance and exit ramp modules 14 , 16 , 18 , 20 . The end supports 38 provide upright extensions to the low height ends 40 , 41 , 42 , 43 and extend to a height corresponding with the height of the opposing ends of the entrance and exit modules 14 , 16 , 18 , 20 , about two feet in a full sized standard container version of the invention. The end supports 38 may be attached to the low height ends 40 , 41 , 42 , 43 by various means, included having mounting tubes thereon inserted into recesses in the appropriate two corners of the modules 14 , 16 , 18 , 20 , fastening the end supports with pins, bolts, screws, interlocks or other such means. [0024] The first entrance module 14 is then positioned on main platform module 22 such that its low height end 40 is centrally positioned on the main platform module 22 , with its opposing end located toward the exit ramp module 18 . [0025] Exit ramp module 18 is similarly moved and positioned on the main platform module 22 . Its low height end 41 and end support 38 are accordingly located adjacent to the low height end 40 and end support 38 of the first entrance ramp module 14 . This is generally seen in FIG. 3 d. [0026] In similar fashion, the second entrance ramp module 16 and the second exit ramp module 20 are reconfigured and stacked on the first entrance ramp module 14 and the first exit ramp module 18 , respectively. Illustrations of the above two steps are seen in FIGS. 3 e and 3 f. [0027] Finally, the second main platform module 24 is positioned on top of the second entrance and exit ramp modules 16 , 20 . (See FIG. 3 g ). In this configuration, the vehicle wash platform 10 has been containerized and bears the dimensions of a standard sized shipping container. [0028] The various modules 14 , 16 , 18 , 20 , 22 , 26 are removeably secured with appropriate mechanisms to interlock or fit together when assembled. Such interlocks and mechanisms may include conventional fasteners, twist locks and other mechanisms, both during containerization and deployment. [0029] As mentioned above, standard ISO fittings are attached either after assembly or built-in to the modules so that the containerized platform 12 can be lifted by standard means and secured to the transport vehicle by standard securement methods. Examples of the lifting means and methods for the containerized platform 12 are shown in FIG. 4 , and are provided such that the containerized platform 12 may be lifted by cranes, front-end lifts or other machinery. An example of such a securement mechanism includes twist-locks. [0030] After containerization, the containerized platform 12 is seen to have recesses 48 or areas within it to store various wash system components such as pumps, spray arches, plumbing means, hoses, etc. [0031] Because of the standard size and ability to be handled by standard means, as indicated in FIG. 5 , and transported by standard means, the containerized platform 12 can easily be transported via truck, rail, ship or air. The containerized platform 12 also will exhibit a good distribution of weight, which will aide in vehicle stability during transportation. If desired, the recesses 48 can be left open in the sides of the containerized platform 12 to reduce the effects of wind during transport. [0032] As can be readily understood by persons of ordinary skill in the art, the vehicle wash platform 10 may include and utilize other suitable devices and combinations. As seen in FIG. 4 , a transportable and rapidly deployable wash system 100 could be provided utilizing more than one container. Such a system 100 includes the vehicle wash platform 10 described above, and also includes one or more other standard sized containers 102 , 104 . The containers 102 , 104 are self-contained and include various other equipment required by the vehicle wash platform 10 , including, without limitation, pumps, valve systems, control systems, water heaters, chemical tanks, water softeners, generators, filters, water tanks, reclamation tanks, etc. Connecting of the containers 102 , 104 and their equipment, to the vehicle wash platform 10 is readily achieved by removing the man-ways 36 of one or both main wash modules 22 , 24 and engaging the appropriate fittings and couplings appropriately provided between the containers 102 , 104 and the main wash platforms 22 , 24 . [0033] The foregoing discussion discloses and describes a preferred embodiment of the invention. One skilled in the art will readily recognize from such discussion, and from the accompanying drawings and claims, that changes and modifications can be made to the invention without departing from the true spirit and fair scope of the invention as defined in the following claims.
A convertible wash platform ( 10 ) for motor vehicles ( 11 ). The wash platform ( 10 ) has a plurality of modules ( 22 ) adapted to be reconfigurable between a first configuration and a second configuration. In the first configuration, the plurality of modules ( 22 ) defines the wash platform ( 10 ). At least some of the modules include water collection portions. In the second configuration, the plurality of modules ( 22 ) integrally define a transportable unit, whereby the transportable unit can be transferred to a deployment site and can be readily reconfigured into the wash platform ( 10 ) of the first configuration for use at the deployment site.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a collapsible pole for use by snowboarders and/or other outdoor enthusiasts. 2. Description of the Related Art Poles are part of the skier's standard equipment. Ski poles serve a variety of functions, such as for example assisting in traversing flat or uphill terrain; the skier pushes the poles into the snow to propel him- or herself forward. Skiers also use poles when traveling downhill, for example to establish a pivot point (pole plant) when slaloming or otherwise making a short radius turn. Snowboarders generally do not carry poles, and do not generally benefit from poles when traveling downhill. However, there are times when snowboarders could benefit from a pole, particularly when traversing flat or uphill terrain. Without a pole, such traversals can be arduous and frustrating, as the snowboarder's sole means of propulsion is to repeatedly shift body weight in an effort to achieve forward momentum. Often, such an attempt is unsuccessful, forcing the snowboarder to sit down, unbuckle his or her equipment so that one foot is free, and kick him- or herself forward with the free foot while trying to keep an interfering twisted front knee from realigning to its natural position. Then, once the traversal is complete, the snowboarder must re-buckle the equipment. Having a pole would be of great utility to a snowboarder who finds him- or herself in such a position. However, most snowboarders find it too awkward to carry a pole, particularly since they have no use for the pole when traveling downhill. A full-length pole would thereby be a burden more often than it would be of use. Some snowboarders carry telescoping poles, such as those designed for backcountry skiing, telemarking, or trekking. These poles can be made smaller when they are not in use. However, in general such poles are usually adjustable from approximately 25″ to 60″, and therefore cannot be made small enough to be truly convenient for the snowboarder. A limitation of telescoping poles is the inability to provide a large number of pole segments. A telescoping pole includes a number of sliding, overlapping cylindrical segments having successively smaller diameters. The pole is collapsed by sliding smaller segments into larger ones, until only the largest segment (plus the handle) is exposed. Because of required wall thicknesses for each cylinder, and because cylinders must fit inside one another, usually only three segments can be accommodated. As a result, such telescoping poles are typically collapsible only to a size equaling the size of the handle plus one-third of the overall pole length. Given a desired overall length of 60″ and a handle length of 5″, the smallest length for a telescoping pole is approximately 25″, which is too large to be convenient for a snowboarder. Attempting to include additional segments causes some of the segments to be either too thick (which adds excessive weight and bulk) or too narrow (which compromises the strength of the pole). In addition, such telescoping poles are subject to additional disadvantages. They may tend to collapse undesirably and unintentionally when a significant amount of force is applied, for example when using the pole for pushing uphill. Also, they are prone to failure, jamming, icing, and locking up. U.S. Pat. No. 6,217,073, to Hoffman, for “Collapsible Snow Pole,” describes an extendable and retractable snow pole for use by snowboarders. Hoffman's snow pole uses a telescoping mechanism which is subject to the problems and limitations set forth above. U.S. Pat. No. 6,217,072, to Gregg, for “Snowboard Pole System,” describes a collapsible snow pole for use by snowboarders. Again, the described device uses a telescoping mechanism which is subject to the problems and limitations set forth above. U.S. Pat. No. 5,941,435, to Munro et al., for “Collapsible, QuickRelease Snowboarding Pole with Leg Mounting System,” also describes a pole that uses a telescoping mechanism. What is needed, therefore, is a collapsible pole that is not subject to the inherent problems and disadvantages described above with respect to telescoping poles. What is further needed is a collapsible pole that provides sufficient strength for use as a snowboarding pole, and that can be collapsed to a small enough size so that it is easily carried by the snowboarder when not in use. SUMMARY OF THE INVENTION The present invention is a collapsible pole that addresses the above described limitations of the prior art and is designed for use by snowboarders. In one aspect, the present invention is implemented as a collapsible snowboarder pole that is divided into a number of segments. The segments are stored in a housing that also functions as a handle when the pole is in use. Tent pole technology enables the segments to fold out and hold shape. The pole segments mate with one another and are held in place by an elastic cord. The cord provides sufficient elasticity to allow the user to pull apart the pole segments enough to disengage them from one another when collapsing the pole. However, unlike a tent pole, where pole segments are typically flexible so as to provide the appropriate type of structural support for a tent, the pole segments of the present invention are rigid so as to function effectively as a snow pole when mated together. In one aspect, the pole segments fit within a hollow housing, or handle, when they are disengaged from one another. In one aspect, the pole segments attach to one another by fitting a smaller-diameter end of one pole into a larger-diameter end of another pole. In other aspects, a sleeve or protrusion affixed to or forming part of an end of one pole mates with an end of another pole. In one aspect, a hollow handle is provided. The handle is shaped to be easily grippable when the snow pole is in use, and can be used as a convenient storage area for housing the pole segments when not in use. In one aspect, the handle of the collapsible pole includes one or more retractable tools, such as a flat head screwdriver, a Philips head screwdriver, a knife, a compass, and the like. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings illustrate several embodiments of the invention and, together with the description, serve to explain the principles of the invention. FIG. 1 is a perspective view of a handle for a collapsible snowboarder pole according to one embodiment. FIG. 2A is a side view of a handle for a collapsible snowboarder pole according to one embodiment. FIG. 2B is a front view of a handle for a collapsible snowboarder pole according to one embodiment. FIG. 2C is a top view of a handle for a collapsible snowboarder pole according to one embodiment. FIG. 3A depicts an embodiment of the present invention where a series of pole segments are being pulled out of the handle. FIG. 3B depicts rotation of the first pole segment about a fulcrum in the handle. FIG. 3C depicts a collapsible snowboarder pole in its extended position, according to one embodiment. FIG. 4 depicts an embodiment for mating two pole segments, wherein a first pole segment end fits inside the end of a second pole segment. FIG. 5 depicts a technique for unmating pole segments so that that the pole can be collapsed, according to one embodiment. FIG. 6 is a cross-sectional view showing two pole segments mating with one another, according to one embodiment. FIG. 7 is a detail view showing a pole segment attached to a handle, according to one embodiment. FIG. 8 depicts an alternative embodiment for mating two pole segments, wherein a sleeve affixed to a first pole segment end mates with an end of a second pole segment. FIG. 9A illustrated detachability of two grips of the handle. FIG. 9B depicts retractable tools that fit within the handle of the snowboarder pole according to one embodiment. FIGS. 10A and 10B depict an example of the use of the snowboarder pole of the present invention to propel oneself by pushing off. FIGS. 11A , 11 B, and 11 C depict an example of the use of the snowboarder pole of the present invention to propel oneself by pulling with two hands. FIGS. 12A and 12B are cross-sectional views of the handle of the present invention showing storage of pole segments therein. DETAILED DESCRIPTION OF THE EMBODIMENTS The present invention is now described more fully with reference to the accompanying Figures, in which several embodiments of the invention are shown. The present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather these embodiments are provided so that this disclosure will be complete and will fully convey the invention to those skilled in the art. In the following description, the invention is set forth in the context of a collapsible pole for use by a snowboarder. However, one skilled in the art will recognize that the invention can be implemented or used for other purposes as well. In fact, the invention can be used to provide a collapsible pole (with attached handle) for any type of use. Referring now to FIG. 1 , there is shown a perspective view of a handle 100 for a collapsible snow boarder pole according to one embodiment. FIGS. 2A , 2 B, and 2 C show a side view, front view, and top view of handle 100 , respectively. In one embodiment handle 100 is hollow so that it can serve as a housing for pole segments. For illustrative purposes, FIG. 2C shows overall dimensions of handle 100 ; however, one skilled in the art will recognize that the present invention is not limited to the dimensions shown, and can be implemented using other dimensions. In one embodiment, handle 100 is 8″ high and 1.625″ wide. In one embodiment, the wall thickness of handle 100 is ¼″. Pole segments can be stored side-by-side within handle 100 . For example, in one embodiment handle 100 can hold five cylindrical pole segments of approximately ½″ diameter and approximately 6″ length. Assuming one inch of overlap from one pole segment to the next, this would yield a pole of 25″ total length (not including handle 100 ). Referring now to FIGS. 12A and 12B , there are shown cross-sectional views of handle 100 depicting examples of storage arrangements for pole segments 301 A, 301 within handle 100 . FIG. 12A shows one possible arrangement of pole segments 301 A, 301 . FIG. 12B shows another possible arrangement of pole segments 301 A, 301 . In one embodiment, handle 100 is 1.625″ wide (outer dimension). In one embodiment, pole segments 301 A, 301 have an outer diameter of 0.5″ and an inner dimension of 0.3″. In one embodiment, handle 100 provides sufficient space to allow for a ⅛″ buffer zone between segments 301 A, 301 to provide adequate spacing for segments 301 A, 301 . In one embodiment, as discussed below, pole segment 301 A is attached to and swivels out from handle 100 , while remaining pole segments 301 are attached to segment 301 A via an elastic cord (described in further detail below). In one embodiment, handle 100 includes vertical grip 101 that is gripped by the snowboarder when using the pole for pulling, and upper horizontal grip 102 that is gripped by the snowboarder for both pushing and pulling. Depending on the terrain and circumstances, snowboarders can use the pole of the present invention for either pushing or pulling. Referring now to FIGS. 10A and 10B , there is shown an example of the use of the snowboarder pole of the present invention to push off. Snowboarder 1000 puts the pole in the snow and pushes down on upper horizontal grip 102 of handle 100 in order to propel him- or herself. Referring now to FIGS. 11A , 11 B, and 11 C, there is shown an example of the use of the snowboarder pole of the present invention to pull oneself forward. Snowboarder 1000 puts the pole in the snow, and grips vertical grip 101 with one hand and horizontal grip 102 with the other hand. Snowboarder 1000 then has sufficient leverage to pull on handle 100 in order to propel him- or herself. In one embodiment, both grips 101 , 102 are shaped to fit a snowboarder's hand within a glove or mitten. In one embodiment, handle 100 includes door 103 that can be opened, for example by pressing on release button 104 , to gain access to pole segments within. According to various embodiments, door 103 can be designed to open in any number of ways, whether by button, lever, or latch, and can be pushed open either manually or via a spring-loaded mechanism (not shown). Referring briefly to FIG. 7 at the bottom of door 103 is notch 702 which aligns with notch 701 in the bottom of handle 100 to provide an opening through which a first pole segment can protrude. In one embodiment, door 103 contains a latch or clip (not shown) that holds it in the closed position until button 104 is pressed again. In one embodiment door 103 is spring-loaded so that once opened it stays open until pressed shut. Referring now to FIG. 3A , there is shown a series of pole segments 301 being pulled out of handle 100 . Segments 301 may be disposed to fall out of handle 100 when button 104 is pressed; alternatively, segments 301 may be launched out of handle 100 by a spring-loaded action, or they can be pulled out manually by the user. As shown in FIG. 3B , first segment 301 A pivots around fulcrum 303 located near the bottom end of handle 100 , and protrudes through notch 701 in the bottom of handle 100 . Referring now also to FIG. 7 , there is shown a detail view showing pole segment 301 A attached to handle 100 , according to one embodiment. When door 103 is closed, first segment 301 A is locked in place by the combination of notch 702 in door 103 and notch 701 in handle 100 . Notches 701 and 702 match up with one another to provide an opening through which pole segment 301 A protrudes. In one embodiment, segments 301 are attached to segment 301 A and to one another via “tent pole” mechanism; an elastic cord runs through the segments 301 , 301 A to hold them together when mated. Segments 301 , 301 A are hollow, and in one embodiment are cylindrical in shape. Referring now to FIG. 4 , there is shown a mechanism for mating two pole segments 301 according to one embodiment. Smaller male end 302 of one pole segment 301 fits inside larger female end 402 of another pole segment 301 . The user unfolds the pole by fitting each male end 302 into a corresponding female end 402 . As elastic cord 401 contracts, it pulls the female and male parts 402 , 403 of the mating pole segments 301 together and holds them in place while the pole is being used. Smaller male end 302 may either be an integral part of pole segment 301 , or it may be a protrusion attached to the end of pole segment 301 . Referring now to FIG. 6 , there is shown a cross-sectional view depicting two pole segments 301 mating with one another, according to one embodiment. In the example shown, segments 301 are hollow cylinders. Male end 302 of one segment 301 is mated with female end 402 of the other segment 301 . Cord 401 runs through the centers of segments 301 to keep them mated with one another. Referring now to FIG. 8 , there is shown an alternative mating mechanism. Sleeve 801 is affixed to segment 301 AA so that the end of sleeve 801 extends beyond the end of segment 301 AA, forming a seat for receiving of an end of segment 301 AB. The two segments 301 AA, 301 AB are mated with one another by inserting an end of segment 301 AB into sleeve 801 . The inner diameter of sleeve 801 is sized to approximately match the outer diameter of segments 301 AA and 301 AB so as to provide a snug fit. Elastic cord 401 keeps segments 301 AA, 301 AB mated with one another as described above. One skilled in the art will recognize that other mating techniques can also be used. For example, the ends of segments 301 can be threaded to match one another, so as to provide extra strength, particularly when pulled on. Referring now to FIG. 3C , there is shown collapsible snowboarder pole 310 in its extended position, according to one embodiment. Segments 301 , 301 A are mated with one another, and segment 301 A is held in place within handle 100 . In one embodiment, the last segment 301 has a pointed end 306 and a round basket 305 mounted transversely near end 306 to keep pole 310 from penetrating too far into the snow. When pole 310 is fully extended, the resulting structure has strong compression strength to enable the snowboarder to push off, and strong bending strength to enable the snowboarder to pull himself or herself forward. The torsion strength of pole 310 , the elastic cord 401 , is strong enough to keep segments 301 from sliding apart from one another, yet mild enough to enable the user to pull apart segments 301 for folding. In one embodiment, elastic cord 401 is made of rubber, elastic thread, cotton, polyester, acrylic, polypropylene, nylon, rayon, or any combination thereof. In one embodiment, segments 301 A, 301 are made of aluminum or carbon fiber. After use, as shown in FIG. 5 , the user folds up the pole by pulling segments 301 apart, stretching elastic cord 401 and detaching the female and male parts 402 , 403 from one another. With the extra slack in cord 401 , the user folds segments 301 back onto each other. The user presses button 104 to open door 103 , pivots first segment 301 A around pivot point 303 , places all segments 301 , 301 A inside handle 100 , and closes door 103 . In one embodiment, grips 101 and 102 can be separated from one another, as shown in FIG. 9A . A latch or button (not shown) releases the two portions of handle 100 so that they can be separated. In one embodiment, retractable tools are provided within handle 100 . For example, as shown in FIG. 9B , tools such as knife 901 , flathead screwdriver 902 , and Philips screwdriver 903 can be folded out from grip 102 . In the above description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the invention. It will be apparent, however, to one skilled in the art that the invention can be practiced without these specific details. For example, one skilled in the art will recognize that the pole of the present invention can be used for other purposes than snowboarding, including any activity where a pole is useful but where collapsibility is an advantage. Reference in the specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment. As will be understood by those familiar with the art, the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. For example, the particular architectures depicted above are merely exemplary of one implementation of the present invention. The functional elements and method steps described above are provided as illustrative examples of one technique for implementing the invention; one skilled in the art will recognize that many other implementations are possible without departing from the present invention as recited in the claims. Likewise, the particular capitalization or naming of the modules, protocols, features, attributes, or any other aspect is not mandatory or significant, and the mechanisms that implement the invention or its features may have different names or formats. In addition, the present invention may be implemented as a method, process, user interface, computer program product, system, apparatus, or any combination thereof. Accordingly, the disclosure of the present invention is intended to be illustrative, but not limiting, of the scope of the invention, which is set forth in the following claims.
A collapsible snowboarder pole is divided into a number of segments. The segments are stored in a housing that also functions as a handle when the pole is in use. Tent pole technology enables the segments to fold out and hold shape. The pole segments mate with one another and are held in place by an elastic cord. The cord provides sufficient elasticity to allow the user to pull apart the pole segments enough to disengage them from one another when collapsing the pole.
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CROSS REFERENCES TO RELATED APPLICATIONS [0001] This application is a continuation of and claims the benefit and priority of U.S. Non-Provisional patent application Ser. No. 11/042,945 filed Jan. 24, 2005 METHOD AND APPARATUS FOR REMOVABLY HOLDING MEDICAL DEVICE, the contents of which are incorporated by reference herein and which application relates to and incorporates by reference Japanese Patent application No. 2004-015671 filed on Jan. 23, 2004. BACKGROUND OF THE INVENTION [0002] 1. Technical Field of the Invention [0003] The present invention relates to a method and apparatus for removably holding various medical devices such as endoscopes used, for example, during surgical operations in cranial nerve surgery. [0004] 2. Related Art [0005] An apparatus for holding medical devices (medical-device holding apparatus) has been known, which has a polyarticular arm equipped with a holder that holds medical devices and joints equipped with brakes to selectively lock/unlock the turns of the arm. This medical-device supporting apparatus allows the holder to support, for example, an endoscope so that the endoscope is positioned to face a desired portion to be examined of a patient. In this attitude of the holder, the joints are locked to prevent a field of view of the endoscope from deviating outside the portion to be examined. Thus a surgeon is able to concentrate on the surgical operation, without being bothered by positional adjustment operations of the endoscope. [0006] Meanwhile, as described in Japanese Patent Publication (unexamined) No. 2002-345831, the medical-device holding apparatus has a grasping member which is used to move the holder (i.e., the endoscope), wherein the grasping member is arranged close to the holder. That is, in order to lock and unlock the brakes in the joints, the grasping member is arranged to substantially be perpendicular to an insertion axis assigned to the endoscope and is equipped two operation switches secured thereon. Thus a surgeon grasps the grasping member and, at the same time, pushes those two operation switches by, usually, the first and middle fingers. This push operation allows the brakes to be activated, so that each joint is released from being locked. In other words, in the condition where both the two operation switches are not pressed at the same time (, or together), each joint will not be released from being fixed. It is therefore possible for a surgeon to worry about erroneous release operations of the brakes during a surgical operation, so that the surgeon can concentrate on the operation. [0007] Further, in operating the medical-device holding apparatus, it is required that a surgeon's touch to the arm will not move the arm under the condition in which the brakes have been locked in the joints. To realize such a situation, a large amount of fixing force should be given to each brake. In contrast, with the arm made free (i.e., the locks are released), it should be constructed such that a medical device that has been held by the apparatus can be moved freely with a light amount of operator's force. In addition, with taking malfunctions and others of the joints, design is made such that the brakes sustain a certain specific level of braking force to prevent the arm from moving in such malfunction cases. SUMMARY OF THE INVENTION [0008] Accordingly, an object of the present invention is to provide a method and apparatus holding a medical device, which has the capability of selectively locking and unlocking the joints of an arm unit holding the medical device in a proper manner. [0009] As one aspect, the present invention provides an apparatus for holding a medical device, comprising: an arm unit spatially movably holding a single medical device; an operation unit equipped with a plurality of operation members to be operated by an operator to enable the arm unit to move spatially; a determination unit determining whether or not an operator's operation at the plurality of operation members corresponds to an improper state deviating from a properly operated state in which at least two operation members of the operation members have been operated within a predetermined period of time; and a movement controller prohibiting, in a controlled manner, a spatial movement of the arm unit when the determination unit determines that the operation at the plurality of operation members corresponds to the improper state. [0010] For making the arm unit holding the medical device movable, it is required for an operator to operate at least two predetermined operation members among a plurality of operation members secured on an operation unit. Only when a properly operated state is established where the “at least two operation members” are operated within a predetermined period of time (for example, a few seconds), the operator is allowed to move the arm unit, so that the arm unit can be moved to spatially move the medical device such as endoscope at operator's will. [0011] However, the operator's operation is in the improper state deviating from the “properly operated state,” the arm unit is not allowed to move. In other words, the medical device is not allowed to move spatially; of course, cannot be moved at operator's will. Hence the medical device is obliged to keep its locked (fixed) state at the same spatial position. The “improper state” includes an “improperly operated state,” in which an operator has not operated the foregoing “at least two operation members” within a predetermined period of time; an “accidentally operated state,” in which only part of the foregoing “at least two operation members” is operated due to, for example, a push from any obstacle; and a “malfunctioning state,” in which a signal resulting from operational failures of the operation unit is outputted from the operation unit, the signal showing a situation where only part of the foregoing “at least two operation members” is operated. Incidentally, though the states deviating from the “properly operated state” includes a “non-operated state,” but this is omitted from the explanations in the present invention, because such a state does not relate to the movement of the arm unit any longer. [0012] As another aspect of the present invention, there is provided an apparatus for holding a medical device, comprising: an arm unit spatially holding the medical device; an electric driver spatially moving the medical device and being secured to the arm unit; an operation unit equipped with a plurality of operation members to be operated by an operator to control a spatial movement of the medical device; a determination unit determining whether or not an operator's operation at the plurality of operation members corresponds to an improper state deviating from a properly operated state in which at least two operation members of the operation members have been operated within a predetermined period of time; and an electric operation controller prohibiting the electric driver from being operated in a controlled manner, in cases where it is determined by the determination unit that the operation is in the improper state. Hence the improper states (i.e., the improperly operated state, accidentally operated state, and malfunctioning state) are found to prohibit the operations of the electronic driver, resulting in that the medical device is locked from its spatial movement. [0013] Still, as another aspect of the present invention, there is provided a method for holding a medical device to be spatially movable, the medical device being held by an arm unit by allowing an operator to operate a plurality of operation members, the method comprising steps of: determining whether or not an operator's operation at the plurality of operation members corresponds to an improper state deviating from a properly operated state in which at least two operation members of the operation members have been operated within a predetermined period of time; and prohibiting, in a controlled manner, a spatial movement of the arm unit when it is determined that the operation at the plurality of operation members corresponds to the improper state. This holding method also copes with the forgoing improper states in the same way as the above. BRIEF DESCRIPTION OF THE DRAWINGS [0014] In the accompanying drawings: [0015] FIG. 1 is a perspective view showing the configuration of a medical-device holding apparatus according to a first embodiment of the present invention; [0016] FIG. 2 is a side view, partly sectioned, showing a holder employed by the holding apparatus in the first embodiment; [0017] FIG. 3 is a block diagram of hardware elements of a controller employed by the holding apparatus in the first embodiment; [0018] FIG. 4 is a functional block diagram of the controller employed by the holding apparatus in the first embodiment; [0019] FIG. 5 is a flowchart showing the operations of the controller; [0020] FIG. 6 is a perspective view showing a holder employed by a medical-device holding apparatus in a second embodiment according to the present invention; [0021] FIG. 7 is a flowchart showing the operations performed by a controller in the second embodiment; [0022] FIG. 8 is a perspective view showing a medical-device holding apparatus in a third embodiment according to the present invention; [0023] FIG. 9 shows a block diagram of an electric field-of-view driver according to the third embodiment; [0024] FIG. 10 illustrates a block diagram of a control circuit according to the third embodiment; and [0025] FIG. 11 is a perspective view indicating a holder adopted by a medical-device holding apparatus according to a modification directed to the third embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0026] Various embodiments of medical-device holding apparatuses according to the present invention will now be described with reference to the accompanying drawings. First Embodiment [0027] Referring to FIGS. 1-5 , a medical-device holding apparatus according to a first embodiment will now be described. [0028] As shown in FIG. 1 , the medical-device holding apparatus is provided with a support base 11 , a polyarticular arm 12 whose one end is attached to the support base 11 , and a holder 13 sustained at the other end of the polyarticular arm 12 . [0029] The support base 10 is detachably attached to an attaching member, such as floor or patient bed. The polyarticular 12 is provided with three arms consisting of first to third arms 12 a - 12 c , three joints 13 a - 13 c arranged at one end of the first arm 12 a , between the first and second arms 12 a and 12 b , and between the second and third arms 12 b and 12 c , respectively, and a ball joint attached to the top of the third arm 12 c . Therefore, on the support base 10 , the arms 12 a , 12 b , and 12 c are connected to each other in this order so that the arms 12 a - 12 c can be moved rotatably in the three-dimensional space via the joints 13 a , 13 b , and 13 c . In addition, a pillar 15 is suspended from the ball joint 14 attached to the headmost arm 12 c , and a holder 13 to which a medical device is held is secured to the pillar 15 . [0030] The ball joint 14 incorporates a known fluid clutch 28 d (refer to FIG. 3 ) that uses fluid, such as air, as a pressure transmission medium. The fluid clutch 28 d is electrically connected to a control box 16 composing as control means and responds to a command from the control box 16 in such a manner that a clutch portion (i.e. a brake not shown) of the fluid clutch 28 d are selectively controlled between two states of being clutched and non-clutched. The clutch portion connects both the pillar 15 (that is, the holder 13 ) and the third arm 12 c . Thus, when the clutch portion is in its clutched state, the pillar 15 (holder 13 ) is positionally fixed to the third arm 12 c (i.e., positionally fixed). In contrast, in cases where the clutch portion is in its non-clutched state, the pillar 15 (i.e., the holder 13 ) will not be positionally fixed to the third arm 12 c , and can be moved freely. To be short, the fluid clutch 28 d responds to the existence and non-existence of fluid pressure to be supplied so that the holder 13 is positionally fixed to the ball joint 14 or positionally released from being fixed to the ball joint 14 in a selective manner. [0031] As described, the holder 13 is coupled with the third arm 12 c via the ball joint 14 with the fluid clutch 28 d , and can be rotated and moved with suspending from the third arm 12 c under the fluid clutch 28 d is unclutched (i.e., released). [0032] The fluid clutches 28 a - 28 c (refer to FIG. 3 ) employing fluid such as air and having the similar construction and function are incorporated in the joints 13 a - 13 c , respectively, and can selectively be switched between their clutched or non-clutched states in answer to a control signal from the control box 16 . The fluid clutches 28 a - 28 c are constructed to release the clutch portion in response to an application of pressure. In such a control manner, the first arm 12 a is able to selectively realize the position-fixed state or position-free state to the support base 11 , the second arm 12 b to the first arm 12 a , and the third arm 12 c to the second arm 12 b. [0033] On the headmost end of the holder 13 , as shown in FIGS. 1 and 2 , an endoscope 17 serving as one of medical devices to treat and observe the inside of a patient to be examined is detachably loaded and supported. In FIG. 1 , a reference P depicts a patient to be observed and treated and by the endoscope 17 . [0034] By way of example, the holder 13 is formed into a cuboid-like member having a specific thickness and a section perpendicular to its longitudinal axis formed into a rectangle. This holder 13 , which can be grasped by a user, has switches loaded thereto which can be operated by the user. The size of the cuboid-like member is set to an appropriate amount which makes it possible that the user grasps the member well. [0035] On a base-side end of the holder 13 , one end of the foregoing pillar 15 is secured, while at the head-side end, a loading hole is formed therethrough. The endoscope 17 is loaded in the loading hole in a detachable manner. [0036] On upper and lower surfaces of the holder 13 are formed a first switch and a second switch 18 and 19 , which serve as input means of operation signals, consist of microswitches, respectively. The upper and lower surfaces are defined as upward and downward surfaces of the holder 13 when an operator can grasp the holder 13 from a direction which makes the endoscope 17 downward, as shown by a chain double-dashed line W in FIG. 2 . [0037] The first and second switches 18 and 19 are formed to provide switch signals to the control box 16 through lead wires respectively connecting to the control box 16 . As will be described later, the control box 16 has the configuration that uses the switch signals to produce control signals in which the states indicated by the switch signals are reflected, the control signals being fed to the fluid clutch 28 d of the ball joint 14 and the fluid clutches 28 a - 28 c of the joints 13 a - 13 c. [0038] The structures of the first and second switches 18 and 19 will now be described. As illustrated in FIG. 2 , the first and second switches 18 and 19 are embedded in two locations of the holder 13 ; to be specific, when a user grasps the holder 13 , one switch 18 is located close to the holder near to an endoscope-loading region of the holder 13 , that is, a head-side given position of the holder 13 to which the thumb is approximately touched on the upper surface and the other switch 19 is located at a given position of the holder 13 to which the first finger is approximately touched on the lower surface. The first switch 18 is embedded to have its operating portion opened from the upper surface, whilst the second switch 19 is embedded to have its operating portion opened from the lower surface. [0039] More specifically, a first and second concave switch accommodating rooms 20 and 21 are formed at given positions of the holder 13 , which are close to the head thereof. These accommodating rooms 20 and 21 are formed to provide their main opening opened from the upper and lower surfaces of the holder 13 , but are slightly positionally shifted with each other in a longitudinal direction of the holder 13 . In the first and second concave switch accommodating rooms 20 and 21 , the first and second switches 18 and 19 are accommodated with their operating directions upside down with each other. Specifically, in FIG. 2 , the operating direction to the first switch 18 is a downward direction and that to the second switch 19 is an upward direction. The lead wires of the first and second switches 18 and 19 are electrically coupled to the control box 16 , respectively. [0040] Of the above switch accommodating rooms 20 and 21 , the first switch accommodating room 20 accommodates the first switch 18 together with a switch lever 22 and a hinge 23 , where the switch lever 22 faces the first switch 18 to freely rotate thanks to the hinge 23 . To the switch lever 22 is provided a pushing force via a first spring member 24 in the clockwise in FIG. 2 (corresponding to a direction that turns the first switch 18 “on”). This first spring member 24 has a base portion engaging with a tip of an operation-force-amount adjusting member 25 in an adjustable fashion. This adjusting member 25 has a middle portion held by holder 13 in a screw-adjustable manner and a base portion to which an operating portion 26 is secured so that the operating portion 26 can be operated. The operating portion 26 is located to protrude from the lower surface of the holder 13 . Accordingly, rotating the adjusting member 25 makes the adjusting member 25 itself advance against the first spring member 24 , whereby the pushing force of this first spring member 24 can be adjusted. An amount of force required to operate the switch lever 22 can be adjusted. [0041] As shown in FIG. 3 , each of the foregoing fluid clutches 28 a - 28 d is coupled with an electromagnetic valve 29 via a duct PG. The electromagnetic valve 29 is coupled with a fluid-pressure source 29 a , which is for example a gas container placed in an operation room. Hence, responsively to the open and close of the electromagnetic valve 29 , the fluid of a given pressure (e.g., air) is supplied to the fluid clutches 28 a - 28 d , respectively, from the fluid-pressure source 29 a. [0042] As shown in FIG. 3 , the control box 16 is provided with a CPU 30 , in which processing on software executed by the CPU 30 provides desired calculation functions. The calculation part of the control box 16 , however, is not always limited to the computer configuration that uses the CPU, but may be configured into a hardware construction that provides desired functions using logic circuits such as AND and OR circuits. [0043] The control box 16 according to the present embodiment is provided with, besides the CPU 30 , peripheral devices including a ROM 31 , RAM 32 , clock circuit 33 , input interface 34 , and output interface 35 , a D/A converter 36 connected to the output interface 35 , and a driver 37 . In the ROM 31 , programs are stored in advance, which are computer-readable and define procedures of calculation for control of the clutches which will be described later. When the CPU 30 is activated, it therefore reads in the programs from the ROM 31 , and executes calculation in sequence based on the procedures defined by the read-in programs. The RAM 32 is a memory temporarily used during the calculation of the CPU 30 . The clock circuit 33 is placed to provide a reference clock signal to the CPU 30 . [0044] Connected to the input interface 34 are the first and second switches 18 and 19 , so that on/off information from the switches 18 and 19 is transmitted to the CPU 30 . A control signal produced through the calculation executed by the CPU 30 is sent to the D/A converter 36 via the output interface 35 , thereby being subject to D/A conversion. The resultant control signal is amplified by the driver 37 , and then supplied to the electromagnetic valve 29 . [0045] The control box 16 is also provided with, as information means, a buzzer 38 and an LED 39 , which are connected to the CPU 30 . [0046] Calculating functions realized by the CPU 30 can be depicted as shown in FIG. 4 . Concretely, with its software processing, the CPU 30 is able to present the functions for a switch detection circuit “A,” determination circuit “B,” and drive/control circuit “C.” [0047] Of these functions, the switch detection circuit “A” detects the on/off states of the first and second switches 18 and 19 , and operates on the basis of the detected results such that it outputs an “on” signal to the drive/control circuit “C,” only when both the first and second switches 18 and 19 are turned “on” almost simultaneously (that is, at the same time or within a predetermined period of time). Responsively to the “on” signal, the drive/control circuit “C” outputs a drive signal to open the electromagnetic valve 29 . When the electromagnetic valve 29 is opened, fluid pressure is applied from the fluid-pressure source 29 a to the fluid clutches 28 a , 28 b , 28 c and 28 d , thus releasing the fluid clutches 28 a - 28 d . As a result, the joints 13 a - 13 c and boll joint 14 presents their position-free states, that is, released states from their position-fixed states. [0048] Meanwhile, in cases where, of the first and second switches 18 and 19 , either one switch is turned “on” over a predetermined period of time or more, the determination circuit “B” determines that either one switch has been pressed alone, and provides no control signal with the drive/control circuit “C” (i.e., “off” state). That is, the electromagnetic valve 29 becomes its closed state or keeps its closed state. In this closed state of the electromagnetic valve 29 , no fluid pressure is applied from the fluid-pressure source 29 a to the fluid clutches 28 a - 28 d , with the result that fluid clutches 28 a - 28 d are kept clutched, whereby the joints 13 a - 13 c are kept locked (i.e., in their position-fixed states). [0049] The determination circuit “B” has a timer function (realized by a timer BT in FIG. 4 ) in order to measure a state where either the first or second switch 18 or 19 solely becomes “on” over a predetermined period of time or more. [0050] Referring to FIG. 5 , practical procedures of calculation on the software processing executed by the CPU 30 will now be described. [0051] The CPU 30 determines, at step S 1 , whether or not the first switch 18 is in the “on” state. If the determination is NO (that is, the first switch 18 is in the “off” state), the processing in the CPU 30 proceeds to step S 2 , whereat the CPU 30 determines whether or not the second switch 19 is in the “on” state. When the determination is NO (that is, the second switch 19 is in the “off” state), the CPU 30 makes the processing to proceed to step S 3 , where the CPU 30 commands the electromagnetic valve 29 to be or kept “off.” The processing is then made to advance to steps S 4 -S 6 in sequence, where the CPU 30 commands the buzzer 38 to be or kept “off” (step S 4 ), commands the LED 39 to be or kept “off” (step S 5 ), and commands the timer BT to initialize its count (step S 6 ). Then the processing returns to step S 2 . [0052] In addition, when it is determined “YES” at step S 1 , the CPU 30 makes the processing to step S 7 , whereat it is further determined whether or not the second switch 19 is in the “on” state. If the determination at step S 7 is “YES,” the processing is shifted to step S 8 to allow the electromagnetic valve 29 to be or kept “on.” The processing is then made to advance to steps S 9 -S 11 in sequence, where the CPU 30 commands the buzzer 38 to be or kept “off” (step S 9 ), commands the LED 39 to be or kept “off” (step S 10 ), and commands the timer BT to initialize its count (step S 11 ). Then the processing returns to step S 2 . [0053] Moreover, in cases where it is determined “yes” at step S 2 or “no” at step S 7 , the processing in the CPU 30 is shifted to step S 12 , where it is determined whether or not the timer BT is in operation. The determination at step S 12 reveals the timer BT is not in operation (NO), the processing is shifted to step S 13 to cause the timer BT to start its count operation. The processing at step S 14 is then executed to allow the electromagnetic valve 29 to be “off.” Further, at step S 15 , the buzzer 38 is made or kept “off,” and then, at step S 16 , the LED 39 is made or kept “off,” before returning to step S 1 . [0054] In the case that the determination at step S 12 is YES, that is, it is determined at step S 12 if the timer BT is in operation or not, the CPU 30 shifts its operation to step S 17 , where it is determined if or not the timer BT has counted a predetermined period of time (for example, 3 seconds) or more. If YES at step S 17 , the processing at steps S 18 , S 19 , and S 20 is executed in turn. Specifically, the electromagnetic valve 29 is brought into or kept “off” (step S 18 ), the buzzer 38 is turned or kept “on” (step S 19 ), and then the LED 39 is turned or kept “on” (step S 20 ), before returning to step S 2 . [0055] In contrast, when it is determined NO at step S 17 , the processing at steps S 14 -S 16 is executed by the CPU 30 as described above. To be specific, the electromagnetic valve 29 is made or kept “off” (step S 14 ), the buzzer 15 is made or kept “off” (step S 15 ), and the LED 39 is made or kept “off” (step S 16 ). [0056] Accordingly, through the foregoing processing conducted by the CPU 30 , the control signal supplied to the electromagnetic valve 29 is kept “off,” when either the first or second switch 18 or 19 is turned “on” solely. The electromagnetic valve 29 thus keeps its closed valve state, which keeps the clutched states of the fluid clutches 28 a , 28 b , 28 c and 28 d . Since the joints 13 a , 13 b and 13 c are positionally kept locked (clutched), the polyarticular arm 12 is also positionally kept locked, so that the endoscope 17 is positionally fixed (i.e. the position-fixed state). [0057] In addition, during the position-fixed state being kept, the system is able to cope with an operator's operation that only either the first or second switch 18 or 19 is turned “on” and the “on” state lasts for a predetermined period of time (in the present embodiment, three seconds). Even if such an operation is carried out, the foregoing locked state of the polyarticular arm 12 is kept, while the buzzer 38 honks and the LED 39 flashes. Thus the operator is able to steadily know that the medical-device holding apparatus has failed to release its locked state (i.e., position-fixed state), which requires succeeding necessary operations such as unlocking re-operation. Hence the operator's operation can be smoothened. [0058] Additionally, in cases where the endoscope 17 or polyarticular arm 12 is moved to rotate during a surgical operation, it may happen that the drape is pulled to accidentally push either the first or second switch 18 or 19 . It may also happen that such a rotary operation involves an interference with other devices which may cause only either the first or second switch 18 or 19 to be turned “on” by mistake. Even such situations are caused, the foregoing information means immediately informs the operator of the currently operated state, thereby alleviating the operator from anxiety that the operator should take care of operations at all times. This reduces an operator's burden on the operations. [0059] By the way, the exemplified processing shown in FIG. 5 , which is executed by the CPU 30 , can further be modified with regard to, for example, the order of on/off determinations for the first and second switches 18 and 19 . The second switch 19 may be subjected to the on/off determination, before that for the first switch 18 . With regard to the buzzer 38 and LED 39 serving as the information means, only one of the buzzer 38 and LED 39 may be employed. [0060] Further, a period of time to be measured by the timer at step S 17 cannot always be limited to 3 seconds, but may be a minimum period of time which can sense steadily the state in which “either the first or second switch 18 or 19 is “on”-operated alone. In other words, such a period of time can be defined as a time interval for measuring simultaneity for operator's operations. Hence, for example, an appropriately selected period of time, such as 1 second, 2 seconds, or 4 seconds, can be adopted, depending on design conditions or other necessary factors. [0061] Moreover, as described, in the processing shown in FIG. 5 conducted by the CPU 30 , the detection is made to recognize the state both the first and second switches 18 and 19 are operated “on” and a span of time from the “on” operation at one switch 18 ( 19 ) to that at the other switch 19 ( 18 ) is within a predetermined period of time. This manner of detection can be applied to detection of malfunctioning states of either the first or second switch 18 or 19 . For example, in cases where either switch is in fault condition due to a fusion-bonded switch contact, the processing shown in FIG. 5 can also be used for detecting the malfunction. In order to achieve this, the CPU 30 is set to execute the processing shown in FIG. 5 at specific intervals (for example, at intervals of a few minutes or at a time when the apparatus is activated). Hence, when either the first or second switch 18 or 19 is out of order (in other words, no operation is made but the switch is in the “on” state), this state is detected, resulting in that the buzzer 38 honks and the LED 39 flashes. Using an LED dedicated to this detection, which is different from the LED 39 designated as means to inform the foregoing improperly operated states or accidentally operated states, makes it easier for an operator to immediately recognize the malfunctioning states of the various switches. In this case, of course, either one of the buzzer and LED can be used as informing means. [0062] Moreover, signals to be detected at steps S 1 , S 2 and S 7 in FIG. 5 are not be limited to signals from the first and second switches 18 and 19 , but may be signals from electric circuits electrically connected to these switches, respectively. For instance, in a configuration where a relay is arranged to each of the first and second switches 18 and 19 to provide a switch signal via each relay, a signal outputted from each relay can be an object to be detected. Thus, the object to be detected can be developed to peripheral circuits of the switches, such as relay whose contact is fusion-bonded, which may not be confined to the detection of malfunction of the switch itself. This way of detection can raise reliability for the arm-move prohibiting control. Second Embodiment [0063] Referring to FIGS. 6 and 7 , a second embodiment of the medical-device holding apparatus according to the present invention will now be described. In the second and subsequent embodiments, the configuration elements identical or similar to those in the first embodiment will be referred by the same reference numerals for the sake of simplified or omitted explanations. [0064] The configurations in the second embodiment differ from those in the first embodiment in the shape of the holder 13 and the locations of the first and second switches disposed in the holder 13 . In addition, a further difference from the first embodiment is how to escape from a locked state where the joints are locked due to the fact that either the first or second switch is alone operated for a predetermined period of time or more. [0065] As shown in FIG. 6 , in order that the fluid clutches in the joints of the polyarticular arm 12 (arms 12 a - 12 c ) have clutched and unclutched in a selective manner, there are provided two operation switches 3 a and 3 b mounted on the holder 13 handled for moving the endoscope 17 . The two operation switches 3 a and 3 b are arranged on both sides of the plate-like holder 13 in such a manner that they are located at the same position in the longitudinal direction of the holder 13 . The LED 39 is mounted on the endoscope-side tip of the holder 13 . Incidentally, in the present embodiment, the buzzer is omitted from being arranged. When an operator such as surgeon holds grips the holder 13 to press the two operation switches 3 a and 3 b by the thumb and first finger at the same time (simultaneously or almost simultaneously), the fluid clutches operates to release the fixed state of each joint (i.e., unclutched). Thus as long as the two operation switches 3 a and 3 b are not pressed at the same time or within a predetermined period of time, each joint will not be from its clutched state. [0066] In this medical-device holding apparatus, it may happen that rotating the endoscope 17 or arms 12 a - 12 c during a surgical operation causes the drape to be tightened or an interference with other equipments, so that the operation switches 3 a and 3 b are pressed by mistake. To prevent such situations, the CPU 30 executes the processing according to the flowchart shown in FIG. 7 . [0067] That is, at step S 21 in FIG. 7 , it is determined whether or not one operation switch 3 a , of the two operation switches 3 a and 3 b , is in “on.” When this determination shows NO, the processing is shifted to step S 22 , where the other operation switch 3 b is subjected to the determination whether or not it is made “on.” If the determination at step S 22 is NO, the processing goes to step S 23 to turn or keep the electromagnetic valve 29 “off.” Further, the processing is performed at step S 24 to turn or keep the LED 39 “off” and, at step S 25 , to initialize the timer BT, before returning to step S 21 . [0068] Meanwhile when it is determined YES at step S 21 , the processing is shifted to step S 26 , where the determination switch 3 b is subjected to the determination whether or not it is made “on.” The determination of YES allows the processing to be performed at step S 27 , where the electromagnetic valve 29 is made or kept “on.” Then at step S 28 , the LED 39 is made or kept “off,” and at step S 29 , the timer BT is initialized, before being shifted to step S 21 . [0069] In the case of the determination of YES at step S 22 or NO at step S 26 , the processing is shifted to step S 30 , where it is determined whether or not the timer BT is in operation. If the determination is NO (not in operation), the processing at steps S 31 to S 33 is carried out in sequence. The timer BT is started to count the time (step S 31 ), the electromagnetic valve 29 is kept “off” (step S 32 ), and the LED 39 is kept “off” (step S 33 ). Then the processing is made to return to step S 21 . [0070] On the other hand, if it is determined “YES” at step S 30 , that is, it is found that the timer BT is in operation, the processing is shifted to step S 34 to further determine whether or not the count of the timer BT shows three seconds (i.e., a predetermined period of time) or more. If the determination at step S 34 is YES, i.e., a period of 3 seconds or more is counted, the processing is carried out such that the electromagnetic valve 29 is in its “off” state (step S 35 ) and the LED 39 is turned “on” (step S 36 ). The processing is then shifted to step S 37 to determine whether or not the operation switches 3 a and 3 b both are in their “off” states. If this determination is NO, this termination processing is repeated to wait for a situation where the operation switches 3 a and 3 b both become “off.” When both the switches 3 a and 3 b are released from being pushed (the determination at step S 37 is YES), the processing escapes from the repeated determinations at step S 37 . The CPU 30 returns the processing to step S 21 . [0071] When the determination at step S 34 is NO (i.e. a predetermined period of 3 seconds or more has yet to come), the processing at steps S 32 and S 33 is performed as described before. [0072] As a result of the foregoing processing, when either one of the operation switches 3 a and 3 b attached to the holder 13 is made “on” and its “on” state lasts for the predetermined period of time (e.g., 3 seconds in the present embodiment, but not limited to this period of time), the electromagnetic valve 29 becomes “off.” The arms 12 a - 12 c are therefore locked to not allow any moves thereof. At the same time, the LED 39 is turned “on” to notify the surgeon (i.e., operator) that the current operation toward the switches is improper. This locked state can be released only when the switches 3 a and 3 b both are made “off,” thanks to the processing at step S 37 in FIG. 7 . Third Embodiment [0073] Referring to FIGS. 8-10 , a third embodiment of the medical-device holding apparatus according to the present invention will now be described. [0074] As shown in FIG. 8 , a holder 204 , which holds endoscope 17 , is attached to the head-side arm 12 a via the ball joint 14 . To the holder 204 is attached an electric view-change driver 204 a which will be described later, which is in charge of changing an observing direction of the endoscope 17 by selectively moving it in the X-axis, Y-axis and Z-axis directions. The electric view-change driver 204 a is eclectically connected to a foot switch box 206 via a control box 205 . [0075] Using FIGS. 9 and 10 , the holder 204 , control box 205 , and foot switch box 206 will now be described. [0076] The control box 205 is provided with, in addition to the foregoing electromagnetic valve 29 , a switch detection circuit 207 and a motor control circuit 208 , wherein the switch detection circuit 207 is electrically connected to the electromagnetic valve 29 . Additionally, electrically connected to the switch detection circuit 207 are a joystick switch 209 and a drive switch 210 , which are equipped in the footswitch box 206 . The joystick switch 209 is provided with a four-way switch which operates to move the endoscope 17 in the upward, downward, and lateral directions. By way of example, the switch detection circuit 207 is functionally configured with the aid of the software processing carried out by a CPU, like the foregoing control box in the first embodiment. [0077] The holder 204 is provided with the foregoing first and second switches 18 and 19 and an LED 211 , which are electrically connected with the switch detection circuit 207 . The holder 204 is also provided with an X-axis motor 212 , Y-axis motor 213 , and Z-axis motor 214 , which are all electrically coupled with the motor control circuit 208 . Operator's operations at the joystick switch 209 allow the motor control circuit 208 to drive the X-, Y- and Z-axes motors 212 , 213 and 214 mounted in the holder 204 concurrently or selectively so that the view of the endoscope 17 can be moved in a controlled manner. [0078] The electric view-change driver 204 a is structured as schematically shown in FIG. 9 , in which there are provided with an X-axis housing 212 a , Y-axis housing 213 a , Z-axis housing 214 a . The X-axis housing 212 a is arranged to engage with an X-axis motor 212 with a motor shaft having a pinion gear 215 at one end thereof. This pinion gear 215 is engaged with an X-axis rack 215 a slidably formed on the X-axis housing 212 a in the X-axis direction. [0079] The Y-axis housing 213 a is mounted on the X-axis rack 215 a . The Y-axis housing 213 a is arranged to engage with a Y-axis motor 213 with a motor shaft having a pinion gear 216 at one end thereof. This pinion gear 216 is engaged with a Y-axis rack 216 a slidably formed on the Y-axis housing 213 a in the Y-axis direction. [0080] Moreover, the Z-axis housing 214 a is mounted on the Y-axis rack 216 a . The Z-axis housing 214 a is arranged to engage with a Z-axis motor 214 with a motor shaft having a pinion gear 217 at one end thereof. This pinion gear 217 is engaged with a Z-axis rack 217 a slidably formed on the Z-axis housing 214 a in the Z-axis direction. This Z-axis rack 217 a finally holds the endoscope 17 , as illustrated in FIG. 9 . [0081] Thus, a surgeon (operator) can grip the holder 204 to push down the first and second switches 18 and 19 , for example, by the thumb and first finger at the same tame or within a predetermined period of time. This push activates, with the aid of the switch detection circuit 207 , the electromagnetic valve 29 to release the fluid clutch of each joint from being clutched. In contradiction to this, in the remaining cases where the first and second switches 18 and 19 are not pushed down at the same time or within the predetermined period of time, unlike the above, the switch detection circuit 207 will not permit each joint to be released from being fixed. Of course, when only one of the two switches 18 and 19 is continuously made “on” the predetermined period of time (e.g., 3 seconds) or more, the switch detection circuit 207 will issue a signal to light up the LED 211 in order to inform the operator about the improper operation, which is similar to that in the second embodiment. [0082] This control for the operator's operations at the two switches 18 and 19 may be realized in the same or similar way as or to the processing based on the flowchart shown in FIG. 5 or 7 , which can be assigned to the control box 205 . [0083] The joystick switch 209 on the footswitch box 206 is operated to decide a direction, information indicative of the decided information being displayed on a monitor M as shown in FIG. 8 . After the decision of this direction, the drive switch 210 is turned “on,” so that the electric view-change driver 204 a is driven in response to this instruction. And as long as the joystick switch 209 is operated within a predetermined period of time (for example, 5 seconds) starting from the switch “on” of the drive switch 210 , that is, both the switches 209 and 210 are operated (“on”) within the predetermined period of time in the similar manner to the forgoing, the switch detection circuit 207 and motor control circuit 208 jointly operate to instruct the electric view-change driver 204 a to drive the X-, Y- and Z-axis motors 212 , 213 and 214 . [0084] However, in the case that only either one of the joystick switch 209 and drive switch 210 is operated (“on”) continuously the predetermined period of time or more, a signal from the switch detection circuit 207 will cause the LED 211 to light to inform an operator of this improper operation. Concurrently, the X-, Y- and Z-axes motors 212 - 214 in the electric view-change driver 204 a are locked not to be driven, whereby the view will be prohibited from being changed. [0085] This control for the operator's operations at both the joystick switch 209 and the drive switch 210 can also be performed in the same manners as above based on based on the flowchart shown in FIG. 5 or 7 , which can be assigned to the control box 205 . MODIFICATIONS [0086] FIG. 11 shows a modification of the third embodiment, wherein the holder 204 is provided with both the joystick switch 209 and drive switch 210 . Hence an operator can grip the holder 204 , during which time the operator operates both the switches 209 and 210 . In this modification, there is no necessity of employing the footswitch box 206 , thus simplifying the switch constructions. [0087] In addition, though the foregoing various embodiments have been described about the construction in which the endoscope serving as the medical device is employed, however, this is not a definitive list. Any other types of medical treatment devices can be used as a medical device, so that the similar advantages to the foregoing can be provided. [0088] In each of the foregoing embodiments, the polyarticular arm consisting of three joints has been described, but the number of joints is not confined to three. The polyarticular arm having a desired number of joints can be applied to the present invention to enjoy the foregoing advantages which are characteristic of the present invention. [0089] Although the description above contains many specificities, these should not be construed as limiting the scope of the invention but as merely providing illustrations of some of the presently preferred embodiments of the present invention. Thus the scope of the present invention should be determined by the appended claims. For example, in the third embodiment, the control for locking the electric view-change driver may be reduced in practice solely, separately from the control for lock and unlocking the polyarticular arm.
An apparatus for holding a medical device has an arm unit equipped with, for example, a polyarticular arm, which holds the medical device such as endoscope movably in the space. Additionally to a determination unit and a controller, the holding apparatus has an operation unit equipped with a plurality of operation members with which an operator's operation causes the arm unit to be moved spatially. The determination unit determines whether or not operator's operations at the plurality of operation members corresponds to an improper state deviating from a properly operated state in which at least two predetermined operation members have been operated within a predetermined period of time which is set to measure simultaneity for operations. If it is determined that the operation is in the improper state, the controller prohibits the arm unit from moving. As long as the operation is proper, the arm unit can be moved.
0
CROSS-REFERENCES TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application No. 60/726,498, filed Oct. 12, 2005, and U.S. Provisional Application No. 60/778,004, filed Feb. 28, 2006, the contents of which are incorporated by reference herein and made a part of this application. FIELD OF THE INVENTION [0002] The present invention relates generally to submersible vehicles, and particularly to unmanned autonomous submarines, and sometimes referred to as “small” submarines. BACKGROUND OF THE INVENTION [0003] There have been numerous unmanned submarines designed to explore or perform other underwater tasks and functions, as required. The submersible vehicle (i.e., a submarine) includes various systems, such as a ballast system for submersing or floating the submarine, a propulsion system for propelling the submarine, a navigation or steering system for maneuvering the submarine, and various sensors and controllers for controlling the submarine and providing information regarding the underwater environment. [0004] For example, U.S. Pat. Nos. 1,571,833, 5,235,930, 5,711,244, and 6,655,313 disclose a submarine body from separate sections that are joined together and include seals. U.S. Pat. Nos. 1,310,877, 1,488,067, 3,379,156, 3,478,711, 3,667,415, 3,800,722, 3,818,523, 3,943,869, 3,946,685, 4,029,034, 4,265,500, 5,129,348, 6,371,041 and 6,772,705 disclose ballast means combining water and air through a system of valves and piping for controlling the depth direction of a submarine. U.S. Pat. Nos. 3,122,121, 3,176,648, 3,474,750, 3,492,965, 3,550,386, 6,065,418, 6,807,921 and 6,581,537 disclose fluid propulsion of a vessel through the handling of the fluid from the bow to the stem of the vessel. U.S. Pat. Nos. 3,561,387, 6,269,763, 6,484,660, 6,662,742 and U.S. Publication No. 2002/0134294 disclose use of a plurality of sensors and structural concepts and relate generally to the state of the art. U.S. Pat. Nos. 6,926,567, 6,800,003, 6,716,075, 6,629,866, 6,453,835, 3,301,132, 340,237, U.S. Patent Publication No. 2001/0010987 and Japanese Pat. Application No. 356071694 relate to fluid deflection. [0005] None of the known patents or publications disclose or suggest an unmanned autonomous submarine as disclosed and claimed herein. SUMMARY OF THE INVENTION [0006] In general, it is an object of the present invention to provide an unmanned autonomous small size submarine as described herein. This submarine is a surface/underwater vehicle which can float, dive and move in water to perform various tasks. One important feature of the submarine is the pressurized cabin which is necessary for the diving and flotation system to work properly. This also helps to increase its sealing power against water leakage into the cabin. The submarine is autonomous, that is, automatic and self controlled. It is propelled by water jet propulsion. It can be programmed to dive to preset depths, move along preset trajectories, and return to the base after completing the assigned tasks. In addition to the autonomous part, a remote control option is provided for emergency situations or in order to perform special tasks. The submarine is equipped with several sensors that can measure depth, orientation, attitude, location and speed. It is also equipped with an underwater video camera that can send wireless video pictures from underwater to a monitor above water surface. [0007] Various objectives of the unmanned autonomous submarine are to perform several tasks above and under water replacing human divers who can be subjected to danger in such environment; minimize the cost of underwater operations such as exploration, rescue, photography, and inspection of submerged structures, such as ship hulls, oil rigs, dams, etc.; monitor various objects under water and transmit live video and pictures to the operator on board of a commanding boat above water; be used as a carrier and base for underwater robotics, among other undersea functions and tasks. [0008] In one embodiment, the unmanned autonomous submarine comprises a hull formed by at least two hull sections and defining an interior cabin therein and adapted to retain pressurized air. A plurality of fasteners are affixed to the hull sections and adapted for joining the at least two hull sections. The plurality of fasteners can e internally and/or externally affixed to opposing connecting ends of the hull sections. [0009] A plurality of hydrofoils is attached to opposed external side surfaces of the hull sections for providing stability and maneuverability of the hull. The submarine further includes a propulsion system for providing propelling force to the hull. [0010] A ballast system is included for raising and submersing the hull. The ballast system comprises a ballast tank adapted to receive a predetermined level of water externally from the submarine and a predetermined amount of the pressurized air from the cabin; and a compressor coupled to the ballast tank to form a closed loop system. The compressor is adapted to force air into the cabin from the ballast tank to increase the water level in the tank and thereby cause the hull to submerge, and the compressor being adapted to force air into the ballast tank from the cabin to decrease the water level in the tank and thereby cause the submarine to ascend. [0011] In one embodiment, the submarine includes a sealable opening formed in the upper portion of one of the hull sections. The sealable opening provides access into the interior cabin. [0012] In one embodiment, the plurality of fasteners includes a plurality of clamps. Alternatively, the plurality of fasteners can include a plurality of bolts positioned on one of the connecting ends of a hull section and threaded into a corresponding plurality of nuts affixed to an opposing connecting end of an adjacent hull section. [0013] In one embodiment, the submarine further comprises an o-ring inserted between each adjacent hull section. In an alternative embodiment, the submarine includes a reinforcing ring inserted between each adjacent hull section, either with or without the o-ring. [0014] In one embodiment, the ballast tank comprises a plurality of partitions to prevent water in the tank from destabilizing the submarine. Further, the ballast tank can include a sealable opening formed at its bottom for controlling flow of water in or out of the tank. Additionally, the ballast system can include at least one solenoid valve for controlling air flow between the cabin and the ballast tank. [0015] In one embodiment, the propulsion system includes a first water pump positioned in the cabin, a forward inlet port formed in a forward hull section of the hull sections and coupled to the pump via a first conduit, and an aft outlet port formed in an aft hull section of the hull sections and coupled to an output of the first pump via an aft conduit. The first pump draws water external to the hull through the forward inlet port and first conduit, and forces the water through the aft outlet port to propel the submarine in a forward direction. Alternatively, the first water pump draws water external of the hull through the aft outlet port and the aft conduit, and forces the water through the forward inlet port to propel the submarine in a reverse direction. [0016] The propulsion system can further include a second aft outlet port formed in the aft hull section and coupled to the first pump via a second aft conduit. The aft conduits are regulated to control water flow therethrough to provide steering of the submarine. [0017] In another embodiment of the propulsion system, a second water pump is serially coupled to the first water pump. The second water pump is deactivated while the first pump is activated to propel the submarine in the forward direction. Similarly, the first pump is deactivated while the second pump is activated to draw water external to the hull through the aft outlet port and aft conduit, and force the water out of the forward inlet port to propel the submarine in a reverse direction. [0018] In yet another embodiment of the submarine, a plate is pivotably attached in a vertical direction in the aft outlet port. The vertically positioned plate is rotatable to direct the water jetted out of the aft outlet port at a predetermined angle to steer the submarine. Preferably, a vertical rudder rotatable attached to the aft hull section, and a link coupled between the rudder and vertical plate. Rotation of the plate is controlled by rotation of the rudder. [0019] In yet another embodiment of the propulsion system, the propulsion system includes a forward water pump positioned in the cabin, a forward inlet port formed in a forward hull section of the hull sections and coupled to the forward pump via a forward conduit, and a pair of parallel water pumps positioned in the cabin. The parallel pumps are coupled to the forward water pump via a Y-shaped conduit. A pair of aft outlet ports is formed in an aft hull section of the hull sections. Each aft outlet port is coupled to a corresponding one of the parallel water pumps via a second conduit. [0020] At least one of the parallel water pumps draws water external to the hull through the forward inlet port and forward conduit, and forces the water out of the corresponding aft outlet port to propel the submarine in a substantially forward direction. Preferably, the forward water pump is deactivated when the pair of parallel water pumps is activated to propel the submarine in a substantially forward direction. Alternatively, the pair of parallel pumps can be deactivated while the forward pump is activated to draw water external to the hull through the aft outlet ports and Y-shaped conduit, and force the water out of the forward inlet port to propel the submarine in a reverse direction. [0021] In another embodiment, the pumps can be utilized to steer the submarine. In particular one of the parallel pumps is either throttled back or deactivated while the other parallel pump is activated to steer the submarine in a predetermined direction. [0022] In one embodiment, the submarine further includes a vertical rudder rotatably attached to the aft hull section of the hull sections for steering the submarine. Further, the plurality of hydrofoils can include a pair of aft hydrofoils rotatably attached to opposing side surfaces of an aft hull section of the hull sections. The rotatably attached hydrofoils enable the submarine to submerge and ascend. Additionally, the plurality of hydrofoils can include a pair of forward hydrofoils fixedly attached to the opposing side surfaces proximate a forward hull section of the hull sections. The fixedly attached hydrofoils provide stability for the submarine. Alternatively, the pair of forward hydrofoils is rotatably attached to the opposing side surfaces proximate a forward hull section of the hull sections. The rotatably attached hydrofoils enable the submarine to submerge and ascend. [0023] In one embodiment, the hull sections include a forward hull section, an aft hull section, and a middle hull section attached therebetween the forward and aft hull sections via the plurality of fasteners. [0024] In yet another embodiment of the propulsion system, the propulsion system includes a pair of forward inlet ports formed in a forward hull section of the hull sections, and a pair of parallel water pumps positioned in the cabin. Each parallel pump is coupled to a corresponding one of the pair of forward inlet ports via a forward conduit. A pair of aft outlet ports is formed in an aft hull section of the hull sections, where each aft outlet port is coupled to a corresponding output of one of the parallel water pumps via an aft conduit. At least one of the parallel water pumps draws water external of the hull through the corresponding forward inlet port and forward conduit, and forces the water out of the corresponding aft outlet port to propel and steer the submarine in a substantially forward direction. Alternatively, at least one of the parallel water pumps draws water external to the hull through the corresponding aft outlet port and aft conduit, and forces the water out of the corresponding forward inlet port to propel and steer the submarine in a substantially reverse direction. [0025] In any of the aforementioned embodiments, the submarine can further include a programmable controller for controlling operations of the submarine. Additionally, one or more sensors can be installed on the submarine for providing electrical signals to the controller for further controlling the submarine operations. The one or more sensors can include depth sensors, GPS system sensors, pressure sensors, position and orientation sensors, speed sensors, leakage sensors, audio sensors and video sensors, among other sensors. Further, at least one robotic arm can be mounted to the hull and electrically coupled to the controller. [0026] In any of the aforementioned embodiments, the submarine can further include at least one battery for providing power to the submarine. In one embodiment, the at least one battery is rechargeable. Further, an array of photovoltaic cells can be mounted to the exterior surface of the hull. The array of photovoltaic cells can be used to provide charge to the rechargeable batteries or provide power to the one or more systems in the submarine. [0027] In one embodiment, the submarine includes a receiver for receiving remote command signals to control operations of the submarine. Further, a transmitter can be provided for sending operational information to a remotely located receiver. [0028] Additional features and advantages of the invention will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the invention as described herein, including the detailed description which follows, the claims, as well as the appended drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0029] FIG. 1 is an enlarged front top perspective view of an embodiment of an unmanned autonomous submarine according to the present invention having a plurality of hull sections according to one embodiment of the invention; [0030] FIG. 2 is a front and top perspective view of the unmanned autonomous submarine of FIG. 1 having the hull sections assembled by a plurality of internal clasps; [0031] FIG. 3 is a front and top perspective view of the unmanned autonomous submarine of FIG. 1 having the hull sections assembled by a plurality of external clasps; [0032] FIG. 4 is a side perspective view of a plurality of reinforcing rings for coupling the hull sections of FIG. 1 ; [0033] FIG. 5 is schematic diagram of the reinforcing rings of FIG. 4 ; [0034] FIG. 6 is a graphical view illustrating the depth and maximum tangential component of stress affecting the submarine of FIG. 1 ; [0035] FIG. 7 is a schematic diagram of a pneumatic circuit for effecting the ascend and descend of the submarine of FIG. 1 in a water environment; [0036] FIG. 8 is a schematic diagram of a first embodiment of a propulsion system of the submarine of FIG. 1 ; [0037] FIG. 9 is an external perspective view of a front port of the propulsion system of FIG. 8 formed in the forward hull section of the submarine of FIG. 1 ; [0038] FIG. 10 is an internal perspective view of the front port of the propulsion system of FIG. 8 , formed in the forward hull section of the submarine of FIG. 1 ; [0039] FIG. 11 is an external perspective view of a rear port of the propulsion system of FIG. 8 , formed in the aft hull section of the submarine of FIG. 1 ; [0040] FIG. 12 is an internal perspective view of the rear port of the propulsion system of FIG. 8 , formed in the aft hull section of the submarine of FIG. 1 ; [0041] FIG. 13 is a top plan view illustrating the rudder, stabilizers and elevators of a maneuvering system of the submarine of FIG. 1 ; [0042] FIG. 14 is a side view of the maneuvering system of the submarine of FIG. 1 ; [0043] FIG. 15 is a front and top perspective view of the maneuvering system of the submarine of FIG. 1 ; [0044] FIG. 16 is a front and top perspective view of one of the side elevators of the maneuvering system of FIGS. 13-15 ; [0045] FIG. 17 is a cross-sectional view of the hydrofoil of FIG. 16 illustrating the flow of water about the elevator; [0046] FIGS. 18 A-C are respective side views of the aft hull section illustrating various maneuvering positions of the elevators of the submarine of FIG. 1 ; [0047] FIG. 19 is a side view of the aft hull section having a thrust vector system for steering the submarine of FIG. 1 ; [0048] FIG. 20 is a cross-sectional view of the aft hull section and thrust vector system of FIG. 19 ; [0049] FIG. 21 is a top side perspective view of the thrust vector system of FIGS. 19 and 20 ; [0050] FIG. 22 is a rear and top perspective view of the aft hull section and thrust vector system of FIG. 19 ; [0051] FIG. 23 is a schematic diagram illustrating maneuvering the submarine of FIG. 1 using the propulsion system and thrust vector system of FIGS. 8-12 and 19 - 22 , respectively; [0052] FIG. 24 is a schematic diagram of an alternative embodiment of a propulsion system suitable for use in the submarine of FIG. 1 ; [0053] FIG. 25 is a front top perspective view of the unmanned autonomous submarine of FIG. 1 having a plurality of photovoltaic cells installed on the exterior surface of the hull; and [0054] FIG. 26 is a schematic diagram of a controller and sensor array for controlling the unmanned autonomous submarine of FIG. 1 . [0055] To facilitate understanding of the invention, the same reference numerals have been used when appropriate, to designate the same or similar elements that are common to the figures. Further, unless stated otherwise, the drawings shown and discussed in the figures are not drawn to scale, but are shown for illustrative purposes only. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0056] Reference will now be made to the preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings FIGS. 1-26 . An exemplary embodiment of an unmanned autonomous submarine of the present invention is shown in FIG. 1 , and is designated generally throughout by reference numeral 100 . [0057] Hull Configuration [0058] Referring to FIGS. 1 and 2 , there is depicted in an enlarged view, with components separated for convenience of illustration, of a submarine hull 102 having a forward hull section 104 , a middle hull section 106 , and an aft ward hull section 108 . The preferred shape of the hull 102 is a slender axi-symmetric body of revolution, where the length is larger than the maximum diameter of the submarine. For example, in one embodiment, the hull 102 of the submarine is 1.645 m long, with a maximum outside diameter of 40 centimeters, although such dimensions are not considered limiting. [0059] Several alternative configurations of the hull (body) 102 of the submarine 100 are possible within the scope of the invention. The submarine 100 can be assembled from two, three, or more hull sections with appropriate sealing devices 120 . The most structurally efficient hull shape of the submarine is a circular cross-section. A hull 102 having a substantially circular cross-section is easy to fabricate and is streamlined for maximum drag reduction. The shape of the hull 102 is not limited to being circular, as other hull section shapes can be utilized to satisfy particular applications or purposes by the submarine 100 . [0060] In one embodiment as shown in FIGS. 1 and 2 , the forward or nose section 104 is a hemisphere, and the aft or rear tail section 108 is a semi-ellipsoid of revolution. The hull sections 102 of the submarine can be fabricated by welding or otherwise fastening together sheet metal strips (e.g. 3 mm thick steel sheets). Alternatively, the hull sections can also be cast from any suitable material. For example, the hull sections 102 of the submarine can be made from steel, fiberglass, among other well known materials and/or a combination thereof which are capable of withstanding the water pressure when submersed at particular depths. [0061] In the embodiment shown in FIGS. 1 and 2 , an opening 110 is formed in the upper side of one of the body sections (preferably the middle hull section 106 ) with a removable cover 112 . The opening 110 is provided for access to the cabin 140 during assembly and servicing of the submarine 100 . The removable cover 112 is provided to seal and protect the interior of cabin 140 of the submarine 100 from the external water environment. Additionally, as discussed in further detail with respect to FIG. 2 , the opening 110 facilitates assembly of the hull sections 108 using internal clamps 116 . Further, although not shown in FIGS. 1-3 , the hull 102 includes a number of fixed or rotatable lifting and steering surfaces preferably made from hydrofoils which provide stability and control (i.e., maneuverability) during operation of the submarine 100 , as is discussed below in further detail with respect to FIGS. 13-19 . [0062] Referring to FIGS. 2 and 3 , the hull sections 102 of the submarine 100 are shown assembled together and secured by internal or external clamps. Referring to FIG. 2 , internal clamps 116 are preferably used, since they do not create any resistance to the submarine motion while submersed in the water and thus produce a smooth continuous surface. The open ends of the forward hull 104 and aft hull 108 sections include circular end ring portions 118 having a diameter substantially equal to the diameter of the middle hull section 106 , to thereby provide a continuous smooth exterior surface where the hull sections are secured together. All three hull sections are joined together within the interior of the submarine by suitable fasteners 116 , such as with spring clamps 116 for quick and easy assembly, or a number of bolt/nut combinations. [0063] In an embodiment implementing a bolt/nut combination, a plurality of bolts are provided on one ring (e.g., on rings 120 formed on opposing ends of the middle hull section 106 ), and each bolt is inserted through thick washers welded to the same ring 120 . The bolts are threaded into mating nuts welded to a second mating ring, for example, circular end rings 118 formed on the forward and aft hull sections. An O-ring 130 is located between each two mating parts of the hull sections 102 in order to provide sealing power against water leakage. The bolts and internal clamps 116 are accessed during assembly through the central body opening 110 . [0064] Referring to FIG. 3 , in an alternative embodiment, the submarine body 102 is assembled by using external clamps 122 . The external clamps 122 are provide easy assembly of the hull sections 102 . [0065] Referring to FIGS. 4 and 5 , the three hull sections 104 , 106 and 108 are joined together and assembled using O-rings 130 , such as rubber O-rings 132 for providing a watertight seal between the joined hull sections lO 2 . The O-rings 130 can optionally include steel reinforcement rings 134 to form a combined steel and rubber reinforcing/coupling O-ring. The steel/rubber O-rings serve as couplers between the hull sections, as well as stiffeners because they increase the rigidity and integrity of the body of the submarine against wrinkling and deformation. [0066] Referring to the graph 600 of FIG. 6 , the relationship between the outside pressure at a certain depth and the maximum tangential component of stress affecting the inner radius of the cylindrical middle hull section 106 of the submarine's hull 102 is shown. Depths from 10 to 50 meters below sea level are considered. Typically, the weakest part of the submarine's hull 102 is the middle cylindrical hull section 106 , as the other elliptical hull sections 104 and 108 of the submarine's hull 102 are not subject to the same levels of radial and tangential stresses. [0067] The average value of axial stress affecting the body of the submarine (for example, a wall thickness of 3 mm) at a depth of 50 meters (corresponding to an external pressure of 5 bars), was observed to be equal to approximately 13.4 MPa (MegaPascals), while the internal cabin pressure in the submarine was approximately equal to 1 bar. [0068] The maximum value of the tangential stress affecting the submarine's cylindrical middle hull section 106 of the hull 102 can be found at the inner radius, and these values are much larger than those of the radial stresses affecting the submarine. [0069] Referring now to FIG. 6 , it can be seen from the graph 600 that as the depth of the submarine increases, the tangential component of stress increases in compression. Comparing the stress to the yield strength (210 MPa) of steel (SAE 1020) used in building the hull of the submarine, it was found that the submarine's hull 102 can handle external pressures of 32 bars (i.e., corresponding to depth of approximately 320 meters). [0070] Ballast System [0071] Referring again to FIG. 1 , the cabin 140 of the submarine is pressurized with air all the time during operation in water. This pressurization is necessary for the proper functioning of the diving and floatation system (ballast system), especially during surfacing of the submarine. Due to the design of the ballast system 700 , low values of gage pressures are necessary (less than 5 bars). This low pressure is sufficient for the operation of the ballast system even for maximum design operating depths for the submarine 100 under water where pressures are much higher. Cabin pressurization can be provided by either an external air pressure source (e.g., an air compressor or a pressure cylinder), or by operating the submarine compressor (i.e., in the ballast tank system) for a predetermined time prior to the submarine being placed in the water (i.e., when the ballast tank is empty, air is sucked from the atmosphere to the cabin 140 through the ballast tank). This pressurization increases the submarine strength and joint resistance against water leakage into cabin 140 . [0072] Referring to FIG. 7 , the diving and floatation (ballast) system 700 includes a ballast tank 702 , a reciprocating air compressor 714 , a plurality of solenoid valves 711 and 715 , at least one check valve 722 , and piping for transferring air between the compressor 714 and ballast tank 702 . In one embodiment, the ballast tank 702 is cylindrical in shape and is installed on the bottom of the inside wall in the middle cylindrical hull section 106 of the submarine 100 . In one embodiment, the tank 702 has a convex cover which causes air inside it to accumulate and go through the air outlet 708 . The tank 702 contains several partitions (baffles) which restrict the motion of water to prevent the water in the tank from destabilizing the submarine. The tank has a small opening 706 at its bottom for water to flow into or out of the tank 702 . [0073] In one embodiment as shown in FIG. 7 , a sealed box, located above the ballast tank 702 , contains the reciprocating air compressor 714 . The compressor 714 removes air from the enclosed space around it through an opening in the box's wall. The removed air can come from the top of the ballast tank 702 through a one-way valve 708 and a water trap, and pumps it to cabin 140 when the submarine is submersing. The same compressor 714 can be used to pump air from the pressurized cabin 140 back to the ballast tank 702 in order to force water out of the tank during the surfacing operation. The solenoid valves are used to accomplish these two processes. The solenoid valves form part of the pneumatic circuit 700 , which control the air flow in a manner which will cause either diving or surfacing of the submarine. [0074] In particular, the submarine 100 is designed to be floating when initially placed in water. Referring to schematic diagram of FIG. 7 , the ballast tank 702 is flooded with water through a water opening 706 in the bottom 704 of the tank 702 by sucking air from the tank through the tank's air outlet 708 (water trap). The air from the tank flows through port 710 , through port 712 , then through the compressor 714 , then through port 716 , and through port 718 into the cabin 140 of the submarine 100 . The air removed from the tank 702 is pressurized and stored in the cabin 140 of the submarine 100 for usage during a reverse operation to force the water out of the tank 702 . The removal of air from the tank 702 creates low pressure inside the tank's body 702 , which in turn causes water to flow therein, thereby enabling the submarine 100 to gain mass and submerge in the water. [0075] During the surfacing or ascending operations of the submarine 100 , the air compressor 714 is operated along with the actuation of the two solenoid valves 711 and 715 , such that air is removed from the cabin 140 through port 713 , port 712 , through the air compressor 714 , through port 716 , through port 717 , through a check valve (non return valve) 722 , and then through the tank's air inlet 724 into the tank's body 702 . This operation causes air to be pressurized back into the tank 702 , thus creating high pressure therein the tank, which in turn causes the discharge of water through the tank's water opening 706 to reduce the mass of the submarine and cause it to ascend and/or float. [0076] In order to provide enough air for the surfacing operation, the interior of the submarine's body (i.e., cabin 140 ) is pressurized with air before any operation is started. Another advantage of the pressurization with air is that this technique increases the sealing power and the resistance against water leakage into the submarine's cabin 140 . [0077] Propulsion System [0078] Referring to FIGS. 8-12 , propulsion of the submarine 100 is provided by a propulsion system 800 having least one water pump 802 . The system 800 provides forward motion to the submarine by sucking water from a first opening or port 804 in the forward hull section 104 , and pumping water from a second opening or port 806 formed in the tail hull section 108 of the submarine. The emerging jet would provide the force needed for the submarine to move. [0079] In one embodiment, a DC-motor-operated water pump 802 , located inside the submarine, sucks water from a front opening 804 in the nose 104 of the submarine via a first pipe 810 and ejects it from another opening in the far end of the tail 108 via a second pipe 812 . [0080] Stopping the submarine (while in forward motion) and giving it a backward motion is achieved using the same system as in described above but with a reverse water flow. This can be done by several means: (a) connecting another identical pump with the first pump back to back and operating the second pump only for the backward motion; (b) using a flow reversal water circuit with solenoid valves and pipe connections; or (c) having a parallel system to the first one but with a reversed flow direction. [0081] Referring to the embodiment of FIG. 8 , the propulsion system 800 includes two pumps 814 and 816 that are used to provide forward and backward motion of the submarine 100 . In order for the submarine 100 to move in the forward direction, the first pump 814 is activated to suck water from the front water opening 804 via pipe 810 and pump the water through the second pump 816 and out of the rear water opening 806 via pipe 812 , which provides sufficient thrust for the submarine 100 to move in the forward direction. To propel the submarine in the reverse direction, the second pump 816 is activated to suck water from the rear water opening 806 through the first pump 814 via pipe 812 , and out of the front water opening 804 via pipe 810 . This reverse operation provides the submarine 100 with sufficient thrust to reduce and stop the forward motion, and then propel the submarine 100 in the reverse direction. [0082] Maneuvering System [0083] Referring to FIGS. 13-15 , maneuvering of the submarine 100 is achieved by the use of a plurality of stabilizing fins 1302 , elevators 1304 , a rudder 1306 , and by water jet thrust vectoring, as described below in further detail. A pair of horizontal stabilizing fins 1302 is attached to opposing sides of the middle hull section 106 , and act as stabilizers to prevent the submarine 100 against rolling. In one embodiment, the fixed stabilizers 1302 are fixedly welded to the body of the submarine and do not move. [0084] A pair of rear elevator fins 1304 is rotatably attached to opposing sides of the aft hull section 108 . The rear elevator fms 1304 assist with maneuvering the submarine and controlling its motion, as well as providing depth stability to the submarine. The rudder 1306 is vertically attached to the aft hull section 108 of the submarine. The rudder 1306 is responsible for steering the submarine 100 in a sideways direction (e.g., left and right). One skilled in the art will appreciate that the forward horizontal pair of stabilizing fins 1302 can also be rotatably attached to the sides of the middle hull section 106 to provide additional maneuverability. [0085] The installation of the rotatable hydrofoil fms 1302 , 1304 and rudder 1306 creates three weak points which are susceptible to water leakage. Leakage problems at these points are solved using special sealing units. These seals provide a resilient, watertight opening for enabling the rotational motion of the hydrofoil fins and rudder in addition to preventing water leakage. [0086] Referring to FIGS. 13-17 , the elevators 1304 , stabilizing fins 1302 , and rudder 1306 are formed, for example, by symmetric hydrofoil sections in order to reduce drag and enable the submarine to ascend (float) and submerge (dive) in the water environment during operation. Referring to FIG. 17 , a circular shaft 1702 is provided at one end of the hydrofoil for attachment to a motorized gear box (not shown) for rotating the hydrofoil, as required. [0087] In one embodiment, the elevators 1304 and rudder 1306 are actuated by two DC motors; one for the elevators and the other for the rudder. In order to rotate the rudder 1306 , the motor is linked to the rudder via a friction disk. The disk is attached to a small shaft that is fixed to the rudder itself. The elevators are actuated by the second DC motor. In order to actuate both elevators at the same time, a power screw is linked to the motor. A nut near the other end of the power screw is then attached to a link which connects the elevators 1304 . Preferably, the elevators 1304 can move between −45 and +45 degrees as illustratively shown in FIGS. 18 A-C, although such range of movement is not considered limiting. [0088] Referring to FIGS. 19 and 20 , in one embodiment, a thrust vectoring mechanism 1900 is installed proximate the second port 806 of the propulsion system which is provided at the rear hull section 108 . The thrust vectoring mechanism 1900 is provided to operate along with the rudder 1306 to assist with steering of the submarine 100 . [0089] Referring to FIGS. 21 and 22 , the thrust vectoring mechanism 1900 includes a link member 1902 that moves a vertical circular plate 1904 , which is installed inside the rear port 806 of the propulsion system. The link 1902 is moved and actuated by the rudder 1306 with minimal motion delay. The small plate 1904 controls the angle at which the water jet leaves the rear port 806 of the submarine 100 , which causes the submarine 100 to change its direction of motion. [0090] Referring to FIG. 23 , there are three possible directions for the water jet to leave the rear port 806 of the submarine 100 . If the water jet exits the rear port 806 along direction 2302 , then the submarine is propelled to the right. If the water jet exits the rear port 806 along direction 2304 , then the submarine is propelled in a straightforward path. Alternatively, if the water jet exits the rear port 806 along direction 2306 , then the submarine is propelled to the left. [0091] FIG. 24 illustrates another embodiment for supporting (or replacing) the rudder 1306 in steering the submarine 100 . In particular, two parallel pumps 2402 are provided, illustratively in the rear hull 108 to propel and steer the submarine 100 , instead of using only one pump as described above with respect to the embodiment of FIGS. 8-12 and 23 . A third forward pump 2404 is located in the forward hull section 104 . The third forward pump 2404 is activated when stopping the submarine or backward motion is desired. [0092] In particular, the forward pump 2404 is connected between the front opening 804 formed in the forward hull section 104 and a Y-connection 2406 that is coupled to a pair of main pipes 2408 , which transfer water from the front opening 804 to the rear parallel pumps 2404 . Each of the pair of pumps 2404 is coupled by a conduit 2412 to a corresponding rear port 2410 formed at the aft hull section 108 . [0093] As shown in FIG. 24 , water enters the submarine 100 from the front opening 804 and into the Y-connection 2406 which splits the flow into two parts delivered to two parallel pumps 2402 . The parallel pumps 2402 operate to force water out of the submarine through two rear ports 2410 to propel the submarine in a forward straight direction. Steering of the submarine can be effected by operating one of the parallel pumps 2402 while shutting down the other, which causes the water jet from the corresponding rear port 2410 to change the direction of the submarine 100 . One advantage of the parallel pump propulsion system 2400 of FIG. 24 is that the thrust vectoring mechanism 1900 is not required, thereby eliminating any possible damage to the links 1902 and 1904 caused by unknown objects (e.g., rocks), which might occur while moving underwater. [0094] In an alternative embodiment, the submarine steering system includes two openings in the tail of the submarine separated by an appropriate distance and on both sides of the first central opening. The two emerging water jets are not parallel but they meet at a point downstream from the tail end of the submarine. Allowing more water to flow in one of these side openings than the other will cause the submarine to turn right or left as desired. One or two water pumps can be used for this configuration. [0095] In the one-pump system, the output of the pump is branched into two pipes to the two openings in the back of the submarine. The flow rate of water in each branch can be controlled via throttling valves. Alternatively, in the two-pump system, two identical water-jet pump systems are installed parallel to each other. The nose of the submarine can have either a common opening or two openings. The flow rate in each branch can be controlled by the voltage supplied to each pump, or alternatively by throttling one branch for a short time to cause a turning moment on the submarine. [0096] Control and Power Systems [0097] Referring to FIG. 26 , an illustrative controller 2600 is provided to control the submarine 100 such that it is completely autonomous. The controller 2600 includes a microprocessor 2602 , support circuitry 2604 , memory 2606 a plurality of sensors 2608 and one or more bus lines (conductors) for providing electrical signals therebetween. In one embodiment, a (Motorola 68HC11A8) microcontroller is chosen to serve as the main control unit of the submarine. The microcontroller utilizes programs and routines stored in memory 2606 to control the submarine and translate the electrical signals from the various sensors 1608 into electrical signals delivered to the various actuators of the submarine's systems. [0098] The microcontroller 2602 can be programmed with special programs that enable the submarine 100 to perform various special tasks. The programs can set certain trajectories for the submarine to follow during its motion. For example, the microcontroller 2602 can be programmed to guide the submarine 100 around a docked ship and inspect the submerged part of its hull. The microcontroller 2602 can also be programmed to direct the submarine 100 to cruise while submerged in the water to search for one or more objects and then surface after finding the object. During its operation, the sensors 2608 enable the submarine to detect obstacles and decide for itself whether to stop, pull back or change its direction of motion to avoid collision. [0099] The support circuitry 2604 can include power supplies, logic circuitry, cache, I/O circuitry, among other conventional support circuits. The memory 2606 can be cache memory, RAM, ROM, programmable memory, and can be apart from and/or integrated with the microcontroller 2602 . [0100] The plurality of sensors 2608 are used to sense the environment and the physical properties surrounding the submarine 100 , such as the surrounding water pressure, and to convert these quantities into electrical signals that can be used by the control media of the submarine 100 to decide a sequence of operation according to the inputs. [0101] The sensors 2608 that can be used and installed in the submarine can include SONAR sensors, used for obstacle detection and for scanning the seabed; a pressure transducer, used for depth measurement; speed measurement sensors; as well as a GPS system, to keep track of the submarine's location; an attitude sensor which keeps track of the direction of motion. [0102] In addition, a video camera and audio equipment can be attached to the submarine 100 to transmit images and sounds to the operator at the surface. The video camera can further be used for control purposes by linking it to the controller 2600 of the submarine, and using some image processing principles. [0103] Further, the submarine can be programmed to perform more specialized tasks by installing additional special links and equipment, such as a manipulator (robotic) arm, which can be used for gathering samples for research and for retrieval of sunken objects; laser sensors for detecting faults and cracks in underwater structures like dams, bases of oil rigs, and underwater pipes and cables; special equipment for detecting faults in submerged parts of ship hulls at seaports; underwater welding equipment, among other specialized devices and equipment suitable for underwater operations. [0104] In order to increase the reliability of the submarine, a remote control (RC) system 2612 is installed in the submarine 100 . The remote control system 2612 includes at least a receiver, and preferably a transmitter and receiver (transceiver) 2614 that enables the operator to override one or more programs of the controller 2260 to take full control of the submarine, for example, in the case of emergency situations. [0105] The receiver 2614 of the RC system 2612 is installed inside the submarine 100 with an insulated antenna 2616 sticking out of the hull 102 . Furthermore, the antenna 2616 can be linked to a floating antenna by a reeling wire in order to guarantee that the signal transmission can not be interrupted as the submarine dives deeper and deeper due to the dispersion of electromagnetic waves in water. [0106] Source of Power: [0107] In one embodiment, the submarine includes a plurality of batteries as the main power source of the submarine. In one embodiment, the batteries include a set of several 12-Volt sealed lead acid rechargeable batteries. These batteries can provide enough power for the systems of the submarine for reasonably long missions. If more power is needed for lengthy missions, special Lithium batteries can be used which can provide more power for such missions. [0108] Referring to FIG. 25 , in one embodiment, photovoltaic cells 2502 are provided to recharge the batteries during the floating period of the submarine 100 , and thus make the submarine more independent for long missions. The photovoltaic cells 2502 are used in a sealed panel that cover the top surface of middle hull section 106 of the submarine. Additional photovoltaic cells 2502 can be installed on the forward and aft hull sections 104 and 106 as well. The photovoltaic cells 2502 can charge the batteries or run the various power components in the submarine during daytime when the sun is shining even when it is diving at shallow depths. [0109] It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention that come within the scope of the appended claims and their equivalents.
An unmanned autonomous submarine which can float, dive and move in water to perform various tasks. The submarine includes a pressurized cabin which is necessary for the diving and flotation system to work properly. This also helps to increase its sealing power against water leakage into the cabin. The submarine is autonomous, that is automatic and self controlled. It is propelled by water jet propulsion. It can be programmed to dive to preset depths, move along preset trajectories, and return to the base after completing the assigned tasks. A remote control option is provided in order to perform special tasks. The submarine is equipped with several sensors that can measure depth, orientation, attitude, location and speed. It is also equipped with an underwater video camera that can send wireless video pictures from underwater to a monitor above water surface.
1
BACKGROUND OF THE INVENTION Method and device for the homogeneous heating of glass and/or glass-ceramic articles using infrared radiation. The invention relates to a process for the homogeneous heating of semi-transparent and/or transparent glass articles and/or of glass-ceramic articles with the aid of infrared radiation, whereby the glass articles and/or the glass-ceramic articles undergo a heat treatment in the range from 20° C. to 3000° C., as well as to a device for the homogeneous heating of translucent and/or transparent glass articles and/or glass-ceramic. Semi-transparent or transparent glass and/or glass-ceramics, for the setting-in of certain material properties, for example ceramization, are heated mostly to temperatures which lie preferably over the lower cooling point (viscosity Z=10 14.5 dPas). In form-giving processes, especially hot after-processing, the semi-transparent or transparent glass and/or the glass-ceramic material is heated up to the processing point (viscosity Z=10 4 dPas) or beyond that. Typical lower cooling points can amount, depending on the type of glass, to between 282° C. and 790° C., and typically the processing point can be up to 1705° C. Hitherto according to the state of the art semi-transparent or transparent glasses and/or glass-ceramics, for example for ceramization, were heated preferably with surface heating. As surface heating there are designated processes in which at least 50% of the total heat output of the heat source is introduced into the surface or surface-near layers of the object to be heated. If the radiation source is black or gray and if it has a color temperature of 1500 K, then the source radiates off 51% of the total radiation output in a wavelength range above 2.7 μm. If the color temperature is less than 1500 K, as in most electric resistance heating elements, then substantially more than 51% of the radiation output is given off above 2.7 μm. Since most glasses in this wavelength range have an absorption edge, 50% or more of the radiation output is absorbed by the surface or in surface-near layers. It is possible, therefore, to speak of surface heating. Another possibility lies in heating glass and glass-ceramics with a gas flame, in which typical flame temperatures lie at 1000° C. Such a heating occurs mainly by direct transfer of the thermal energy of the hot gas onto the surface of the glass or of the glass-ceramic, so that here it is possible to proceed from a predominantly surface/superficial/heating. In general with the earlier described surface heating the surface or surface-near layers are heated in the parts of the glass or of the glass-ceramic that lie opposite the heating source. The remaining glass volume or glass-ceramic volume must accordingly be heated up correspondingly by heat conduction within the glass or the glass-ceramic material. Since glass or glass-ceramic material has as a rule a very low heat conductivity in the range of 1 W (m K), glass or glass-ceramic material must be heated up more and more slowly in order to keep tensions in the glass or glass-ceramics low. A further disadvantage of known systems is that, in order to achieve a homogeneous heating-up of the surface, the surface of the glass or of the glass-ceramic material must be covered as completely as possible with heating elements. Limits are placed there on conventional heating processes. With electrical heating resistances made of Kanthal wire, as they are preferably used, at 1000° C., for example, only a wall load of maximally 60 kW/m 2 is possible, while a full-surfaced (or holohedral) black radiator of the same temperature could irradiate an output density of 149 kW/m 2 . With a denser packing of the heating elements to be equated with a higher wall load, these would heat themselves up reciprocally, which through the resulting heat accumulation would involve an extreme shortening of the useful life of the heating elements. When a homogeneous heating-up of the glass or of the glass-ceramic is not achieved or is only inadequately successful, then this unfailingly results in inhomogeneities in the process and/or in the product quality. For example, any irregularity in the process conducting, in the ceramization process of glass-ceramics leads to a cambering or bursting of the glass-ceramic article. From DE 42 02 944 C2 there has become known a process and a device comprising IR radiators for the rapid heating of materials which have a high absorption above 2500 nm. In order to rapidly introduce, into the material, the heat given off from the IR radiators, DE 42 02 944 C2 proposes the use of a radiation converter from which secondary radiation is emitted with a wavelength range which is shifted into the long-wave direction with respect to the primary radiation. A heating of transparent glass homogeneous in depth with use of short-wave IR radiators is described in U.S. Pat. No. 3,620,706. The process according to U.S. Pat. No. 3,620,706 is based on the principle that the absorption length of the radiation used in glass is very much greater than the dimensions of the glass object to be heated, so that the major part of the impinging radiation is let through by the glass and the absorbed energy per volume is nearly equal at every point of the glass body. What is disadvantageous in this process, however, is that no homogeneous irradiation over the surface of the glass objects is ensured, so that the intensity distribution of the IR radiation source is depicted on the glass to be heated. Moreover, in this process only a small part of the electric energy used is utilized for the heating of the glass. The problem of the invention, therefore, is to give a process and a device for the homogeneous heating-up of semi-transparent or transparent glass and glass-ceramic articles, with which the aforementioned disadvantages are overcome. SUMMARY OF THE INVENTION According to the invention the problem is solved by the means that in a generic process the heating of the semi-transparent and/or transparent glass or glass-ceramic material is achieved by a proportion of infrared radiation acting directly on the glass and/or glass-ceramic material as well as a proportion of infrared radiation acting indirectly on the glass and/or glass-ceramic material, the share of the radiation acting indirectly on the glass or the glass-ceramic material being more than 50%, preferably more than 60%, preferably more than 70%, especially preferably more than 80%, especially preferably more than 90%, in particular more than 98% of the total radiation output. It is preferred if the infrared radiation is short-wave infrared radiation with a color temperature greater than 1500 K, especially preferably greater than 2000 K, most preferably greater than 2400 K, especially greater than 2700 K, especially preferably greater than 3000 K. In a first form of execution of the invention it is provided that the infrared radiation acting indirectly on the glass and/or glass-ceramic material comprises at least a component (proportion) of reflected and/or scattered, especially diffusely scattered, radiation. Advantageously the component of the short-wave infrared radiation that is not absorbed by the glass or glass-ceramic material in the one-time impinging, i.e., reflected, scattered or let through, is on the average more than 50% of the total radiation output given off by the IR radiators. If, for example, it is desired to cool slowly or heat rapidly, then in an advantageous execution of the invention it is provided that the process is carried out in an enclosed space, preferably an IR radiation hollow space. In an especially advantageous execution of such a process it is provided that the reflected and/or scattered infrared radiation is reflected and/or scattered by at least a part of the wall, base and/or cover surfaces. IR radiation hollow spaces are shown for example in U.S. Pat. No. 4,789,771 as well as EP-A-O 133 847, the disclosure content of which is fully taken into account in the present application. Preferably the component (proportion) of the infrared radiation reflected and/or scattered from the part of the wall, base and/or cover surfaces amounts to more than 50% of the radiation impinging on these surfaces. It is especially preferred if the component of the infrared radiation reflected and/or scattered from the part of the wall, base and/or cover surfaces amounts to more than 90%, respectively 95%, in particular more than 98%. A special advantage of using an IR radiation hollow space is, further, that with use of very strongly reflecting or back-scattering wall, base and/or cover materials it is a matter of a resonator of high Q quality, which is affected with only slight losses and, therefore, ensures a high utilization of energy. In an alternative development of the invention it is provided that the infrared radiation acting indirectly on the glass and/or glass-ceramic materials comprises a component of infrared radiation which is absorbed by a carrier or support body, transformed into heat and is given off onto the glass and/or the glass-ceramic material thermally bound with the carrier body. In a first development of this alternative it is provided that as carrier body ceramic plates are used. It is especially advantageous if with the carrier body it is a matter of a highly heat-conductive carrier body of as high as possible emissivity, preferably of SiSiC in the form of plates. Especially advantageously the heat conductivity of the carrier body in the range of the heat treatment temperature is at least five times as great as that of the glass and/or of the glass-ceramic material to be treated. Besides the method, the invention also makes available a device for carrying out the method. The device of the invention is characterized in that means are provided for the generating of an infrared radiation acting indirectly on the glass and/or glass-ceramic materials, which means are arranged and designed in such manner that the component of the radiation acting indirectly on the glass and/or the glass-ceramic material amounts to more than 50% of the total radiation output. In a first development of the invention it is provided that the means for generating an infrared radiation acting indirectly on the glass and/or glass-ceramic materials comprise reflectors and/or diffusors for the reflection and scattering, respectively, of the infrared radiation. As diffusely back-scattering material there are used, for example, ground quarzal plates with a thickness of 30 mm. for example. Also other materials reflecting or backscattering the IR radiation are possible, for example one or more of the following materials: Al 2 O 3 ; BaF 2 ; BaTiO 3 ; CaF 2 ; CaTiO 3 ; MgO; 3.5 Al 2 O 3 ; MgO, SrF 2 ; SiO 2 ; SrTiO 3 ; TiO 2 ; spinell; cordierite; cordierite sinter glass-ceramic If a rapid heating or a slow cooling is sought, then it is advantageously provided to accommodate the device in a bounded space, especially an IR radiation hollow space. In a special development of the invention it is provided that the surface of the walls, of the bases and/or of the cover of the bounded space, preferably of the IR radiation hollow space, comprises the reflectors or diffusors. One form of execution of the diffusor, for example, would be a diffusing screen. It is especially preferred if the reflectors or diffusors are designed in such manner that more than 50% of the radiation impinging on these surfaces is reflected or scattered, respectively. In an alternative form of execution it is provided that the means for the generation of indirect radiation comprise a carrier body which stands in thermal contact with the glass and/or glass-ceramic materials and absorbs a share of the indirect infrared radiation. It is especially preferred if the carrier body comprises ceramic plates, preferably of SiSiC, and the emissivity of the carrier body is greater than 0.5. SiSiC has a high heat conductivity as well as a low porosity as well as a low adhesive tendency with respect to glass. The low porosity has the consequence that only a few undesired particles can collect in the pores. For this reason SiSiC is especially well suited for working in direct contact with glass. In an especially advantageous form of execution it is provided that the heat conductivity of the carrier body, in the range of the heat treatment temperature, is at least five times as great as that of the glass or of the glass-ceramic material to be treated. BRIEF DESCRIPTION OF THE DRAWINGS The invention is to be described in the following by way of example with the aid of the drawings as well as of the examples of execution. In the drawings: FIG. 1 shows the transmission course with a thickness of 1 cm of a typical glass material to be heated; FIG. 2 the Planck curve of the IR radiator used with a temperature of 2400 K FIG. 3A the theoretical construction of a heating device with radiation hollow space. FIG. 3B the remission curve over the wavelength of Al 2 O 3 Sintox Al of the Morgan Matroc, Troisdorf, with a remission degree >95% in the near-IR wavelength range; FIG. 4 the heating curve of a glass material in a heating device comprising diffusors and reflectors; FIG. 5 the heating curve of a glass material in a device with an absorbent carrier body. DETAILED DESCRIPTION FIG. 1 shows the transmission curve over the wavelength of glass material used for the comparative tests of the present invention. The glass material has a thickness of 10 mm. There is clearly to be recognized the typical absorption edge at 2.7 μm, over which the glass or glass-ceramic material is opaque, so that the entire impinging radiation is absorbed on the surface or in the surface-near layers. FIG. 2 shows the intensity distribution of the preferably used IR radiation source. The IR radiators used are linear halogen IR quartz tube radiators with a nominal output of 2000 W at a voltage of 230 V, which have a color temperature of 2400 K. The IR radiators, corresponding to Wiensch's displacement law, have their radiation maximum at a wavelength of 1210 nm. The intensity distribution of the IR radiation sources is yielded correspondingly from the Planck function of a black body with a temperature of 2400 K. It follows then that an appreciable intensity, i.e. an intensity greater than 5% of the radiation maximum, is released in the wavelength range of 500 to 5000 nm, and altogether ca. 75% of the total radiation output falls in the wavelength range above 1210 nm. In a first form of execution of the invention only the annealing material is heated, while the environment remains cold. The radiation passing by the annealing material is led by reflectors or diffusing scatterers or diffusing backscatterers onto the annealing material. In the case of high output densities and preferably of metal reflectors, the reflectors are water-cooled, since otherwise the reflector material would tarnish. This hazard is present especially with aluminum, which, because of its good reflecting properties in the IR range, is gladly used for radiators, especially for those of great radiation output. Alternatively to metal reflectors there can be used diffusely backscattering ceramic diffusors or partially reflecting and partially backscattering glazed reflectors, especially Al 2 O 2 . A construction in which only the annealing material is heated can be used only when, after the heating-up, no slow cooling is required which, without insulating space, is obtainable with an acceptable homogeneity of temperature only with continuous reheating and only with a very high expenditure. The advantage of such a construction is, however, the easy accessibility of the annealing material, for example for grippers which is of great interest especially in hot shaping. In an alternative form of execution the heating device and the annealing material are located in an IR radiation hollow space equipped with IR radiators. This presumes that the quartz radiators themselves are sufficiently temperature stable or are cooled. The quartz glass tube is usable up to about 1100° C. It is preferred to make the quartz glass tube considerably longer than the heating spiral and to lead it out of the heating zone, so that the connections are in the cold zone in order not to overheat the electrical connections. The quartz glass tubes can be constructed with and without coating. In FIG. 3A a form of execution of a heating device according to the invention is represented with which the execution of the process of the invention is possible, without the invention being restricted to this. The heating device shown in FIG. 3A comprises a large number of IR radiators 1 which are arranged underneath a reflector 3 made of strongly reflecting or diffusely backscattering material. By the reflector 3 it is achieved that the glass or glass-ceramic material 5 to be heated is heated from the upper side. The IR radiation given off from the IR radiators penetrates the glass or the glass-ceramic material 5 largely transparent in this wavelength range, and it impinges upon a carrier plate 7 of strongly reflecting or strongly scattering material. Especially well suited for this is quartz, which also in the infrared range backscatters approximately 90% of the impinging radiation. Alternatively to this there could also be used highly pure, sintered Al 2 O 3 , which has a backscattering, i.e. remission degree of approximately 98% with adequate thickness. The glass or glass-ceramic material 5 is emplaced on the carrier plate 7 with the aid of, for example, quarzal or Al 2 O 3 strips 9 . The temperature of the glass or glass-ceramic material underside can be measured through a hole 11 in the carrier plate with the aid of a pyrometer (not represented). The walls 10 , together with reflector 3 as cover and carrier plate 7 as base, with corresponding formation with reflecting material, for example quarzal or Al 2 O 3 can form an IR radiation hollow space of high quality. FIG. 4 shows the heating curve of a borosilicate glass according to a process of the invention, in which the glass sample had dimensions of about 1100 mm with a thickness of 3 mm. The heating process or the heat treatment took place as described in the following: The heating of the glass samples occurred first of all in an IR radiation hollow space walled-in with quarzal according to FIG. 3A , the cover of which was formed by an aluminum reflector with IR radiators present under it. The glass samples or glass-ceramic bodies were borne in a suitable manner on quarzal. In the IR radiation hollow space the glass or the glass-ceramic material was irradiated directly by several halogen IR radiators, which were located at a distance of 10 mm to 150 mm over the glass or the glass-ceramic material. The heating-up of the glass or of the glass-ceramic material now took place by means of orientation (Ansteuerung) of the IR radiators over a thyristor plate on the basis of absorption, reflection and scattering processes, as thoroughly described in the following: Since the absorption length of the used short wave IR radiation in the glass or in the glass-ceramic material is very much greater than the dimensions of the objects to be heated, the major part of the impinging radiation is allowed to pass through the sample. Since, on the other hand, the absorbed energy per volume at very point of the glass or glass-ceramic body is nearly equal, there is achieved a homogeneous heating over the entire volume. In the process according to FIG. 4 the IR radiators and the glass material to be heated are located in a hollow space, the walls and/or cover and/or base of which consist of a material with a surface of high reflectivity or high backscattering capacity, in which at least a part of the wall, base, and/or cover surface scatters back the impinging radiation predominantly diffusely. Thereby the predominant part of the radiation is let through again into the object to be heated and is again partially absorbed. The path of the radiation lest through the glass or the glass-ceramic material also in the second passage is analogously continued. With this process thee is achieved not only a heating homogenous in depth, but also the energy expended is clearly better utilized than in the case of only a single passage through the glass or the glass-ceramic material. It is especially preferred for the process described here that at least a part of the wall, base and/or cover surface does not reflect the impinging radiation directly, but is diffusely backscattered. Thereby the radiation passes from all directions and under all possible angles into the glass or the glass-ceramic material, so that the heating simultaneously occurs homogeneously over the surface and a depiction of the intensity distribution of the radiation source onto the objects to be heated as hitherto in the state of the art. FIG. 5 shows the heating curve of the glass according to an alternative process according to the invention with absorbent carrier body. The diameter of the glass body was 100 mm with a thickness of 10 mm. The heating occurred as described in the following: First the glass sample outside of the radiation hollow space is emplaced on a carrier body of SiSiC with the thickness of 5 mm. Thereupon the carrier made of SiSiC is introduced into a radiation hollow space surrounded with quarzal. Thereupon the glass or the glass-ceramic material is directly irradiated with one or, according to the geometry of the glass of or the glass-ceramic material, also with several halogen IR radiators which are present in a reflector over the glass or the glass-ceramic material at a distance of 10 mm to 150 mm. The heating-up of the glass or of the glass-ceramic material now takes place by the orientation of the IR radiators over a thyristor controller by a combination of direct and indirect heating. Due to the transparency of the glass or of the glass-ceramic material a considerable share of the radiation output will radiate directly onto the carrier. The black SiSiC carrier absorbs nearly the entire radiation and distributes it rapidly and homogeneously over the entire surface of the carrier. The heat of the carrier is now given off likewise homogeneously to the glass or the glass-ceramic material and heats this from the underside. This process represents in the present process the indirect component of the heating-up. The direct contribution to the heating-up is subdivided into two components. The first component is yielded from the fact that at all wavelengths outside of the transparent zone the glass or the glass-ceramic material is opaque and therewith the radiation can heat only the surface or surface-near layers. The second contribution to the direct heating-up is delivered by the slightly absorbed part of the radiation, the wavelength of which lies in a range in which the glass or the glass-ceramic material absorbs weakly. This component leads to a heating-up of deeper layers of the glass or of the glass-ceramic material. The major part of the IR radiation, however, penetrates the glass by radiation and results in an indirect heating-up over the carrier. Also in this process a high temperature homogeneity is achieved over the glass surface and in this manner there is avoided a depicting of the radiation source onto the glass as in the state of the art. According to the invention the indirect component of the heating-up of the glass or of the glass-ceramic material in both the processes described in FIGS. 4 and 5 amounts to more than 50%. With the invention there are given for the first time processes and devices for the heating or supporting or exclusive heating of glass or of glass-ceramic materials which ensure a homogeneous heating of the same, have a high energy utilization as well as avoiding a depicting of the radiation source on the object to be heated. The process and the device can be used in a large number of areas of glass processing. Only by way of example and not exclusively so, let there be listed the following applications of the process of the invention: the temperature-homogeneous heating-up of glass-ceramic blanks in ceramization the rapid reheating of glass blanks for a following hot shaping the homogeneous heating of fiber bundles to drawing temperature the supporting and exclusive heating in mixture fusing the melting and purifying of glass and/or of glass-ceramic materials the supporting or exclusive heating in the shaping, especially in the drawing, in the rolling, in the casting, in the throwing, in the pressing, in the blowing in the blow—blow process, in the blowing in the press-blow process, in the blowing in the ribbon process, for the flat-glass production as well as in the floating the supporting or exclusive heating in the cooling, in the melting, in the thermal solidifying, in the stabilizing or fine cooling for the setting-in of a desired fictitious temperature, of a desired index of refraction, of a desired compaction with subsequent temperature treatment, in the aging of thermometer glasses, in the demixing, in the dyeing of tarnished glasses, in controlled crystallizing, in diffusion treatment, especially chemical solidifying, in reshaping, especially lowering, bending, buckling, blowing, in the separating, especially in the melting-off, breaking, setting, bursting, in the cutting, in the joining as well as in coating.
A method for the homogeneous heating of semitransparent and/or transparent glass and/or glass-ceramic articles using infrared radiation so that the glass and/or glass-ceramic articles undergo heat treatment at between 20 and 3000° C., notably at between 20 and 1705° C. Heating is achieved by a component of infrared radiation which acts directly on the glass and/or glass-ceramic articles and by a component of infrared radiation which acts indirectly on said glass and/or glass-ceramic articles. The radiation component indirectly acting on the glass and/or glass-ceramic articles accounts for more than 50% of total radiation output.
2
BACKGROUND OF THE INVENTION This invention relates generally to respiratory physiology and deals more particularly with a method and apparatus for monitoring apnea. In the field of respiratory physiology, it has long been known that post-operative patients and patients with brain damage and other debilitating injuries are susceptible to the sudden cessation of breathing which is known as apnea. Sudden infant death syndrome is caused by apnea and is triggered by an immaturity in the central nervous system that ordinarily corrects itself by the first birthday. Apneic episodes nearly always occur during sleep. Infants that are likely to be subject to sudden infant death syndrome are presently identified by considering a number of factors such as family history, premature birth, and the age and physical condition of the mother. In the intensive care nursery, likely apnea candidates are carefully monitored, and subsequent close monitoring in the home is usually recommended if any signs of susceptibility to apnea are observed in the nursery. It is not uncommon for an infant to first demonstrate apnea at about two months of age. The various types of apnea monitors that have been proposed are essentially respiration monitors. Among their basic components, they include a transducer which senses respiration and provides a signal, an electronic circuit for conditioning the signal, and an alarm device which provides an alarm following an adjustable time delay after loss of signal. The alarm generates a noise that sometimes awakens the infant such that spontaneous resumption of breathing occurs. If the infant is not awakened, resuscitation is necessary. Apnea monitors differ primarily in the type of transducer employed. Some monitors employ direct techniques which sense the flow of air in the airway. For active babies up to several months old, direct transducers of this type are impractical. The other type of transducer is an indirect type which detects the physical movement accompanying respiratory effort rather than ventilation itself. Indirect transducers can be either contact types or noncontact types. Direct contact transducers require that electrodes or other sensing elements be attached directly to the torso or chest of the infant. This encumbers free movement and can cause skin irritation and related problems. Particularly with large infants such as those monitored in the home, it is common for the electrodes to fall off or be pulled off and for the infant to become entangled in the wires leading from the electrodes. Among the types of noncontact sensors that have been proposed are segmented pneumatic mattresses equipped with an anemometer for sensing the flow of air among the segments, mattresses filled with a conductive elastomer, Doppler ultrasound transceivers, and capacitance type transducers that are either incorporated into a rigid mattress or placed under the mattress. All of these noncontact transducers suffer from numerous problems that have detracted from their commercial success. Typically, they are small and/or rigid in order to focus on a limited area so that stability and reproductability can be achieved. However, this introduces problems relating to changes of position of the infant within the crib or bassinet. Perhaps the most important problem associated with all existing apnea monitors is a lack of reliability. All known monitors are subject to false alarms when apnea does not occur and, even more importantly, they sometimes fail to give an alarm during apnea. Both contact and noncontact transducers are overly sensitive to the beating of the heart and movement of the great vessels, and both types of instruments sometimes interpret this "cardiovascular artifact" as respiration when there is actually an absense of respiration. As a result, the alarm is not given even though apnea has occurred. Another serious problem with existing apnea monitors involves the manner of displaying whether there is normal breathing or an alarm condition and whether or not the instrument is functioning properly. Oscilloscope displays have been attempted but are so large and expensive as to be virtually prohibitive under most circumstances. Since the incoming signal varies over a wide range, the gain during apnea should not be allowed to rise to a level that invites problems with artifact. If apnea should occur and the infant is awakened by the resulting alarm, there is no indication given by most existing instruments that there has been an apnea episode. The episode thus passes unnoticed by the parents or nurse. In existing apnea monitoring instruments, the time delay of the alarm is commonly generated by using a timed zero-crossing technique. If the incoming signal is lost, the timer begins to run but is reset to zero if the signal should reappear before elapse of the time delay period which is typically about 15 seconds. If the infant should twitch during apnea, which is not uncommon, the timer is reset and the alarm is delayed accordingly. Thus, the time delay prior to giving an alarm can be extended such that the alarm is not sounded in sufficient time to either awaken the baby or alert the parents or nurse to the apnea episode. SUMMARY OF THE INVENTION The present invention is directed to an improved apnea monitor and has, as its primary goal, the provision of an improved method and apparatus for detecting apnean in a more accurate and reliable manner than has been achieved in the past. In accordance with the invention, a unique capacitor type transducer pad is constructed in a manner to respond to respiratory movement while rejecting cardiovascular artifact movement. Supression of the cardiovascular artifact is accomplished by forming the pad such that it is least sensitive where the body weight is greatest and most sensitive around the periphery of the body where respiratory effort is most pronounced. The pad is flexible so that it is able to readily withstand being folded and can be easily stored, it is soft and comfortable and is sensitive to respiration of the infant without picking up extraneous outside movement, and it is shielded from water and other liquids that could cause a short circuit. Another important feature of the invention is the gain-set circuit which compensates for the long term instability and variation in the sensitivity of the transducer pad. The strength of the signal from the transducer can vary over a wide range even in the absense of apnea, particularly if the pad is moved between infants of different size and morphology, if the infant assumes a different position, or if the transducer has been folded, rolled up or otherwise deformed immediately prior to use. In any of these situations, the signal level can take up to several hours to stablize. The gain-set circuit corrects for such variations in the input signal strength by automatically adjusting the gain of the signal after delaying long enough to assure that the signal change is not caused by apnea. The invention also includes an improved visual display in the form of a single row of light emitting diodes. Most of the LEDs are yellow and normally flash or blink in sequence in and out from the center of the row to provide an analog representation of the respiratory function. If apnea occurs, a cluster of red LEDs in the center of the row are energized to indicate an alarm condition, and they remain energized until manually reset. Thus, a visible sign remains to indicate that apnea has occurred even if the infant is aroused by the audible alarm and resumes breathing spontaneously. A pair of green LEDs at the opposite ends of the row indicate the status of the gain-set circuit and provide information indicating that the signal gain is proper. The alarm trigger circuit is unique and is improved over the zero-crossing detection technique that can result in undue delay prior to the alarm being given. In contrast to the zero-crossing technique, the present invention has an alarm trigger circuit that generates a control voltage having a current proportional to the signal strength. The control voltage operates a current sensitive LED and its voltage is virtually constant over a wide range of input signals. The control voltage begins decaying exponentially when the input signal is lost due to apnea. When the decaying control voltage drops to the level of a time related voltage introduced into the alarm driver, the alarm is triggered and gives both a visible and audible indication of apnea. This control voltage technique for triggering the alarm assures that the alarm is merely delayed momentarily rather than completely reset if the infant should twitch during apnea. DETAILED DESCRIPTION OF THE INVENTION In the accompanying drawings which form a part of the specification and are to be read in conjunction therewith and in which like reference numerals are used to indicate like parts in the various views: FIG. 1 is a perspective view of an apnea monitoring instrument constructed according to a preferred embodiment of the present invention; FIG. 2 is a fragmentary sectional view taken through the transducer pad included in the apnea monitor; FIG. 3 is a fragmentary sectional view on an enlarged scale of one end portion of the transducer pad; FIG. 4 is a partial schematic diagram of the circuit which produces a transduced signal indicative of the respiratory function; and FIG. 5 is a block diagram of the complete electronic circuit included in the instrument. With initial reference to FIG. 1, the apnea monitoring instrument of the present invention includes capacitance type transducer pad 10 and a cabinet 12 which contains the majority of the circuit elements and which has a visual display on its front panel 12A. A cord 14 extends from pad 10 and carries a plug (not shown) that may be inserted in a mating socket formed on the backside of cabinet 12. Referring additionally to FIGS. 2 and 3, the transducer pad 10 includes a flat inner conductor 16 which forms one capacitor plate of the transducer. The inner conductor 16 is flexible and is preferably formed of a polyester fabric which is embedded with aluminum. Two sheets of insulating film 18 adhere to the top and bottom surfaces of the inner conductors 16. The insulating sheets 18 protect the inner conductor from liquids that might cause a short circuit in the high resistant element. Preferably, sheets 18 are formed from a material such as polyurethane film or a similar substance. Numeral 20 designates an outer conductor which is wrapped around the inner conductor 16 to provide an upper capacitor plate 20A spaced above and parallel to conductor 16 and a lower capacitor plate 20B spaced below and parallel to the inner conductor. The outer conductor 20 is flexible and is preferably formed of a polyester fabric embedded with aluminum. A pair of foam pads 22 are sandwiched between the inner conductor 16 and the upper and lower conductors 20A and 20B. Pads 22 provide the dielectric material of the capacitor and are constructed of a soft resilient material such as polyurethane foam. A thin layer 24 of napped material such as velour adheres to the upper surface of the upper foam pad 22. The upper portion 20A of the outer conductor 20 is located on top of layer 24. Layer 24 has a spring constant considerably less than that of the underlying foam pad 22. In constructing pad 10, after the inner conductor 16 has been enclosed between the film sheets 18 and the inner assembly has been sandwiched between the foam pads 22, the velour layer 24 is applied to the upper pad and the outer conductor 20 is wrapped around the pad assembly. A flexible cover 26 contains the pad, and the pad cover 26 is constructed of a heat welded waterproof plastic material such as a polyurethane sheet. The underside of cover 26 provides controlled leakage to prevent pneumatic damping of the signal. In the assembled pad, the inner conductor 16 is parallel to portions 20A and 20B of the outer conductor 20 to provide parallel capacitor plates. The pad is generally rectangular and is sized to cover the entire bottom surface of a crib or bassinet. A small electronic package 28 is located in a cavity 30 formed in the foam pads 22 near the upper edge of the pad. A wire 32 connects the electronic package 28 with the outer conductor 20 in order to apply a constant electrical charge on the outer plate of the capacitor. Another wire 34 connects the package with the inner conductor 16 in order to permit sensing of the charge which is induced on the inner plate and the voltage of the transduced signal. The cord 14 leads from the electronic package 28. The electronic package includes an electrometer type amplifier such as a field effect operational amplifier 36 (FIG. 4) having a very high resistance 38 to provide the ground return. Since the fixed charge Q which is placed on the outer conductor 20 is substantially constant, the sensed voltage output V of the preamplifier 36 changes in accordance with the relationship ΔV=Q/ΔC in response to changes in the capacitance C due to movement accompanying the respiratory effort of an infant lying on pad 10. The output from the operational amplifier 36 thus provides a transduced signal indicative of respiration. The transducer requires an extremely high terminating resistance (typically 200 megohms), and it is thus preferred for the preamplifier to be housed within the transducer pad 10 in order to shield it from stray electrical fields. Referring now to FIG. 5, the preamplifier 36 serves primarily to provide impedance transformation and also offers some amplification and low pass filtering. The output signal from the preamplifier is applied to an attenuator 40 which, along with the remaining components of the circuit, is housed in the cabinet 12. Since the preamplifier 36 provides a more than adequate signal, the attenuator 40 is utilized, although an amplifier could be used instead if necessary. The attenuator 40 includes an active circuit element such as an operational amplifier or another adjustable gain element having its gain determined by a gain set device 42 which may be an optical coupler or a field effect transistor. The attenuated signal from the attenuator 40 is passed through an electronic filter 44 which, together with the filter in the preamplifier 36, limits the pass band frequencies to 0.4-1.25 Hz which characterizes infant respiration. Respiration rates outside of this frequency band are abnormal, and common artifacts (noise in the signal) other than cardiovascular artifact are outside of these limits. Most of the circuit gain is taken in a variable amplifier 46 which receives the signal from the filter 44. The attenuator 40, filter 44 and variable amplifier 46 condition the incoming transduced signal. The conditioned signal is applied by the variable amplifier 46 to a display drive circuit 48 and also to a control voltage generator 50 which will subsequently be described. Display drive circuit 48 operates a display circuit 52 which controls a visual display located on the front panel 12A of cabinet 12. As shown in FIG. 1, the visual display on panel 12A includes a horizontal row of light emitting diodes that includes in its center four red LEDs 54 that serve to indicate an alarm condition. Extending outwardly from both sides of the center red LEDs 54 are a number of yellow LEDs 56 which are connected in pairs that are symmetric about the center of the row. In other words, the second yellow LED to the left of center is connected with the second yellow LED to the right of center and so forth. The display circuit 52 lights the connectal pairs of yellow LEDs 56 in sequence such that yellow lights flash outwardly along the row on both sides of the center and, when the end of the row is reached, the yellow LEDs flash inwardly toward the center. The result is that the LEDs "swing" symmetrically inwardly and outwardly from the center to normally provide an analog signal indicative of respiration. A single green LED 58 is located at each end of the row. Referring again to FIG. 5, the output from the variable amplifier 46 is applied to the control voltage generator 50 as previously indicated. The control voltage generator 50 generates a control voltage signal having a current which is proportional to the attenuated signal provided by the attenuator 40. This control voltage signal is applied to an automatic gain control circuit 60 which provides automatic gain control for the variable amplifier 46. Short term shifts in signal strength are thus corrected by the automatic gain control circuit to maintain the display "on scale." The control voltage signal is also applied to an alarm driver 62 which receives an adjustable time related voltage (TD set) to provide an alarm time delay controlled by an adjustment knob 64 (FIG. 1) on the front panel of cabinet 12. The time delay can be adjusted up to 25 seconds by properly positioning knob 64. When the control voltage applied to alarm driver 62 drops to the level of the time related voltage introduced on the TD set line, an audio alarm 66 is triggered and provides an alarm noise to indicate apnea. The alarm signal is additionally applied to the display circuit 52 to energize the red LEDs 54 in the center of the display. Once the red LEDs 54 have been energized, they remain energized until manually reset by a reset button 68 located on the front panel of the cabinet. The current of the control voltage signal generated by the control voltage generator 50 is sampled by a gain-set voltage generator 70 which produces a gain-set voltage that is extremely sensitive to changes in the level of the input signal. A gain-set voltage level of about 0.4 volts indicates a properly attenuated input signal in the preferred embodiment of the invention. The gain-set voltage feeds a comparitor circuit 72 which compares the voltage with established voltage limits defining a normal range of the gain-set voltage. For example, the voltage limits can be 0.3 volts and 0.6 volts in order to maintain the gain-set voltage within range. If the gain-set voltage is between the established limits, the comparitor 72 provides a signal to the display circuit 52 which effects constant energization of the green LEDs 58 on the opposite ends of the display row. This provides information indicating that the attenuator 40 is properly adjusted as to its gain. If the gain-set voltage is outside of its normal range (0.3 volts-0.6 volts), the signal delivered by the comparitor 72 to the display circuit 52 causes the green LEDs 58 to initially flash and then become extinguished as the error increases. With the initial flashing of the green LEDs, comparitor 72 initiates a 60-second timer 74. After the elapse of a 60 second time delay, the 60-second timer 74 sets a 15-second timer 76. If an alarm signal is delivered by the alarm driver 62 within the 60 second time delay period, a disable signal is applied to the 15-second timer to disable the gain-set function, since it is not desirable to adjust the sensitivity in the presence of an alarm condition. If there is no alarm condition within the 60 second time delay, timer 74 resets itself and starts the 15-second timer 76 which switches a sample and hold circuit 78 into the "sample" mode. The sample and hold circuit 78 controls the gain-set device 42 in order to adjust the gain of the active circuit element in attenuator 40. The sample and hold circuit 78 includes a memory which retains the previous signal level applied to the gain-set device 42. Immediately upon activation of the 15-second timer 76, the previous signal level applied to gain-set device 42 is transferred from the memory of the sample and hold circuit 78 and applied to a summation amplifier 80. The summation amplifier 80 receives the gain-set voltage generated by the gain-set voltage generator 70 and generates an error signal which is the difference between the ideal value of the gain-set voltage (0.4 volts) and the actual output voltage of the gain-set voltage generator 70. The voltage which is applied to the summation amplifier from the sample and hold circuit is added to or subtracted from the error signal, depending upon the polarity. The resultant signal is then applied to the sample and hold circuit 78. The gain set device 42 then adjusts the gain of attenuator 40 in a manner to return the gain-set voltage to within its normal range. At the end of the 15 second period established by timer 76, equilibrium is established, timer 76 resets, and the sample and hold circuit returns to the "hold" mode. In operation, the apnea monitoring instrument detects apnea and provides both a visual and audio alarm indicitive thereof. When an infant or other patient lies on the transducer pad 10, the body weight distorts the inner conductor 16 slightly and the upper conductor 20A grossly, and also crushes the velour layer 24 between the body and the upper foam pad 22. Due to the body weight, very little movement of the outer conductor with respect to the inner conductor can occur directly under the body during respiration. However, around the periphery of the body where there is minimum body pressure, the velour layer 24 lifts the upper conductor 20A off of the surface of the upper pad 22 during respiration and there is thus considerable relative movement between the inner and outer conductors around the periphery of the body. As a consequence, the sensor pad is least sensitive where body weight is the greatest and where the effects of cardiovascular artifact are greatest. Conversely, the pad is most sensitive where the body weight is the least but where respiratory motion is most significant. Thus, during apnea, the transducer does not pick up cardiovascular motion and interpret such motion as respiration. The transduced signal which results from respiratory effort is applied to the attenuator 40 after impedance matching in the preamplifier 36. The conditioned signal from the variable amplifier 46 is applied to the display drive circuit 48 which operates the display circuit 52 in a manner causing the yellow LEDs 56 to "swing" inwardly and outwardly in response to respiration. The automatic gain control circuit automatically adjusts the gain of the variable amplifier such that the conditioned signal has the proper amplitude to maintain the analog display "on scale". If apnea should occur, the control voltage signal from the control voltage generator 50 immediately begins decaying exponentially and, when sufficient time has elapsed for it to drop to the level of the time related voltage entered into the alarm driver 62, the audio alarm 66 is triggered and the red LEDs 54 are energized on the display surface of the cabinet. The contrast between the swinging movement of the yellow LEDs and the constant energization of the red LEDs permits the condition of the infant to be ascertained with a quick glance at the display panel of the cabinet. The audio alarm 66 can awaken the infant such that spontaneous resumption of breathing occurs. This terminates the audio alarm 66, but the red LEDs 54 remain energized until manually reset by the reset button 68. Therefore, the parents and hospital personnel are alerted to the fact that an apneic episode has occurred even in those situations where resuscitation is not necessary. It is important to note that the alarm trigger circuit provides an adjustable time delay that is not objectionably prolonged by an active patient. Since the current of the control voltage signal is proportional to incoming signal strength and operates a current sensitive light emitting diode, the voltage of the control voltage signal is virtually constant at 1.4-1.5 volts over a wide range of signal level. When apnea occurs, the voltage immediately begins decaying in exponential fashion. Thus, if the infant should twitch during an apnea episode, the alarm is merely delayed momentarily rather than being completely reset. The exponential decay continues immediately after the twitch is terminated. The gain-set circuit and related components act to correct the setting of the attenuator 40 from time to time to compensate for long term or unusual short term fluctuations that are not handled by the automatic gain control circuit. Also, the gain-set circuit maintains the incoming signal level at a prudently low value in order to set a limit on the gain level that can be achieved by the automatic gain control circuit during apnea. Thus, the sensitivity of the system to extraneous physical movement or other artifact is limited during apnea. So long as the gain-set voltage remains within the normal range of 0.3 volts-0.6 volts, the sample and hold circuit 78 remains in the "hold" mode and the gain of attenuator 40 is unaffected. However, if the gain-set voltage departs from its normal range, the comparitor 72 initiates operation of the 60-second timer 74 and, if there is no alarm condition within 60 seconds (the maximum time delay for the alarm is 25 seconds), the sample and hold circuit is placed in the sample mode. Immediately, the most recent signal level applied to gain-set device 42 is transferred from memory to the summation amplifier 80 and is added to or subtracted from the error signal. The gain-set device 42 then adjusts the gain of attenuator 40 appropriately such that the gain-set voltage returns to its normal range. When equilibrium has been established after 15 seconds, the sample and hold circuit returns to the hold mode. If the change in the input signal is due to apnea, the alarm signal generated by alarm driver 62 disables the circuit and prevents adjustment of the gain of the attenuator. It is thus apparent that the present invention provides an apnea monitoring instrument which is insensitive to cardiovascular artifact, primarily due to the unique construction of the transducer pad 10. Also, the circuit automatically adjusts the sensitivity in response to appreciable changes in the signal strength after first making certain that the change in signal strength is not due to an emergency condition. The visual display is improved in comparison to oscilloscope displays and other expensive displays that have been attempted in the past. The control voltage provided by control voltage generator 50 is important to the sophisicated operation of the device in a number of respects. In cooperation with the automatic gain control circuit, the control voltage corrects for short term shifts in signal strength. The current of the control voltage signal is sampled by the gain-set voltage generator which in turn generates a gain-set voltage used to automatically update the attenuator stage 40. Also, the control voltage is used in the alarm trigger circuit to provide a superior means for establishing an alarm time delay that is not sensitive to twitches of the infant. Finally, the control voltage signal can be used in conjunction with an external chart recording device that provides a permanent record of apneic trends. The circuit can be used in other types of physiological monitoring such as monitoring of blood pressure where short term changes are often more important diagnostically than absolute values. From the foregoing, it will be seen that this invention is one well adapted to attain all the ends and objects hereinabove set forth together with other advantages which are obvious and which are inherent to the structure. It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims. Since many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.
An apnea monitor having a capacitance type transducer pad providing a signal indicative of respiration. The resilient dielectric material between the capacitor plates is formed in two layers with the upper layer having a lesser spring constant to make the pad more sensitive around the periphery of the body to respond to respiratory motion while rejecting cardiovascular motion. The transduced signal is monitored and its gain is automatically adjusted to compensate for long term instability by a gain-set circuit arrangement having a time delay to assure that changes in the signal are not caused by apnea. A control voltage generated by the circuit operates the alarm without excessive time delay and is also used to provide a gain-set voltage for adjustment of the signal gain.
0
BACKGROUND OF THE INVENTION 1. Field of the Invention The disclosure relates generally to devices designed to distract, or lengthen, bone sections separated by an osteotomy, in addition to serving as a permanent dental implant device. More particularly, the disclosure relates to distraction devices that are internally implantable in an upper or lower jaw, and that are capable of gradual adjustment to distract osteotomically separated bone sections for the purpose of enhancing bone growth. Devices disclosed herein also serve as permanent implants for purposes of restoring dentition. 2. Description of the Relevant Art The use of dental implants for the replacement of teeth roots and restoration of dentition is known in the art. These devices are typically bullet shaped or screw shaped implants, or anchoring members, with an abutment (post) that extends through the gums and to which the replacement tooth or teeth are attached. The usual practice is to make an incision in the gum to expose the bone, drill a hole in the bone, place an implant in the hole, and then close the gum tissue. The implant is typically left in place for four to six months in order to allow osteointegration, after which the implant is uncovered and a post for rebuilding dentition is placed When there is a deficiency of bone, as occurs when a tooth has been missing for an extended time, for example, then a grafting procedure may be performed with the implant placement, or even four to six months prior to implant placement. A variety of implant devices have been described. U.S. Pat. No. 4,682,951 to Linkow describes an implant device for use in an area of the maxilla adjacent a descendent portion of the maxillary sinus, particularly in patients with enlarged sinus cavities. This device is anchored in a hole that is predrilled through the bone and into the sinus cavity The anchoring device is a basket or cradle containing bone chips that is inserted into the area of the sinus cavity. The presence of this basket or cradle promotes new bone growth and the device becomes osteointegrated. Posts attached to this basket or cradle then serve as implants for the attachment of artificial teeth. U.S. Pat. Nos. 4,744,753 and 4,886,456 to Ross and U.S. Pat. No. 4,906,191 to Soderberg describe devices and methods for forming dental prostheses. Prior to producing a model for use in tooth replacement, an implant is placed in the jaw and allowed to integrate. The replacement dentition is modeled, typically using a heat meltable material that forms around a post or screw attached to the implant. This model is then used in the manufacture of a permanent tooth or teeth. U.S. Pat. Nos. 5,489,210 and 5,611,688 to Hanosh include expandable, bullet-shaped dental implants that are inserted into predrilled holes in the jaw and provide threaded connections for attachment of prostheses. These devices further provide internal threading for insertion of a screw within the device. Activation of this expander screw causes the implant to expand for more secure anchoring in the predrilled hole in the jaw. A dental implant device described in U.S. Pat. No. 5,725,377 includes an internal battery so that a small electrical field generated by the implant stimulates bone growth. Bone distraction devices are also known in the art. Orthopedic distraction, for example, has been used for several decades. One method of promoting bone growth involves cutting the bone, distracting (separating) the two pieces of the bone a desired distance, setting the two ends in place by means of a bridge across the two bone sections, and filling the gap between the bone ends with a bone segment or graft. Devices for gradual bone distraction are described in U.S. Pat. No. 4,096,857 to Kramer and U.S. Pat. No. 3,976,060 to Hildebrand. European Patent Application No. EP 0 791 337 to Razdolsky and Driscoll describes a device for lengthening the jaw by stretching the jaw of a young person during growth, a process that can be accomplished without cutting the jaw bone. The device is also described as useful in older patients and more severe cases when used in conjunction with a corticotomy. Several devices that may be attached externally to the jaw have been described for mandibular distraction. Examples of such devices include those described in European Patent Application No. EP 0 832 613, PCT Publication No. WO 98/09577 and U.S. Pat. No. 5,364,396. There is still a need, however, for devices and methods that allow a practitioner to replace degenerated or otherwise deficient bone, and also to place a permanent implant device to be used for replacement dentition, without requiring separate surgeries for bone replacement and implant placement. SUMMARY OF THE INVENTION A distractor/implant device is disclosed herein that may be used to provide gradual distraction between separated bone sections, thus encouraging bone growth between the distracted sections. The device is inserted into a bone segment, such as a jaw bone segment, preferably in conjunction with an osteotomy. In certain embodiments, the jaw may be predrilled with a hole of compatible size and depth for insertion of the device. An osteotomy may then be made just beneath the predrilled hole, such that when the bone segments are separated, the hole will extend into the separation. After insertion of the device, the bone segments are separated or mobilized. The device then gradually distracts (separates) the bone segments, thus encouraging or promoting new bone growth in the space between the separated bone segments. In certain embodiments the gradual separation of bone segments is continued until a certain distance is obtained, thereby restoring bone to an area of bone depletion, degradation, or other deficiency. As such, the device may be used to improve an area or condition of deficiency of bone due to injury, trauma, disease, decay, neglect, genetic defect, or the like. A distraction device as disclosed herein may also serve as a dental implant. In certain embodiments, a device as described herein may be allowed to osteointegrate, and may thus be effective to provide an implant or anchoring device for a dental abutment or prosthesis. As used herein, "osteointegrate" or "osteointegration" of a device or object have the standard meanings known in the art, and are further defined as a condition or action in which the device or object is left in a living bone for such a time that a portion of bone grows to surround or adhere to the device or object. These terms may also include the meanings that the device or object is tightly held or not easily movable within or relative to the section of bone. In certain embodiments, a device as disclosed herein may serve as a dental implant by providing for the attachment of a dental abutment. A device may be configured to be compatible with standard abutments and dental restoration fixtures known in the art, or it may be configured to be compatible with abutments and restoration fixtures of nonstandard dimensions. Described herein are devices that are compatible with abutments requiring an external hexagonal attachment, an 8° Morse taper configuration, a spline configuration, an internal hexagon, a screw retained abutment, a cement retained abutment, an exterior square post, an exterior octagonal post, an internal square, or an internal octagon, for example. The disclosure of these examples is not intended to be limiting, and other configurations may also be provided. During use, the devices disclosed herein may provide structure and stability for bone distraction and dentition restoration. In certain embodiments these devices also allow for efficient removal of a temporary abutment and placement of a final abutment for restoration of teeth. The devices may be made of any biocompatible materials of sufficient strength and resilience, including, but not limited to titanium, stainless steel, ceramic, a precious metal, or an alloy or combination of these. In alternative embodiments, the devices may include a coating of a substance such as hydroxylapatite or other minerals, or plasma, for example, or texturing to aid the osteointegration process. Such surfaces may be applied by any method known in the art, such as by dipping, painting, spraying, chemical bonding, electroplating, sand blasting, ball peening, or they may be incorporated into the material from which the device is constructed. In addition, the devices may include roughened or grooved surfaces, patterned grooves such as diamond patterns, holes, depressions, projections, or other texturing on or in the exterior surface. Other materials or techniques known in the art to aid retention of a medical implant in a bone are also contemplated to be applicable to the devices disclosed herein. In certain embodiments, the distraction devices include a main body, a base, and an elongated member configured to pass through the main body and contact the base during use. During distraction, the main body is held tightly in the upper bone segment and the elongated member is urged through the main body in the direction of the base, which provides a solid platform. The movement of the elongated member thus separates, or distracts the main body (attached to the upper bone segment) from the lower bone segment, which may contact or possibly contain the base. The main body is preferably elongated and may be substantially cylindrical, bullet shaped, polygonal, or other regular or irregular shape. The main body may include an internal channel or duct, or a threaded internal bore configured to allow the elongated member or shaft to extend through the channel and to engage the main body during use. The main body may also provide a top designed to accommodate a dental abutment as described above and the exterior coatings threading and/or other methods of securing the main body in a bone. The top of the main body may also provide a means for driving the device into the bone. This means may also serve as the attachment for an abutment. For example, an external hex may be used to drive the device into the bone and may then also serve as an attachment for an abutment that requires an external hex. Or the means for driving the device into the bone may be a separate structure such as an internal hex, an internal polygon, a slot, or crossed slots. Any configuration may be used so long as it does not interfere with, or block the channel of the main body, so that the shaft can extend above the main body in the pre-distraction position. The device also includes a base configured to be implanted beneath the main body (distal to the bone crest) in a bone to be distracted. The base may have a proximal surface that is adjacent the main body in the undistracted position, and a distal surface, and the base may be substantially cylindrical, bullet shaped, or tapered inwardly from the proximal to the distal surfaces. The base may also be provided in any shape as described above for the main body. The base may also engage the main body in a way that prevents rotation of the base with respect to the main body. For example, the base may include guide pins or rods that extend from the proximal surface and mate with openings so that the pins are slidable into the main body. Alternatively, the base may include a cylindrical shell that projects from the proximal surface, or the shell may be the outer surface of the base. In either case, the cylinder mates with a complementary opening in the main body so that the two pieces fit together in a telescopic arrangement. A telescopic arrangement, or engaging telescopically, is used herein to mean that one piece slides into the other as is common with the parts of a hand telescope. The base and main body may also include fingers that interdigitate, including fingers and grooves that may be formed on the outer surfaces of the main body and base such that the two bodies are preventing from rotating with respect to each other. Any other means of interaction of the main body and base could also be used, as long as the elongated member is still able to distract the main body away from the base during the distraction process. The interacting means or design may be configured so that the main body and base continue to interact through a part of, or even the entire distraction process, or they may interact only in the pre-distraction position. The exterior of the base may be smooth, or it may also include any of the surface coatings, threading or textures as described above, either together with or independently of, any threading, texture or coating of the main body. The base may include a cavity, depression, indention, or hole that aligns with the channel or duct of the main body to form a contiguous channel during use. In certain embodiments the base includes a closed ended cavity, ending in a base cap, to provide a solid platform to receive an end of an elongated member. During use, the elongated member may extend through the channel in the main body, into the cavity of the base, and contact the base cap at the bottom of the cavity. Other configurations may also be used, so long as the elongated member can be activated and the end of the member is constrained from passing completely through the base. The device may further include an elongated member such as a shaft, rod, bar, or the like configured to be disposed within and extend through the internal channel of the main body and into the base. The elongated member provides a means of engaging the main body so that the main body may be controllably urged along the length of the elongated member when the member is activated. The elongated member is also configured to be held in the base such that, during activation, the base provides a solid distraction surface and does not move relative to the length of the elongated member. In certain embodiments, the base includes a cavity with an opening into the cavity through which the elongated member passes. The shaft of the elongated member is smaller in diameter than the opening into the cavity so that the member can freely rotate in the base. In some embodiments the elongated member includes an enlarged end that is configured to be held in the base. In those embodiments, the end of the elongated member may be larger than the opening into the cavity in the base so that the elongated member may not be easily removed from the cavity. In other embodiments, the diameter of the end of the elongated member is smaller than the diameter of the opening into the cavity of the base so that the member may be easily inserted into or removed from the base. In those embodiments in which activation of the elongated member includes rotating the member, the member may freely rotate in the base, or the base may rotate concurrently with the member so long as the base is immobile with respect to the long axis of the member. In certain embodiments the elongated member may be from about 3 millimeters to about 20 millimeters in length, or longer if needed. The length of the elongated member is determined by a practitioner based on the amount of distraction required. Typically the member is from about 1 to 3 millimeters in diameter, depending on the width of the main body. The elongated member may also include an activation device, effective during activation to distract the main body from the base of the device. The activation device may include, but is not limited to a hexagonal head or cavity, a square head or cavity, a polygonal head or cavity, a slot, or a crossed slot. The activation device may be any effective conformation that allows activation to continue during the latter stages of distraction when the top of the elongated member is contained in the duct of the main body. The device may also include, in certain embodiments, an activation tool, such as a wrench or driver to interact with the activation device. In certain embodiments the internal channel of the main body is threaded and the elongated member is threaded to engage the threads in the channel. In those embodiments, activation includes rotating the elongated member so that the main body is threadably advanced along the elongated member, which may freely rotate in the base. The internal threading near the top of the main body may be configured to accept a threaded dental abutment or prosthesis, or a screw or other threaded member for attaching an abutment. The threading near the top may then serve to engage the elongated member during the distraction process, and then may also serve to engage a threaded abutment after distraction, when the elongated member has moved down into the main body, exposing the top threads. Alternatively, threads at the top of the channel of the main body may be configured to mate with an abutment, but not with the elongated member, which would then pass by the top threads into the channel without engaging the threads at the top of the channel. Certain distraction devices disclosed herein may serve as dental implants. Such devices are configured such that, after the distraction process is complete, a dental abutment or prosthesis may be attached or affixed to the top of the device. In certain embodiments, therefore, the disclosed devices may include a dental abutment, or a dental abutment attached to the main body. The devices described herein may also include an activating tool or an activating wrench. Such a wrench may include a removable ratchet driver and a handle, or it may be constructed of a single piece that includes a handle and a head for interaction with the device. The head may be a fixed piece or it may be a ratchet. Certain activation wrenches may serve to drive the device into the bone, or they may serve to activate the elongated member during distraction, or they may serve both purposes. Activation wrenches that serve to drive the device into the bone also provide a hole for extension of the elongated member above the device. In certain embodiments a dental distraction device comprises a main body, a base, and a shaft. The shaft is used to control the relative position of the main body and base during distraction of an osteotomized bone. The device may be left in the bone after distraction as a dental implant. The main body defines a concentric axial channel with internal threading. The shaft comprises complementary threading such that when the two sets of threads are engaged, rotation of the shaft with respect to the main body causes the main body to move along the shaft. In this embodiment, the base defines a cylindrical, close ended support for an end of the shaft, within which the shaft is freely rotatable. In alternative embodiments, the closed end of the close ended support is either a flat surface or a rounded surface. Described herein are methods of distracting a jaw bone in need thereof. These methods include providing a bone distraction device, as described above; drilling a hole of a size and shape to accommodate the bone distraction device in the bone; making an osteotomy just below the hole; inserting the bone distraction device in the hole; separating the superior osteotomized bone segments and inferior osteotomized bone segments, allowing callus (early bone) to form in the osteotomy; separating the main body and the base by activating the shaft, thus stretching the osteotomy; allowing the bone callus in the osteotomy to grow; and repeating the two previous steps until the desired bone height is reached. A method of providing a dental implant in an area of vertical bone loss is also described herein. The method includes providing a bone distraction device, as described above; drilling a hole of a size and shape to accommodate the bone distraction device in the bone; making an osteotomy just below the hole; inserting the bone distraction device in the hole; separating the superior osteotomized bone segments and inferior osteotomized bone segments, allowing callus (early bone) to form in the osteotomy; separating the main body and the base by activating the shaft, thus stretching the osteotomy; allowing the bone callus in the osteotomy to grow; repeating the two previous steps until the desired bone height is reached; and allowing the bone distraction device to remain in the distracted bone to serve as a permanent dental implant. A part of the disclosure is a method of manufacturing a combination bone distraction and dental implant device. In one embodiment, the method comprises providing a main body, wherein the main body may include an internal channel and a top designed to accommodate a dental abutment. The method also includes providing a base designed to abut or to slidably engage the main body in the undistracted position. The base may include an internal cavity configured to align with the internal channel of the main body to form a contiguous channel. The cavity in the base may terminate in a surface configured to accept an end of a shaft and provide a solid distraction platform against which a shaft is freely rotatable. A shaft is also provided in the method. The shaft or elongated member may range from about 3 millimeters to about 20 millimeters in length. During use, the shaft is disposed within and extending into the internal channel of the main body and the cavity of the base. The shaft may include threads configured to mate with a threaded internal channel of the main body and it may further include an activation device. The activation device may be a hexagonal projection or cavity, a square head or cavity, a polygonal head or cavity, a slot, or a crossed slot. In a further embodiment of the disclosure, a method of anchoring a dental prosthesis in an area of low bone density is described. This method includes providing a bone distraction device as described herein; making an incision in the gum tissue and exposing the bone of the upper or lower jaw; drilling a hole the diameter of the device and tapping the bone to accommodate the main body; screwing or inserting the devise into position; osteotomizing the jaw bone just below the device; allowing the superior osteotomized bone segments and inferior osteotomized bone segments to partially separate; closing the gingiva; and periodically activating the shaft by means of an activation wrench. It is understood that the any of the devices or methods described herein in any of their embodiments, although described in the singular, may be duplicated so that a plurality of implants are provided and are activated in uniform or independently as needed. Thus, a larger section of jaw may be distracted by the use of spaced apart distractor/implant devices to provide support for a dental bridge or for a plurality of artificial teeth. Examples of this are illustrated at least in FIGS. 1 and 2. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be more readily understood by reference of the accompanying drawings wherein like reference numerals indicate like elements throughout the drawing figures, and in which: FIG. 1 is perspective view of an embodiment in a pre-distraction phase. FIG. 2 is a perspective view of an embodiment in a post-distraction phase. FIG. 3 is a cross-sectional view and top view of a shaft. FIG. 4A is a side view and top view of the main body embodying a Morse taper configuration. FIG. 4B is a cross-sectional view of FIG. 4A. FIGS. 5A-C are cross-sectional views of an assembly of the disclosure embodying a Morse taper, in a pre-, mid-, and full-distraction position, respectively. FIG. 6A is a side view and top view of the main body embodying a hex abutment configuration. FIG. 6B is a cross-sectional view of FIG. 6B. FIGS. 7A-C are perspective views of an assembly of the disclosure embodying a hex abutment concept, in a pre-, mid-, and full-distraction position, respectively. FIG. 7D is a cross-section view of 7C. FIG. 8 is a cross-sectional view of a base. FIG. 9 is a cross sectional view and top view of a device that includes a slot to drive the device into a bone. FIG. 10 is a side view of an embodiment in which the base includes pins that engage the main body. FIG. 11 is a side view of a device in which a finger on the base interdigitates with the exterior surface of the main body. FIG. 12 is a side view of a device in which the base telescopically engages the main body. DETAILED DESCRIPTION OF THE INVENTION Turning first to FIG. 1, there is shown a distraction/implant device 10 (device) in a pre-distraction phase or position. As shown in this embodiment, the gingiva or gum tissue 23 has been cut to expose the bone 20 of an upper or lower jaw. In the embodiment shown, a hole may have been drilled in the bone 20 to accommodate the insertion of a device 10. The device 10 as shown includes a main body 24, base 26 and an elongated member or shaft 22. In certain methods of use of the device as shown in FIG. 1, the bone is tapped to accommodate external threads 30 that may be provided on the main body 24. External threads may also be present on the base 26. The device 10 is inserted into position in the pre-drilled hole, and in certain embodiments, screwed into the hole using the external threads. As seen in FIG. 1, the device may be implanted to a depth such that the top 28 of the main body is positioned near the crest of the bone 20 and the elongated member 22 extends above the bone. An osteotomy (cut made in the jaw bone) is just below the device 10 to create superior osteotomized bone segments 20 (superior segments) and inferior osteotomized bone segments 21 (inferior segments), which may be separated by a gap 32. During use, after the device is in place, the gingiva (gum tissue) 23 is closed. While the device 10 is in the pre-distraction position, as shown in FIG. 1, for example, a base 26 is adjacent to and may contact a main body 24 of the device. As shown in FIG. 5A, in the pre-distraction position an elongated member or shaft passes through an opening or internal bore 50 of the main body 24 and extends into the cavity 66 of the base 26. The bottom 62 of the shaft 22 may rest on the base, against the bottom of the cavity, or on base cap 64 to provide a distraction platform. The internal bore 50 preferably includes internal threading 52 that mates with external threading 42 of the shaft 22, so that turning of the shaft 22 with respect to the main body 24, or turning of the main body 24 with respect to the shaft 22 results in displacement of the main body 24 along the shaft 22. Other structures that allow implementation of a controllable, incremental movement of an elongated member 22 through a main body 24 may also be used in certain embodiments. For example, one may use a ratcheting arrangement including one or more notches on the elongated member that interact with a projection or tooth to control the motion, or one may utilize one or projections on an elongated member to interact with one or more slots, for example, included in a main body 24. Now turning to FIG. 2, an embodiment of the disclosure is shown in a post-distraction phase. Approximately three to seven days after a device 10 is implanted, or at a time determined by the practitioner to be acceptable to avoid complications, a shaft 22 of the device 10 is activated, or turned, preferably using an activation device 60 (shown in FIG. 3), which is configured to interact with a wrench or other tool. In particular embodiments, an activation device 60 may be a square cavity configured to receive a square head of a wrench or driver. Upon turning the shaft 22 in the appropriate direction, as dictated by the threading in those embodiments employing threading, the shaft is urged by the threading to move through the internal bore 50 of the main body 24. The end of the shaft 62 abuts the base cap 64, which rests in or on the solid bone segment 21, providing a solid resistance for the shaft. Activating the shaft 22, therefore, may move the main body 24 away from the base 26, creating or enlarging a gap 32 between the superior bone segments 20 and the inferior bone segments 21. This action may stretch the bone callus between the superior segments 20 and the inferior segments 21, and encourage generation of new bone (callus) 40. This process may be repeated in small increments until the crest of the bone 20 reaches the desired height and the shaft 22, preferably no longer extends above the main body 24. After distraction, the device may be left in the bone and may be used as a permanent implant. In FIG. 3 there is illustrated an elongated member or shaft 22 of a device 10. The shaft 22 may include an activation device 60 external threading 42 and an end or base 62 for interacting with the base cap 64. A top view of a shaft is also shown, depicting an embodiment in which the activation device 60 is a square cavity for receiving a square headed wrench or driver. The length of distraction needed is determined by the practitioner based on the extent of bone loss or deficiency and a shaft 22 of the proper length is chosen for the distraction device. Typical distraction lengths may include any length from about 2 millimeters, up to about 20 millimeters, and would include, of course, any length in between. In certain embodiments, shafts or elongated members may be provided in various lengths, to be selected and used interchangeably as needed. In such a packaging arrangement shafts of from about 5 millimeters to about 8 millimeters to about 11 millimeters to about 15 millimeters or even to about 18 millimeters in length may be included in any combination as a set, for example. It is also understood that a shaft may be shortened as needed by a practitioner or other user by cutting, sawing or grinding, for example. All such modified shafts would also fall within the scope and spirit of the present disclosure. One example of a device is shown in cross-section in FIGS. 5A-5C, which demonstrate a device 10 in a pre-distraction position (FIG. 5A), a mid-distraction position (FIG. 5B) and a post-distraction position (FIG. 5C). The base 26 and the main body 24 are adjacent in the pre-distraction position, and the shaft 22 extends above the main body 24. As distraction progresses, the main body 24 travels along the shaft 22, moving away from the base 26 as shown in FIG. 5B, until the distraction is complete (FIG. 5C). FIG. 5C shows the main body 24 as having moved along the shaft 22 until only the top of the shaft is contained within the main body 24. Although there is no requirement that the main body 24 move that far, preferably the top of the shaft 22 is far enough down in the internal bore 50 that it does not interfere with any abutment that is to be attached to the top of the implant device. As discussed above, the main body 24 and the base 26 may be urged apart by the interaction of internal threading 52 of the internal bore 50 of main body 24 and the external threading 42 of the shaft 22 as the shaft 22 is turned by an activation wrench, for example. The cavity 66 of the base 26 holds the shaft end 62 and may allow the shaft 22 to rotate freely against the base cap 64, thus providing a solid distraction platform against which the force of the turning threads may be applied, urging the main body 24 to move along the shaft 22. In certain embodiments the bottom 62 of the shaft 22 may be of a larger diameter than the entrance 70 into the cavity 66 such that the shaft 22 is retained within the base 26, and freely rotates but is not easily removable. Such an arrangement may be helpful to a practitioner in inserting the device. In certain embodiments the entrance 70 may be large enough with respect to the end 62 of the shaft 22 so that the shaft is easily insertable and removable. In certain preferred embodiments, the device 10 comprises a top 28 that is configured to be compatible with a dentition abutment, so that an abutment or restorative fixture may be attached thereto. The top 28 of a device 10, which may contain a connector for an abutment may be designed to be compatible with an abutment or fixture of any size or shape known in the art. As such, the device 10 may include an external member or projection (male connector) that is configured to mate with a complementary internal shape (female connector) contained in an abutment. Alternatively the device 10 may include an internal cavity or female connector configured to mate with an external or male connector contained on an abutment. The described connectors may be of any appropriate shape and are in many cases hexagonal. Any polygonal shape such as a square, a triangle, a rectangle, an octagon or a dodecagon, for example may also be used. Irregular shapes may also be used, such as a shape that orients the abutment in a particular direction relative to the implant device. Also contemplated are junctions of the device and an abutment in which projections are present on a device and offset projections are also present on the abutment so that the two sets of projections slide past each other during use to form a tight fit. This type of connection may be particularly useful as radial projections in a circular connector. Typically abutments are attached by a screw or other securing means. In such embodiments, the connector of the abutment has a hole through the center thereof, which may or may not be threaded or provide other appropriate means for securing the connection. In a preferred embodiment, a hole or threaded opening through an abutment connector is alignable with the bore or opening 50 in a device 10 when the connectors arc joined to form a contiguous channel for connection of an abutment. Should the opening in the abutment not be threaded, a screw may still be used that is compatible with threading in the internal bore 50 of a device 10. This threading may also be used in the distraction process when the abutment screw and a shaft 22 have the same size and pitch threading. In certain embodiments, a shaft 22 may have a smaller diameter than an abutment screw so that the shaft does not contact the threads in an upper portion of the bore 50. As used herein the term "bore" is meant to describe a structural feature of a device that may be threaded or unthreaded, and the term is not meant to limit the structural feature to any particular method of manufacture or configuration. An opening 50, through a device 10 may be described as a bore, tunnel, channel, hole, opening, passage, duct, conduit, or the like. FIGS. 4A and 4B depict an embodiment of the disclosure in which a connector 54 of a device is configured to be compatible with an abutment configured in an 8° Morse taper 58, as is well known in the art. Also shown in FIG. 4B is an internal hexagon configuration 56 used for driving or screwing the device into the bone. FIGS. 6A and 6B depict an embodiment in which another type of standard abutment may be attached to an implant device. This embodiment comprises a top 28 of the main body 24 comprising an external hexagon 44 for attachment of compatible standard abutments known in the art. The hex 44 may also serve to drive or screw the device into the bone. FIGS. 7A-7C depict an external hex embodiment in the pre-distraction, mid-distraction and post-distraction positions, respectively. Other abutment connection mechanisms, such as a spline configuration, an internal hexagon, a screw retained abutment, a cement retained abutment, an exterior square post, an exterior octagonal post, an internal square, an internal octagon, or others that are currently known or may be developed in the future may also be compatible with the implant devices disclosed herein. Appropriate abutment connections may also be used to drive or screw the device into a bone. Configurations for driving the device would also include, but would not be limited to external or internal polygons such as squares, triangles, hexagons, octagons, dodecagons, slots, crossed slots, or star patterns, for example. FIG. 9 depicts an embodiment of the device configured to attach to an abutment with a Morse taper configuration and in which a slot 74 is used to drive the device into bone. FIG. 8 is a cross-sectional view of a base 26. A base may include a cavity or a closed ended hole 66 in the base 26 and a base cap 64. An opening 70 into the cavity 66 may be narrower than the cavity in order to retain a shaft end 62 within the base, and still allow the shaft to rotate freely against the base cap 64. In such embodiments, the shaft end 62 is smaller in diameter than the cavity 66, but larger in diameter than the opening 70. In certain embodiments the shaft end 62 may pass freely through the opening 70 for easy removal of a shaft 22. The base may be formed or milled from a single piece, or it may be constructed of at least two pieces and welded or otherwise bonded together. The base may provide external threading to facilitate placement of the device in a predrilled hole, or the external sides may be smooth or textured. The exterior of a base may also be coated as described above regarding a main body 24. The internal cavity 66 is configured to align with an internal bore or duct 50 of a main body 24, during use, however the cavity 66 may be of a slightly larger diameter and unthreaded in order to allow the shaft 22 to rotate freely in the cavity 66. FIGS. 10-12 show embodiments of the disclosed devices that include various types of interactions between the main body and base. In the embodiment shown in FIG. 10, a plurality of pins 80 extend upward from the proximal surface of the base 26 and slide into holes in the main body 24 when the device is assembled. The device is shown in a slightly distracted position. This arrangement prevents the base from rotating with respect to the main body during activation of the elongated member 22, but does not prevent rotation of the elongated member with respect to the main body or base. FIG. 11 shows an embodiment in which one or more fingers 82 project from the proximal surface of the base 26 and are configured to fit into the same number of grooves on the surface of the main body 24. In this embodiment, as in the pin arrangement, the base is prevented from rotating with respect to the main body during activation of the elongated member 22, but the elongated member is free to rotate with respect to the main body and the base. FIG. 12 shows an embodiment in which the base 26 includes a cylindrical projection that telescopically fits into a groove in the main body 24. The projection may be a complete or partial cylinder. In embodiments that are partially cylindrical, such that a two dimensional projection is one or more arcs rather than a complete circle, the base would again be prevented from rotating with respect to the main body. In the embodiments shown in FIGS. 10-12, an external hex is shown for driving the devices into the bone. It is understood that any means as described herein for driving the device into the bone, and also for attaching an abutment, or any combination of these could be combined with these embodiments. In the practice of the methods and use of the devices disclosed herein, the device 10 may be left in place after the full distraction has been accomplished to serve as a permanent implant device. Typically, after distraction is complete, a temporary abutment may be attached to the implant for a period of from four to six months and then replaced with a permanent abutment in order to restore dentition.
Disclosed is an internal mandibular distractor comprising a substantially cylindrical main body, a base, and a shaft. The device is used to gradually separate osteotomized bone sections to promote new bone growth in an area of bone loss. The device is then left in the jaw to also serve as a permanent dental implant for restoring dentition.
0
BACKGROUND [0001] The invention relates generally to mounting apparatus, and more particularly to mounts for transom-mounted trolling motors. SUMMARY [0002] In one embodiment, a trolling motor mount includes a mounting base, a bracket, and a lock. The mounting base has a cavity extending therethrough and a motor receiving portion configured to clamp a trolling motor thereon. The bracket is pivotably coupled to the mounting base for rotation generally perpendicular to the mounting base cavity. The bracket selectively defines a lower edge of the mounting base cavity, and the bracket is slidable as well as pivotable relative to the mounting base. The lock is operably coupled to the mounting base for removably fastening the mounting base to a watercraft. [0003] In another embodiment, a trolling motor mount includes a mounting base, two locks, and a bracket operably coupled to the mounting base. The mounting base has two side walls, a motor receiving portion for clamping a trolling motor thereon, and a cavity configured to latch on to a side of a watercraft. The cavity extends through and between the two side walls. One of the locks is adjacent each side wall, and the locks are rotatably coupled to the mounting base for removably fastening the mounting base to a watercraft. The locks are rotatable generally perpendicular to each of three interior walls defining the cavity, and the locks are further movable to enter and exit the cavity varying degrees. [0004] In yet another embodiment, a trolling motor mount includes a mounting base, a bracket, and a lock. The mounting base has a cavity extending therethrough and a motor receiving portion configured to clamp a trolling motor thereon. The bracket is pivotably coupled to the mounting base, and the bracket has at least a front surface, two side surfaces, and at least one channel for allowing the bracket to be slidable relative to the mounting base. The lock is operably coupled to the mounting base for removably fastening the mounting base to a watercraft. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS [0005] Illustrative embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein: [0006] FIG. 1 is a front perspective view of an adjustable mount; [0007] FIG. 2 is an exploded view of the adjustable mount of FIG. 1 ; [0008] FIG. 3 is a side perspective view of the adjustable mount of FIG. 1 , while it is mounted to a watercraft; [0009] FIG. 4 is another perspective view of the adjustable mount of FIG. 1 , while it is mounted to the watercraft; [0010] FIG. 5 a is a rear perspective view of the adjustable mount of FIG. 1 , while it is mounted to the watercraft; [0011] FIG. 5 b is another side perspective view of the adjustable mount of FIG. 1 , while it is mounted to watercraft; [0012] FIG. 6 is another perspective view of the adjustable mount of FIG. 1 , wherein a trolling motor attached to the adjustable mount is in a stowed position; [0013] FIG. 7 is another perspective view of the adjustable mount of FIG. 1 , wherein the adjustable mount is mounted to a watercraft differently than shown in FIG. 3 . DETAILED DESCRIPTION [0014] FIGS. 1-7 show one embodiment of an adjustable mount 100 for use in mounting trolling motors 400 on a watercraft 300 . As described in more detail below, the adjustable mount 100 includes a mounting base 110 , a bracket 150 , and at least one lock 180 . [0015] As shown in FIG. 1 , the mounting base 110 may have an interior surface 112 , an exterior surface 114 , and two side surfaces 116 on opposite ends of the base 110 . The two mounting base side surfaces 116 each have an interior wall 116 i and an exterior wall 116 e. The two side surface interior walls 116 i face each other, while the two side surface exterior walls 116 e face away from each other. [0016] The mounting base 110 may have two channel surfaces 126 that are adjacent and substantially parallel to the side surfaces 116 . Each channel surface 126 has an interior wall 126 i that faces the side surface interior wall 116 i, and an exterior wall 126 e that faces away from the nearest side surface interior wall 116 i. Channels 128 are formed between the channel surface interior walls 126 i and the side surface interior walls 116 i. [0017] The mounting base 110 has a motor receiving portion 118 with a top wall 118 t, a front wall 118 f, and a rear surface 119 , each of which extend between, and are in contact with the two side surface interior walls 116 i. The rear surface 119 has an exterior wall 119 e and an interior wall 119 i ( FIG. 5 a ). The motor receiving portion front wall 118 f is part of the base interior surface 112 , while the motor receiving portion rear surface 119 is part of the base exterior surface 114 . The motor receiving portion top wall 118 t is substantially perpendicular to the motor receiving portion front wall 118 f and the rear surface exterior wall 119 e. [0018] The motor receiving portion 118 may have a support surface 120 ( FIG. 1 ) that is part of the base interior surface 112 , and that has an exterior wall 120 e and an interior wall 120 i. The support surface exterior wall 120 e lies beneath and is generally perpendicular to the motor receiving portion front wall 118 f. A small part of the exterior wall 120 e is in contact with the side surface interior walls 116 i, while the remaining part of the support surface exterior wall 120 e is in contact with and terminates at the channel surface exterior wall 126 e. [0019] The mounting base interior surface 112 may also include a border surface 121 ( FIG. 1 ), which is substantially parallel to the motor receiving portion front wall 118 F. The border surface 121 lies beneath and is substantially perpendicular to the motor receiving portion support wall 120 , and has an interior wall 121 i and an exterior wall 121 e. The border surface exterior wall 121 e extends between and contacts the channel surface exterior walls 126 e. Thus, as shown in FIG. 1 , the motor receiving portion front wall 118 f, the support surface exterior wall 120 e, and the border surface exterior wall 121 e create a stepped configuration. [0020] A cavity 124 is defined by the interior wall 119 i, the interior wall 120 i, and the interior wall 121 i, and extends through the base side surfaces 116 . A groove 122 may further be included, as shown in FIG. 1 . [0021] Attention is now directed to the bracket 150 ( FIGS. 1 and 5 a through 6 ), which has a front surface 160 and two side surfaces 162 . The front surface 160 has an interior wall 160 i and an exterior wall 160 e, and the side surfaces 162 each have an interior wall 162 i and an exterior wall 162 e. The bracket 150 may have two channels 164 that extend through a majority of each side surface 162 , and that may extend partway through the front surface 160 . [0022] As shown in FIGS. 1-2 , the bracket side surfaces 162 are connected to the mounting base side surfaces 116 with bolts 166 which go through the channels 164 , such that the bracket side interior wall 162 i is adjacent and may come into contact with the mount side surface exterior wall 116 e. The bolts 166 may be used in conjunction with a washer 168 to connect the bracket 150 to the mounting base 110 . And, with the bolts 166 being the pivot points, the bracket 150 may be rotatable substantially perpendicular to the X-axis ( FIG. 1 ). Moreover, by virtue of the channels 164 , the bracket 150 may be moved forwards or backwards, such that the front surface interior wall 160 i gets closer to or moves father away from the rear surface interior wall 119 i. Thus, the bracket 150 is both rotatable around the bolts 166 and movable along the channels 164 . As shown in FIG. 1 , the front surface 160 and the side surfaces 162 of the bracket 150 may be of unitary construction; however, it is possible for the bracket 150 to not have an extended front surface 160 , or for the bracket 150 to have a front surface 160 that is not constructed unitarily with the side surfaces 162 . As shown in FIG. 2 , the rear surface interior wall 119 i may have a ripple-like pattern 115 , which may enhance the visual appearance of the adjustable mount 100 , and also enhance the structural integrity of the mounting base 110 . [0023] As shown throughout the drawings, the adjustable mount 100 has two locks 180 , though more of fewer locks 180 may also be appropriate. The locks 180 include threaded bolts 182 , knobs 184 extending from the bolts 182 , and ball and cap joint clamps 186 . The knobs 184 can be rotated such that the clamps 186 move closer to or father away from the interior wall 119 i. In use, an object can be inserted into the cavity 124 , and then the clamps 186 can be tightened to ensure that the clamps 186 grip the object firmly. While the locks 180 are shown and described as having threaded bolts 182 , knobs 184 , and ball and cap clamps 186 , those skilled in the art will readily understand that the locks 180 may not include the knobs 184 and may not be threaded, or that the locks 180 may utilize different mechanisms to clamp the object than the threaded bolts 182 or the ball and joint clamps 186 . [0024] Threaded bearings 188 ( FIGS. 2-3 ) extend from the base side surfaces 116 through the respective channels 128 and into the respective channel surfaces 126 , and are configured to receive the threaded bolts 182 . The threaded bolts 182 are connected to the mount 100 by the threaded bearings 188 such that the head of each threaded bolt 182 is to one side of a respective threaded bearing 188 , while the clamps 186 are on the other side of the threaded bearings 188 . The threaded bearings 188 are rotatable substantially perpendicular to the X-axis ( FIG. 1 ), and so, the threaded bolts 182 may be rotated substantially perpendicular to the X-axis with the threaded bearings 188 as the pivot points. The channels 128 ensure that the threaded bolts 182 can rotate with the threaded bearings 188 unobstructed. Thus, the clamps 186 can be moved closer to or farther away from the interior wall 119 by virtue of the threading of bolts 182 , and the clamps 186 can be rotated closer or farther away from the groove top wall 122 t by virtue of the rotatable threaded bearings 188 . [0025] Attention is now specifically directed to the mount 100 in use with a watercraft 300 , as shown in FIGS. 3-7 . The watercraft 300 includes a side surface 302 having a front wall 302 f, a top wall 302 t, and a rear wall 302 r. The mount 100 is moved towards the watercraft side surface 302 such that the watercraft side surface 302 enters the cavity 124 , with the support surface interior wall 120 i being generally above the watercraft top wall 302 t ( FIG. 3 ), the border surface interior wall 121 i being generally in front of the watercraft front wall 302 f ( FIG. 4 ), and the rear surface interior wall 119 i being generally behind the watercraft rear wall 302 r ( FIG. 5 a ); in other words, the mounting base interior surface 112 is generally atop the watercraft side 302 or inside the watercraft 300 , while the mounting base exterior surface 114 is generally outside the watercraft 300 . It is possible for the watercraft top, front, and rear walls 302 t, 302 f, 302 r to align perfectly with the interior walls 120 i, 121 i, 119 i respectively; however, such alignment is not typical. [0026] A trolling motor 400 ( FIGS. 3 through 7 ) may be clamped onto the motor receiving portion 118 with trolling motor clamps 402 ( FIG. 4 ). As can be seen from viewing FIGS. 4 and 5 a together, the clamps 402 of the trolling motor 400 can be clamped onto the motor receiving portion front wall 118 f such that a trolling motor rear wall 404 firmly grips the base rear surface exterior wall 119 e. The trolling motor 400 may also be placed in a stowed position, as shown in FIG. 6 , or in an upright position as shown in FIGS. 3-5 b and 7 . [0027] The bracket 150 , as shown in FIG. 5 b , may be rotated around the bolts 166 and moved forwards or backwards along the channels 164 such that all or part of the bracket front surface exterior wall 160 e comes into contact with and grips a watercraft hull 304 . The bolts 166 may then be tightened such that the bracket front surface exterior wall 160 e tightly grips the watercraft hull 304 . [0028] The trolling motor 400 , once it is attached to the trolling mount 100 and placed in the operative position, may remain vertical and contact the water at about 90 degrees regardless of which side of the watercraft 300 the mount 100 is attached to. The rotatable bracket 150 can be adjusted to ensure that this positioning is achieved. More particularly, the rotatable bracket 150 can be rotated around the bolts 166 , and moved inward and outward along channels 164 such that all or part of the bracket front surface exterior wall 160 e conforms to the boat hull 304 at any side, or at least firmly grips the boat hull 304 at any side. For example, the mount 100 is attached to a different side surface 302 of the watercraft 300 in FIG. 7 as compared to FIG. 3 , as manifested by the different angles at which the mount 100 is gripping the water craft side 302 (compare e.g., the clamps 186 and interior wall 120 i in FIG. 7 , and FIG. 3 ); however, by virtue of the adjustable bracket 150 , the trolling motor 400 may be attached to the mount 100 such that the trolling motor 400 is substantially perpendicular to the water upon contact in both locations. [0029] The clamps 186 (which are initially retracted such that they come close to the threaded bearing 188 and do not obstruct the cavity 124 ) may be tightened after the bracket 150 is adjusted, such that they clamp on to the watercraft 300 ( FIG. 3 ). As discussed above, by virtue of the rotatable threaded bearing 188 , the threaded bolts 182 can be moved perpendicular to the X-axis ( FIG. 1 ) along the channels 128 such that the clamps 186 clamp different parts of the watercraft 300 . The clamps 186 can be adjusted along with the bracket 150 to ensure that the trolling motor 400 remains substantially perpendicular to the water upon contact. [0030] In sum, the mount 100 may allow a trolling motor 400 to be attached to different sides of a watercraft 300 , including the bow or the stern, regardless of the hull angle, while ensuring that the trolling motor 400 remains substantially perpendicular to the water or as otherwise desired in its operative position. [0031] Many different arrangements of the various components depicted, as well as components not shown, are possible without departing from the spirit and scope of the present invention. Embodiments of the present invention have been described with the intent to be illustrative rather than restrictive. Alternative embodiments will become apparent to those skilled in the art that do not depart from its scope. A skilled artisan may develop alternative means of implementing the aforementioned improvements without departing from the scope of the present invention. [0032] It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations and are contemplated within the scope of the claims. Not all steps listed in the various figures need be carried out in the specific order described.
One trolling motor mount includes a mounting base having a cavity extending therethrough and a motor receiving portion configured to clamp a trolling motor thereon, a bracket, and a lock operably coupled to the base for removably fastening the base to a watercraft. The bracket is pivotably coupled to the base for rotation generally perpendicular to the cavity, and selectively defines a lower edge of the cavity. The bracket is also slidable relative to the base. Another trolling motor mount includes a mounting base having a cavity extending therethrough and a motor receiving portion configured to clamp a trolling motor thereon, a bracket pivotably coupled to the base, and a lock operably coupled to the base for removably fastening the base to a watercraft. The bracket has front and two side surfaces, and at least one channel for allowing the bracket to slide relative to the base.
1
COPYRIGHT A portion of the disclosure of this patent document contains material which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent disclosure, as it appears in the Patent and Trademark Office patent files or records, but otherwise reserves all copyright rights whatsoever. FIELD OF THE INVENTION The invention relates generally to a device and method suitable for use in monitoring blood pressure. BACKGROUND In medicine it is often desirable to monitor blood pressure, for example, over the course of an invasive procedure. Blood pressure is most reliably measured using an arterial line. The fitting of an arterial line is invasive and is most commonly performed under anaesthetic. Ways and means of measuring blood pressure non-invasively are also known. The most common method of measuring blood pressure non-invasively is via an inflatable cuff placed around the upper arm. Whilst accurate, these measurements obstruct blood flow to the limb and therefore may only be taken intermittently. Alternative methods of measuring blood pressure that maintain the blood flow through the interrogated artery are known. The “vascular unloading technique,” as described in U.S. Pat. No. 6,669,648, U.S. Pat. No. 7,390,301 and U.S. Pat. No. 8,114,025 and US patent applications US 2011/0105917 and US 2011/0105918, continuously measures the blood pressure through an inflatable cuff fitted to a finger. This known method allows blood flow to be maintained through the interrogated artery thus making long term continuous measurement possible. The pressure load on and blood congestion in the interrogated artery is limited by providing a second finger cuff on a second finger and alternating between the two cuffs when taking blood pressure measurements. It will be appreciated that it may not be possible to directly compare blood pressure measurements taken with different measurement techniques or on different points of the body, not least due to the difference in blood pressure between the smaller arteries, for example in a finger, and the major arteries. For this reason it may be beneficial to calibrate blood pressure measurements. SUMMARY OF INVENTION According to an embodiment of the invention there is provided a device for use in monitoring blood pressure comprising a controller configured to monitor a first blood pressure measurement based on a first blood pressure signal. The controller is further configured to initiate acquiring a second blood pressure measurement based on a second blood pressure signal if the first blood pressure measurement exceeds a predetermined threshold. The decision to initiate acquiring the second blood pressure measurement is based on only one blood pressure measurement, such as the first blood pressure measurement. By focussing the monitoring of the blood pressure measurement on a single measurement discomfort to the patient is further reduced. According to a second embodiment of the invention there is provided a method of monitoring blood pressure comprising receiving a first blood pressure signal, monitoring a first blood pressure measurement based on the first blood pressure signal and initiating acquiring a second blood pressure measurement based on a second blood pressure signal if the first blood pressure measurement exceeds a predetermined threshold. The decision to initiate acquiring the second blood pressure measurement is based on only one blood pressure measurement. The predetermined threshold may be a minimum or maximum threshold. The first blood pressure signal may be a continuous and/or non-invasive blood pressure signal, such as that provided from a single finger cuff (such as one of the finger cuffs described in the above US patent, for example). The second blood pressure signal may be provided by or obtained from/through measurement equipment/spygmamometer using an inflatable arm cuff. The device for use in monitoring blood pressure may itself comprise some or all pressure cuffs or other devices needed for acquiring the first and/or second blood pressure signals. The device may thus further comprise an arm cuff and/or a finger cuff. Alternatively, the device may simply be a monitoring and control unit that receives blood pressure signals from known blood pressure measurement devices already in clinical use. The device may be form part of a haemodynamic monitor. In monitoring the first blood pressure measurement the controller can determine when it is desirable (in keeping with the above discussed threshold) for the calibration of the first blood pressure measurement to be checked. By only initiating a calibration measurement when the blood pressure measurement exceeds a predetermined threshold the number of calibration measurements are minimised. This is advantageous as a large amount of secondary calibration measurements may cause the subject discomfort and may temporarily interfere with the first blood pressure measurement. The controller may be configured to base the decision to initiate acquiring the second blood pressure measurement on pulse pressure calculated using the first blood pressure signal. The pulse pressure (PP) is the difference between the systolic (P sys ) and diastolic (P dia ) pressures, that is: PP=P sys −P dia The controller may initiate acquiring the second blood pressure measurement if the pulse pressure exceeds a predetermined threshold. Pulse pressure usually stays within a certain range. A healthy resting pulse pressure for a normal adult is around 30-40 mmHG. If very high or very low pulse pressures are measured then such values can be taken as an indication that the calibration of the first blood pressure measurement may require checking. In one embodiment the controller is configured to initiate acquiring the second blood pressure measurement if the pulse pressure falls below 15 mmHG and/or if the pulse pressure exceeds 150 mmHG. Additionally or alternatively a large change in pulse pressure occurring over a short time may be an indication that the calibration of a blood pressure measurement should be checked. The controller may be configured to initiate acquiring the second blood pressure measurement if the change in pulse pressure over a period of time exceeds a predetermined threshold. The period of time may be a fixed time period, such as over the preceding 90 seconds. In one embodiment the controller is configured to initiate acquiring the second blood pressure measurement if the pulse pressure decreases by more than 50% within 90 seconds and/or if the pulse pressure increases by more than 100% within 90 seconds. Alternatively or additionally changes in pulse pressure can be monitored over a period of time that has started at a fixed point in time. The controller may, for example, be configured to initiate acquiring the second blood pressure measurement if the pulse pressure changes by a predetermined amount since the last previous acquisition of the second blood pressure signal. An increase in pulse pressure by more than 60% since a previous second blood pressure measurement and/or a decrease in pulse pressure by more than 150% since a previous second blood pressure measurement have been particularly found to be indicative of a situation where a check of the calibration of the blood pressure measurement is desirable. Such large variations in pulse pressure over a short period of time are not normally encountered as a result of physiological or pathological events and can therefore be good indicators that the calibration of the first blood pressure signal may require checking. A further parameter that has been found to be a good indicator that a calibration check may be required is the med-dia ratio. The med-dia ratio is the difference between the mean arterial pressure (MAP) and the diastolic pressure (P dia ) divided by the pulse pressure (PP), i.e.: MD = MAP - P dia P sys - P dia The controller may be configured to initiate acquiring a second blood pressure measurement based on med-dia-ratio calculated based on the first blood pressure signal. The controller may be configured to initiate acquiring the second blood pressure measurement if the med-dia-ratio exceeds a predetermined threshold. In one embodiment, the controller is configured to initiate acquiring the second blood pressure measurement if the med-dia-ratio falls below 21% and/or exceeds 51%. Once the second blood pressure measurement has been received/acquired, the first blood pressure measurement may be re-calibrated based on the second blood pressure measurement. Calibrating the first blood pressure measurement may involve amplifying it or adding a bias to it so that certain values closely match those of the second blood pressure measurement. On the other hand, if the first and second blood pressure measurements do not differ significantly, then the first blood pressure measurement may simply be retained as accurate and recalibration may not be performed. The controller may be configured to calibrate the first blood pressure measurement based on the second blood pressure measurement if it differs from the second blood pressure measurement by a predetermined amount. The controller may, for example be configured/programmed to compare the systolic blood pressure values of the first and second blood pressure measurements or the diastolic blood pressure values of these two measurements, or both. It was found that, if the first and second blood pressure measurements differ by 13 mmHG or less re-calibration can be omitted and the controller maybe configured accordingly. Where a calibration check has not resulted in recalibration, i.e. where a difference between the first and second blood pressure measurements was deemed too small to warrant re-calibrating the first blood pressure measurement, it may be advantageous to temporarily inhibit automatic recalibration checks to prevent the device from repeatedly rechecking measurements that are known to be accurately calibrated. In one embodiment, the controller is configured to inhibit any steps of initiating acquisition of a second blood pressure measurement if a second blood pressure measurement has been taken during a predetermined preceding period of time and the first blood pressure measurement was not re-calibrated. The decision to inhibit initiating the acquisition of a second blood pressure signal may be applied by the controller so that none of a plurality of thresholds is used for assessing the need for acquiring a second blood pressure signal in the predetermined period of time. The controller may also configured to not initiate acquiring a second blood pressure measurement based on a specific predetermined threshold being exceeded, if, during a predetermined preceding period of time, a second blood pressure measurement has been taken based on said predetermined threshold being exceeded and the first blood pressure measurement was not recalibrated. This is particularly advantageous for absolute value thresholds, such as maximum and minimum pulse pressure or med-dia-ratio. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be understood and appreciated more fully from the following detailed description taken in conjunction with drawings in which: FIG. 1 shows a system for continuously measuring blood pressure and automatically recalibrating, in accordance with an embodiment of the present invention; FIG. 2 shows a flowchart detailing a method for determining whether it is desirable to check the calibration of a monitored blood pressure signal; FIG. 3A illustrates the definition of pulse pressure; and, FIG. 3B illustrates the calibration of a blood pressure measurement. DETAILED DESCRIPTION FIG. 1 shows a system for continuously monitoring blood pressure and automatically recalibrating, in accordance with an embodiment of the present invention. Blood pressure monitor 100 is connected via continuous BP interface 106 to a set of finger cuffs 120 (only one of which is used at any one time) to receive a continuous blood pressure signal, and via calibration BP interface 108 to arm cuff 140 to receive a calibration blood pressure signal when requested. Interfaces 106 and 108 are connected to controller 102 which may calculate a calibrated continuous blood pressure signal based on the blood pressure signals received from finger cuffs 120 and arm cuff 140 through interfaces 106 and 108 . The controller executes its functions based on executable software code stored in memory 104 . The controller 102 analyses the calibrated continuous blood pressure signal and issues instructions to the arm cuff blood pressure measurement device 140 to take a calibration blood pressure measurement when a threshold associated with the calibrated continuous blood pressure signal exceeds a predetermined threshold (as discussed with reference to FIG. 2 ). The controller 102 may issue an instruction for the arm cuff 140 to take a calibration blood pressure measurement at other times, such as at the start of a continuous blood pressure measurement or when requested by the user via user interface 110 . Blood pressure signals may be stored in the memory 104 for future analysis and patient records. The calibration blood pressure signal is analysed by the controller 102 and used to calculate a calibration function. The calibration function is applied by the controller 102 to the continuous blood pressure signal to calculate a calibrated blood pressure signal. The calibrated blood pressure signal may then be outputted via output 112 . The output 112 may be a monitor, a network connection, a memory device or any other output. The finger cuffs 120 may be such as those disclosed in US patents U.S. Pat. No. 6,669,648 and U.S. Pat. No. 7,390,301 and US patent application US 2012/0059233. Two finger cuffs 120 are provided which may measure the blood pressure in two fingers. One finger is measured at a time and the measurements are periodically swapped between each finger in order to reduce the discomfort and stress applied to the fingers. Upon changeover, the new finger measurements are, in the embodiment, calibrated against the last continuous blood pressure values without any arm cuff measurements being taken. The finger cuffs 120 may be located on the arm opposite to the arm carrying the arm cuff 140 to avoid an activation of the arm cuff 140 interrupting a measurement using a finger cuff 120 . Alternatively, the arm 140 and finger cuffs 120 may be located on the same arm to allow the other arm to be free for other uses during the medical procedure. It should be noted that other means of continuously measuring blood pressure and of providing a calibration blood pressure signal may be used and that the present invention is not limited to working in conjunction with finger and arm cuffs. FIG. 2 shows a flowchart detailing a method 200 for determining whether a continuous blood pressure signal requires recalibration, in accordance with an embodiment of the present invention. The method may be implemented by the apparatus described above. Before measurements are recorded the continuous blood pressure signal is initially calibrated 210 using a calibration blood pressure signal. The continuous blood pressure signal and calibration blood pressure signal may, for example, be obtained using the finger cuffs 120 and arm cuff 140 shown in FIG. 1 respectively. Using arm cuffs for calibration measurements is preferred as such measurements at present are considered the gold standard. Once the blood pressure signal has been calibrated, calibrated continuous blood pressure measurements may be taken 220 . The calibrated blood pressure signal is continuously monitored to check whether one or more preselected threshold values have been exceeded 230 . If one of the threshold values is exceeded, then a new calibration blood pressure measurement is taken 240 . If the calibrated continuous blood pressure measurement signal differs from the calibration signal by a predetermined amount, then the continuous blood pressure signal is recalibrated 260 . If the calibrated continuous blood pressure signal does not differ from the calibration signal then no calibration is required and measurement 220 is continued. It will be appreciated that step 250 may be omitted so that the continuous blood pressure signal is recalibrated whenever the threshold in step 230 is exceeded. Once the continuous blood pressure signal is recalibrated 260 , calibrated continuous blood pressure measurements are continued 220 . By continuously monitoring the blood pressure measurements and recalibrating whenever threshold values are exceeded, the number of calibration measurements may be limited whilst still ensuring the accuracy of the measurements. FIG. 3A shows typical blood pressure variations over a cardiac cycle. The ordinate displays blood pressure, whilst the abscissa shows time. The maximum pressure over one cardiac cycle is the systolic pressure (P sys ) whilst the minimum pressure is the diastolic pressure (P dia ). The average pressure over one cardiac cycle is the mean arterial pressure (MAP). The difference between the systolic (P sys ) and diastolic (P dia ) pressure is the pulse pressure (PP): PP=P sys −P dia It has been found that deviations in pulse pressure from expected patterns provide a good indication that the calibration of blood pressure measurements should be checked. In particular, it was found that, if the pulse pressure falls outside of a predetermined pressure range this could indicate that the blood pressure measurements are no longer accurate. A drop of pulse pressure to below about 15 mmHG or a rise of pulse pressure to above about 150 mmHG were, for example, found to occur sufficiently rarely in normal physiology that they can reliably be considered to indicate miss-calibration and can consequently be taken as an indicator that the calibration of the measurement should be checked. Additionally, it was found that a rapid change in pulse pressure may indicate that the calibration of the measurement may no longer be correct. The embodiment therefore uses a rate of change in pulse pressure as an additional or alternative trigger for checking the calibration of the blood pressure measurements. An arm cuff measurement for checking the calibration is in particular triggered if the pulse pressure decreases by more than 50% within 90 seconds or increases by more than 100% within 90 seconds. While this trigger event uses a predetermined fixed time period for assessing the rate of change of pulse pressure an alternative or additional way of assessing the rate of change is to consider the amount of change in pulse pressure from a set/defined point in time onwards. A large change in pulse pressure since the last calibration or calibration check, for example, may indicate that a check of the current calibration is required. In the embodiment the signal is recalibrated if the pulse pressure decreases by more than 60% since the last calibration or calibration check or increases by more than 150% since the last calibration or calibration check. A further parameter which was found to be a reliable indicator of mis-calibration is the med-dia ratio, that is the difference between the mean arterial pressure (MAP) and the diastolic pressure (P dia ) divided by the pulse pressure (PP), i.e.: MD = MAP - P dia P sys - P dia The med-dia ratio is approximately ⅓ under normal conditions as, at normal resting rates MAP can be approximated as: MAP ≈ 1 3 ⁢ P sys + 2 3 ⁢ P dia It has been found that a check of the calibration may be required if the med-dia ratio falls outside a predetermined band. In particular med-dia ratios of less than 21% (0.21) or more than 51% (0.51) have been identified as reliable triggers for calibration checks. In order to filter out short-term fluctuations, a moving average may be applied to the parameters measured, such as pulse pressure and med-dia-ratio. This should improve the signal to noise ratio, allowing for a clearer blood pressure signal, and ensure that noise or short-term miscalibrations do not cause initiation of a calibration check or recalibration. A further method of filtering such noise or short-term miscalibrations is a median filter applied to the parameters measured, where the median of the moving window is use instead of the moving average. Once a threshold has been exceeded, a calibration measurement is taken. This may be used to calibrate the continuous blood pressure signal; however, in order to maintain consistency of measurements, it may be beneficial to only recalibrate the calibrated continuous blood pressure signal if it differs from the calibration measurement by a predetermined amount. It has been found that calibration may be required if either the systolic or diastolic pressures of the calibrated signal differ from those measured in the calibration signal by 13 mmHG. In the embodiment the user is free to request re-calibration or a swap between finger cuffs used at any time. Where the user requests a calibration measurement, or where the user requests the finger cuff measurements to swap to the other finger, recalibration is performed regardless of the difference between the calibrated and calibration signals. If a calibration measurement does not differ sufficiently from the calibrated blood pressure measurement, then the system is likely to be calibrated correctly, and the device inhibits automatic re-calibration for a predetermined period, for example for five minutes in an embodiment. Furthermore, if a calibration check is initiated as a result of an absolute value exceeding a threshold, such as maximum pulse pressure, and no recalibration is required, then the threshold may be disregarded for a period afterwards, such as until the source of the blood pressure signal is next changed/finger cuffs are next swapped between fingers. Calibration measurements may also be taken between finger changes. In an embodiment a calibration measurement may, for example, be taken if the time elapsed since the last finger change or since the last calibration measurement is longer than four minutes. If a calibration measurement is being taken then any timed finger change may be delayed. FIG. 3B shows how a calibrated blood pressure signal may be calculated based on an input blood pressure signal and a second calibration blood pressure signal. The input blood pressure signal is amplified such that it has the same amplitude, or pulse pressure, as the calibration signal. This amplified blood pressure signal is offset by a bias pressure so that the mean arterial pressure is matched to the calibration signal. The final calibrated measurement should therefore have similar systolic and diastolic pressures to the calibration signal. It should be noted that calibration may involve only matching one of the pulse pressure or the mean arterial pressure. Equally, other factors may be used to calibrate the input signal. To more accurately calibrate an input continuous blood pressure signal, the average values over multiple cardiac cycles may be used, for instance, the last ten beats recorded in the continuous blood pressure signal. The factors calculated from the calibration signal are used to form a calibration function which is continuously applied to the input continuous blood pressure signal from the time of calibration onwards. When each recalibration is performed, a new calibration function is calculated and applied to the continuous blood pressure signal to provide a calibrated continuous blood pressure measurement. While certain embodiments have been described, the embodiments have been presented by way of example only, an area not intended to limit the scope of the inventions. Indeed, the novel methods, apparatus and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the methods and systems described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
A device and method for use in monitoring blood pressure. The device comprises a controller configured to monitor a first blood pressure measurement based on a first blood pressure signal. The controller is configured to initiate acquiring a second blood pressure measurement based on a second blood pressure signal if the first blood pressure measurement exceeds a predetermined threshold. The decision to initiate acquiring the second blood pressure measurement is based on only one blood pressure measurement.
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This is a division of application Ser. No. 08/127,862, filed Sep. 27, 1993, now U.S. Pat. No. 5,463,051. BACKGROUND OF THE INVENTION The present invention relates to a process for preparing intermediates useful in the preparation of benzazepines having activity as selective D1 receptor antagonists. U.S. Pat. No. 4,973,586 discloses fused benzazepines, and in particular the compound known as SCH 39166, having the structure ##STR4## as selective D1 antagonists useful in the treatment of psychoses, depression, pain and D1 dependent neurological disorders. Methods for preparing such compounds are also described therein. Berger, et al, J. Med. Chem., 32, 1913-1921 (1989), discloses a process for preparing SCH 39166 comprising acid promoted cyclization of a compound of the formula (1) to give a 1:1 mixture of cis and trans benzazepines (cis-2 and trans-2, respectively). Compound trans-2 is then converted to racemic compound I via a multi-step procedure. Compound I is resolved via its di-O,O'-p-tolyltartrate salt and hydrolyzed with HBr and HOAc to give SCH 39166. ##STR5## The prior art process suffers from several shortcomings. It is inefficient, producing a 1:1 mixture of cis and trans benzazepines in the cyclization step. In addition, conducting the resolution step at a late stage of the synthesis is very costly and adds further inefficiency. Therefore, it was desirable to develop a chemically efficient and cost effective process for preparing SCH 39166 of high optical purity. It was also desired that the resolution be performed at an early stage of the process or that the chiral centers be introduced using inexpensive chiral starting materials, thereby avoiding the need for resolution. SUMMARY OF THE INVENTION The present invention comprises a process for preparing a compound of the formula I ##STR6## comprising the steps: (a) Reacting an aziridinium salt of the formula ##STR7## wherein Q is a group of the formula ##STR8## wherein R is C 1 -C 6 alkyl, and X - is a counterion, with a reagent of the formula ##STR9## wherein M is selected from MgL, ZnL, TiL 3 , CeL 2 , MnL or CuL, and L is a halide selected from Br, Cl or I; to form a compound of the formula ##STR10## wherein Q is as defined above; and (b) cyclizing the product of step (a). The present invention further comprises a process, designated Process A, wherein the aziridinium salt of step (a) is prepared, as a racemate or a single enantiomer, by a process comprising the steps: (A1) epoxidizing 1,2-dihydronaphthalene to form an epoxide of the formula ##STR11## as a racemate by reacting with: (i) H 2 O 2 in the presence of a base; or as a single enantiomer by reacting with: (ii) NaOCl in the presence of Mn(III) salen catalyst; or (iii) OsO 4 in the presence of NMMO and dihydroquinine 4-chlorobenzoate, followed by treating the resulting cis diol with (C 6 H 5 ) 3 PBr 2 in the presence of a tertiary amine base; (A2) regioselectively reacting the epoxide of step (A1) with CH 3 NH 2 to form an aminoalcohol of the formula ##STR12## (A3) N-alkylating the aminoalcohol of step (A2) with a compound of the formula J-CH 2 --Q, wherein J is a leaving group, and Q is as defined above; and (A4) cyclizing the product of step (A3) by treating with an alkyllithium reagent and a sulfonyl chloride. In an alternative embodiment, the present invention further comprises a process, designated Process B, wherein the aziridinium salt of step (a) is prepared in optically active form by a process comprising the steps: (B1) Reacting S-(+)-2-amino-4-phenylbutanoic acid with ClCO 2 R 2 to form a carbamate of the formula ##STR13## wherein R 2 is benzyl or C 1 -C 6 alkyl; (B2) reacting the carbamate of step (B1) with a chlorinating agent, then cyclizing the resulting acid chloride by treating with a Lewis acid to form a ketone of the formula ##STR14## wherein R 2 is as defined above; (B3) reducing the ketone of step (B2) by reacting with a hydride reducing agent to form a compound of the formula ##STR15## (B4) reacting the product of step (B3) with a compound of the formula J-CH 2 --Q, wherein J and Q are as defined above; and (B5) cyclizing the product of step (B4) by treating with an alkyllithium reagent and a sulfonyl chloride. In a second alternative embodiment, the present invention further comprises a process, designated Process C, wherein the aziridinium salt of step (a) is prepared by a process comprising the steps: (C1) converting 1,2-dihydronaphthalene to an epoxide of the formula ##STR16## by the process of step (A1); (C2) reacting the epoxide of step (C1) with an amine of the formula HN(R 1 )--CH 2 --Q, wherein R 1 is H or CH 3 , and Q is as defined above, to form an amino alcohol of the formula ##STR17## (C3) (I) where R 1 is H, cyclizing the product of step (C2) to form an aziridine of the formula ##STR18## by reacting with: (i) (C 6 H 5 ) 3 PBr 2 ; or (ii) mesyl chloride or tosyl chloride in the presence of a tertiary amine base; followed by N-methylating the resulting aziridine by treating with: (iii) CF 3 SO 3 CH 3 ; or (iv) (CH 3 ) 3 OBF 4 ; or (II) where R 1 is CH 3 , cyclizing the product of step (C2) by treating with an alkyllithium reagent and a sulfonyl chloride. In a third alternative embodiment, the present invention further comprises a process, designated Process D, wherein the aziridinium salt of step (a) is prepared in optically active form by a process comprising the steps: (D1) resolving a trans-amine of the formula ##STR19## by treating with L-(+)-tartaric acid in an alcohol solvent to form the tartrate salt, recrystallizing the tartrate salt from an alcohol solvent, then treating the tartrate salt with base to form a chiral amine of the formula ##STR20## (D2) reacting the chiral amine of step (D1) with a compound of the formula J-CH 2 --Q, wherein J and Q are as defined above, in the presence of a base to form a compound of the formula ##STR21## (D3) cyclizing the product of step (D2) by treating with an alkyllithium reagent and a sulfonyl chloride. Preferred is a process wherein: Q is --CH(OCH 3 ) 2 ; the counterion X - is Cl - , BF 4 - , CH 3 C 6 H 4 SO 3 - , C 6 H 5 SO 3 - , CH 3 SO 3 - or CF 3 SO 3 - ; M is MgBr; and the cyclization of step (b) is carried out by treating with a strong acid, followed by treatment with a hydride reducing agent, preferably BH 3 .tBuNH 2 or NaBH 4 . Also preferred is a process according to Process A wherein: the base of step (A1)(i) is NaHCO 3 or KHCO 3 ; the tertiary amine base of Step (A1)(iii) is Et 3 N; in Step (A3) J is Br; the alkyllithium reagent of Step (A4) is n-butyllithium; and the sulfonyl chloride of Step (A4) is tosyl chloride, nosyl chloride, brosyl chloride, benzene sulfonyl chloride or mesyl chloride. Another preferred process is a process according to Process B wherein: the chlorinating agent of step (B2) is oxalyl chloride or SOCl 2 ; the Lewis acid of step (B2) is AlCl 3 ; the hydride reducing agent of step (B3) is LiAlH 4 ; in Step (B4) J is Br; the alkyllithium reagent of Step (B5) is n-butyllithium; and the sulfonyl chloride of Step (B5) is tosyl chloride, nosyl chloride, brosyl chloride, benzene sulfonyl chloride or mesyl chloride. Yet another preferred process is a process according to Process C wherein: the tertiary amine base of step (C3)(ii) is Et 3 N; the alkyllithium reagent of Step (C3)(II) is n-butyllithium; and the sulfonyl chloride of Step (C3)(II) is tosyl chloride, nosyl chloride, brosyl chloride, benzene sulfonyl chloride or mesyl chloride. Still another preferred process is a process according to Process D wherein the alcohol solvent of step (D1) is methanol; the base of step (D2) is NH 4 OH, Na 2 CO 3 or K 2 CO 3 ; J is Br; the alkyllithium of step (D3) is n-butyllithium; and the sulfonyl chloride of Step (D3) is tosyl chloride, nosyl chloride, brosyl chloride, benzene sulfonyl chloride or mesyl chloride. The process of the present invention does not suffer the shortcomings of the prior art processes. It is chemically efficient and, by utilizing inexpensive chiral starting materials, or by utilizing enantioselective transformations on prochiral compounds, or alternatively by performing a resolution step at an early stage of the synthesis, produces a chiral product (compound I) which is readily converted to SCH 39166 by known methods. The present invention further comprises compounds of the formula ##STR22## wherein: X - is halide, BF 4 - or R 3 SO 3 - , wherein R 3 is C 1 -C 6 alkyl, CF 3 , benzyl, phenyl or Z-substituted phenyl, wherein Z is C 1 -C 6 alkyl, nitro or bromo; and Q is a group of the formula ##STR23## wherein R is C 1 -C 6 alkyl, useful as intermediates in the preparation of benzazepines having activity as selective D1 receptor antagonists. Preferably such compounds have the absolute stereochemistry shown in the formula ##STR24## The present invention also comprises compounds of the formula ##STR25## wherein Q is a group of the formula ##STR26## wherein R is C 1 -C 6 alkyl, useful as intermediates in the preparation of benzazepines having activity as selective D1 receptor antagonists. Preferably such intermediates have the absolute stereochemistry shown in the formula ##STR27## In another embodiment, the present invention comprises chiral compounds of the formula ##STR28## wherein R 1 is H or CH 3 ; and Q is a group of the formula ##STR29## wherein R is C 1 -C 6 alkyl, useful as intermediates in the preparation of benzazepines having activity as selective D1 receptor antagonists. DETAILED DESCRIPTION In general, stereochemical representations are meant to denote relative stereochemistry. However, where optically active starting materials are employed, such as in the embodiment denoted as process B, the stereochemical representations denote absolute as well as relative stereochemistry. Therefore, by using such optically active starting materials, compounds of the formula I can be prepared as a single enantiomer. Similarly, by utilizing stereoselective transformations on prochiral compounds to generate chiral compounds, or by performing a resolution step (such as in Process D), a single enantiomer of compounds of the formula I is produced. In those embodiments where the present invention relates to chiral compounds, the stereochemical purity of such compounds is generally given in terms of the enantiomeric excess (e.e.). As used herein the term "alkyl" means a straight or branched alkyl chains of 1 to 6 carbon atoms; "tertiary amine base" means a tertiary amine selected from pyridine, di-isopropylethylamine or a tri-(C 1 -C 6 alkyl)amine, such as triethylamine; "base" means a water soluble base, such as NH 4 OH, KHCO 3 , K 2 CO 3 , NaHCO 3 or Na 2 CO 3 ; "strong base" means an alkali metal hydroxide, such as NaOH, KOH or LiOH, or an alkaline earth metal hydroxide such as Ca(OH) 2 ; "leaving group" means a group which can be readily displaced by a nucleophile, preferably --Cl, --Br, --I, --OSO 2 CH 3 , --OSO 2 CF 3 or --OSO 2 C 6 H 4 CH 3 ; "sulfonyl chloride" means a compound of the formula R 3 SO 2 Cl, wherein R 3 is C 1 -C 6 alkyl, CF 3 , benzyl, phenyl or Z-substituted phenyl, and Z is C 1 -C 6 alkyl, nitro or bromo, with preferred sulfonyl chlorides including tosyl chloride, nosyl chloride, mesyl chloride, brosyl chloride and benzene sulfonyl chloride; "alkyllithium" means an alkyllithium reagent, such as n-butyllithium, methyllithium, sec-butyllithium or tert-butyllithium; "strong acid" means a protic acid having a pKa<2, such as H 2 SO 4 or CH 3 SO 3 H; "Lewis acid" means a Lewis acid capable of catalyzing a Friedel-Crafts type reaction, such as AlCl 3 ; "hydride reducing agent" means a metal hydride reducing agent, such as NaBH 4 , NaBH 3 CN, LiBH 4 or LiAlH 4 , or a borane amine complex, such as borane-methylamine, borane-tert-butylamine, borane-piperidine, borane-triethylamine, borane-N,N-diisopropylethylamine, borane-N,N-diethylaniline, borane-morpholine, borane-4-ethylmorpholine or borane-4-phenylmorpholine complex; "counterion" means an anion selected from a halide, BF 4 - , and R 3 SO 3 - , wherein R 3 is C 1 -C 6 alkyl, CF 3 , C 1 -C 6 alkylphenyl, benzyl, nitrophenyl, bromophenyl or phenyl; and "halide" means a chloride, bromide, fluoride or iodide anion. As used herein the following reagents and solvents are identified by the abbreviations indicated: para-toluenesulfonyl chloride (tosyl chloride, TsCl); para-bromobenzenesulfonyl chloride (brosyl chloride); para-nitrobenzenesulfonyl chloride (nosyl chloride); N-methylmorpholine-N-oxide (NMMO); methanesulfonyl chloride (mesyl chloride, MsCl); tetrahydrofuran (THF); iso-propanol (i-PrOH); methanol (MeOH); ethyl acetate (EtOAc); tert-butyl methyl ether (TBME); borane-tert-butylamine complex (BH 3 .tBuNH 2 ); triethylamine (Et 3 N); chloro 2,2'- 1,2-cyclohexane-diylbis(nitrilomethylidyne)!bis 4,6-bis(1,1 -dimethyl-ethyl)phenolato!!(2-)-N, N', O, O'-manganese (Mn(III) salen catalyst); trifluoroacetic acid (TFA). The aziridinium salts of step(a) of the process of the present invention exist in conjunction with a counterion identified as X - . The counterion is a suitable anion such as halide, BF 4 - or R 3 SO 3 - , wherein R 3 is C 1 -C 6 alkyl, CF 3 , C 1 -C 6 alkylphenyl, benzyl, nitrophenyl, bromophenyl or phenyl. The present invention comprises a process for preparing a compound of the formula I as shown in Reaction Scheme 1. The stereochemical representations depict the preferred stereoisomers. The process can be carried out using a racemic aziridinium salt, in which case the stereochemical representations designate the preferred isomers having the relative stereochemistry shown. Alternatively, the process can utilize a single enantiomeric aziridinium salt to produce a single enantiomer of compound I, wherein the stereochemical representations further designate absolute stereochemistry. ##STR30## In Scheme 1, Step (a), a Grignard reagent (III), wherein M is MgBr, is prepared from 5-bromo-2-chloroanisole and Mg in a suitable solvent, such as THF, at -10° to 60° C., preferably at 40° to 45° C., then reacted with the aziridinium salt (II) in a suitable solvent, such as THF, at -80° to 0° C., preferably at -30° to -20° C., for 1 to 10 hours, preferably about 5 hours, then at 0° to 70° C., preferably about 25° C., to form a compound of the formula IV, wherein Q is as defined above. Alternatively, in Step (a) the aziridinium salt (II) is treated (under substantially the same conditions as described for the Grignard reagent) with a reagent (III) wherein M is ZnL, TiL 3 , CeL 2 , MnL or CuL, and L is a halide ligand selected from Br, Cl or I. Where more than one such ligand L is present the individual ligands can be the same or different; In Step (b), compound IV, wherein Q is --CH(OR) 2 and R is as defined above, is combined with a strong acid, such as CH 3 SO 3 H, in a suitable solvent, such as CH 2 Cl 2 , at -30° to +20° C., preferably 0° to +5° C., then warmed to 20° to 60° C., preferably about 40° C. The resulting mixture is concentrated by warming at 30° to 60° C., preferably about 50° C., under reduced pressure, and the residue is dissolved in a suitable solvent, such as CH 2 Cl 2 , then treated with a hydride reducing agent, preferably NaBH 4 , and an alcohol solvent, preferably isopropanol, to give a compound of the formula I. Alternatively, in Step (b), compound IV, wherein Q is --CH(OR) 2 and R is as defined above, is combined with a strong acid, such as H 2 SO 4 , in a suitable solvent, such as CH 2 Cl 2 , at -20° to +20° C., preferably 0° to +5° C., then warmed to 10° to 60° C., preferably about 25° C. The mixture is cooled to -20° to +20° C., preferably about 0° C., then treated with a hydride reducing agent, preferably BH 3 .tBuNH 2 , and warmed to 10° to 60° C., preferably about 25° C., to give a compound of the formula I. The present invention further comprises a process as described above wherein the aziridinium salt of Step (a) is prepared according to Process A, as shown in Reaction Scheme A. ##STR31## In Reaction Scheme A, Step A1, 1,2-dihydronaphthalene (V) is treated with H 2 O 2 , preferably 30% H 2 O 2 (aqueous), and a base, preferably KHCO 3 or NaHCO 3 , in a suitable solvent, such as a mixture of CH 3 CN and an alcohol solvent, preferably CH 3 CN and MeOH, at 0° to 50° C., preferably at 25° to 30° C., for 2 to 24 hours, preferably about 17 hours, to form the racemic epoxide VI. Alternatively, 1,2-dihydro-naphthalene (V) is converted to a single enantiomer of the epoxide VI as described in Step C1 of Method C. In Step A2, the epoxide VI is reacted with CH 3 NH 2 in a suitable sealed container, preferably a teflon® lined bomb, at 50° to 130° C., preferably at 80° to 110° C., and most preferably about 100° C., for 12 to 36 hours, preferably about 22 hours, to form the aminoalcohol VII. Alternatively, in Step A2, the epoxide VI is reacted with an excess of 40% CH 3 NH 2 (aqueous) at 0° to 50° C., preferably about 25° C., for 12 to 36 h, preferably about 24 h, to form the aminoalcohol VII. The reaction is carried out via substantially the same procedure as described in Crabb, et al., Mag. Res. in Chem., 24, 798 (1986) and Lukes, et al., Coll. Czech. Chem. Comm., 25, 492 (1960). In Step A3, compound VII is combined with a compound of the formula J-CH 2 --Q, wherein J and Q are as defined above, in a suitable solvent, such as CH 3 CN or DMF, in the presence of a base, preferably Na 2 CO 3 or K 2 CO 3 , and the resulting mixture heated at 30° to 100° C., preferably at reflux, for 1 to 8 days, preferably about 6 days, to form compound VIII. In Step A4, compound VIII is treated with an alkyllithium, preferably n-butyllithium, in a suitable solvent, such as anhydrous THF, at -60° to +20° C., preferably about 0° C., for about 10 minutes. The resulting mixture is then treated with a sulfonyl chloride, preferably tosyl chloride, at -20° to +20° C., preferably about 0° C., for about 15 minutes to form the aziridinium salt II, wherein Q is as defined above, and X - is R 3 SO 3 - , wherein R 3 is as defined above, which is used directly in Step (a) above. In an alternative embodiment, the present invention further comprises a process as described in Reaction Scheme 1 wherein a single enantiomer of the aziridinium salt of Step (a) is prepared according to Process B as shown in Reaction Scheme B. ##STR32## In Reaction Scheme B, Step B1, a combination of the chiral amino acid IX, a strong base, preferably NaOH, most preferably 1N aqueous NaOH, and a base, preferably Na 2 CO 3 , at -20° to +20° C., preferably about 0° C., is treated with ClCO 2 R 2 , wherein R 2 is as defined above, preferably CH 3 , then warmed to 0° to 40° C., preferably about 25° C., for 1 to 5 hours, preferably about 3 hours, then treated with HCl to form the carbamate X. In step B2, the carbamate X is combined with a chlorinating agent, such as SOCl 2 or oxalyl chloride, preferably SOCl 2 , in a suitable solvent, such as CH 2 Cl 2 , and heated at 30° to 70° C., preferably at reflux, for 1 to 10 hours, preferably about 3 hours, then cooled to about 25° C. The resulting mixture is treated with a Lewis acid, preferably AlCl 3 , in a suitable solvent, such as CH 2 Cl 2 , for 1 to 10 hours, preferably about 3 hours, to give the ketone of the formula XI. In Step B3, the ketone XI is treated with a hydride reducing agent, preferably LiAlH 4 , in a suitable solvent, such as THF, at -60° to 20° C., preferably about 0° C., for about 1 hour, then heated at 30° to 80° , preferably at reflux, for 1 to 10 hours, preferably about 2 hours, to form a compound of the formula XII. In Step B4, compound XII is treated with a compound of the formula J-CH 2 --Q, wherein J and Q are as defined above, in a suitable solvent, such as CH 3 CN, in the presence of K 2 CO 3 , Na 2 CO 3 or KF and alumina, and the resulting mixture heated at 40° to 120° C., preferably at reflux, for 1 to 4 days, preferably about 2 days, to form compound XIII. In Step B5, compound XIII is treated with an alkyllithium, preferably n-butyllithium, in a suitable solvent, such as THF, at -60° to +20° C., preferably about 0° C., for about 10 minutes. The resulting mixture is then treated with a sulfonyl chloride, preferably tosyl chloride, at -20° to +20° C., preferably about 0° C., for about 15 minutes to form a single enantiomer of the aziridinium salt II, wherein Q is as defined above, X - is R 3 SO 3 - , wherein R 3 is as defined above, and wherein the absolute stereochemistry is as shown in Reaction Scheme B, which is used directly in Step (a) of Reaction Scheme 1 above. In a second alternative embodiment, the present invention further comprises a process as described in Reaction Scheme 1 wherein the aziridinium salt of Step (a) is prepared according to Process C as shown in Reaction Scheme C. ##STR33## In Reaction Scheme C, Step C1: 1,2-dihydronaphthalene (V) is converted to the racemic epoxide VI as described above for Step A1 of Method A. Alternatively, 1,2-dihydronaphthalene (V) is treated with OsO 4 and NMMO in a suitable solvent, such as a mixture of acetone and water, at -60° to +20° C., preferably at about 0° C., for 10 to 48 hours, preferably about 26 hours, to give cis-1,2,3,4-tetrahydro-1,2-napthalenediol. The treatment with OsO 4 and NMMO can optionally be carried out in the presence of hydroquinine 4-chlorobenzoate, as described in Sharpless, et al, J. Org. Chem., 57, 2768-2771 (1992), in which case predominantly one enantiomer of the cis-diol is produced. The diol is treated with (C 6 H 5 ) 3 PBr 2 in the presence of a tertiary amine base, preferably triethylamine, in a suitable solvent, such as CH 3 CN, at 0° to 50° C., preferably at about 25° C., for 10 to 30 hours, preferably about 20 hours, to form predominantly one enantiomer of the epoxide XI, having the absolute stereochemistry indicated in Reaction Scheme C. In another alternative, 1,2-dihydronaphthalene (V) is treated with NaOCl, preferably an aqueous solution of NaOCl, and a suitable manganese catalyst, preferably chloro 2,2'- 1,2-cyclohexane-diylbis(nitrilomethylidene)!bis 4,6-bis(1,1-dimethylethyl)phenolato!!(2-)-N,N',O,O'-manganese, as described in Zhang, et al, J. Org. Chem., 56, 2296-2298 (1991 ). The reaction is carried out in a suitable solvent, such as CH 2 Cl 2 , in the presence of 4-phenylpyridine N-oxide, at -60° to +20° C., preferably at about 0° C., for 30 to 90 minutes, preferably about 45 minutes, to form the chiral epoxide VI, 90% e.e., having the absolute stereochemistry indicated in Reaction Scheme C. The epoxide VI can also be obtained as a single stereoisomer from commercial sources for use in Step C2. In Step C2, the epoxide VI is treated with an amine of the formula Q--CH 2 --NH(R 1 ), wherein Q and R 1 are as defined above, in a sealed container, preferably in a Teflon® lined bomb, at 60° to 120° C., preferably at about 95° C., for 10 to 48 hours, preferably for 20 to 24 hours, to form compound XIV. In Step C3 (I), compound XIV, wherein R 1 is H, is reacted with (C 6 H 5 ) 3 PBr 2 and a tertiary amine base, preferably triethylamine, in a suitable solvent, such as CH 3 CN, at -40° to +20° C., preferably at about 0° C., for 1 to 2 hours, preferably about 90 minutes to form the aziridine XV. Alternatively, compound XIV is converted to the aziridine XV by treating with MsCl or TsCl and a tertiary amine base, preferably triethylamine, in a suitable solvent. Aziridine XV is reacted with (CH 3 ) 3 OBF 4 in a suitable solvent, such as CH 2 Cl 2 , at -60° to 0° C., preferably at about -20° C., for 10 to 30 hours, preferably about 20 hours, to form the aziridinium salt II, wherein X - is BF 4 - . Alternatively, the aziridine XV is treated with CF 3 SO 3 CH 3 in a suitable solvent, such as THF, at 0° to 50° C., preferably at about 25° C., for 10 to 60 minutes, preferably about 20 minutes, to form the aziridinium salt II, wherein X - is CF 3 SO 3 - . In Step C3 (II), compound XIV is converted to the aziridinium salt II as described for Step A4 of Method A. In a third alternative embodiment, the present invention further comprises a process as described in Reaction Scheme 1 wherein a single enantiomer of the aziridinium salt of Step (a) is prepared according to Process D as shown in Reaction Scheme D. ##STR34## In Reaction Scheme D, In Step D1, the racemic transamine VII is treated with L-(+)-tartaric acid in a alcohol solvent, preferably methanol, at 0° to 50° C., preferably about 20° C., to form a solution of the tartrate salt. The tartrate salt solution is cooled to -20° to +20° C., preferably about -5° C., to give the crystalline tartrate salt. The tartrate salt is dissolved in an alcohol solvent, preferably methanol, at 30° to 100° C., preferably at reflux temperature, then cooled to -20° to +20° C., preferably about -5° C., to give the recrystallized tartrate salt. The recrystallized tartrate salt is treated with a base, preferably 10% NH 4 OH (aqueous) to give the amine (+)-VII as a single enantiomer. In Step D2, the amine (+)-VII is converted to a single enantiomer of compound VIII via the process described for Step A3 of Reaction Scheme A. In Step D3, compound VIII is converted to the aziridinium salt II as described for Step A4 of Reaction Scheme A. Starting compounds of the formula V, IX and XVIII are commercially available. Compounds of the formula J-CH 2 --Q are commercially available or can be prepared via known methods, such as the methods described by Gribble, et al, in J. Org. Chem., 46. 2433-2434 (1981). Compounds of the formula VII can be prepared as described above or by Process E as shown in Reaction Scheme E. ##STR35## The conversion of XVIII to VII is carried out via substantially the same procedures as described by: Braun, et al., Chem Berichte. 54, 597 (1921 ); Braun, et al., Chem Berichte, 55, 3648 (1922); and Lukes, et al., Coll. Czech. Chem. Comm., 492 (1960). In Step E1, 1,2,3,4-tetra-hydronaphthalene XVIII is treated with Br 2 at 60° to 110° C., preferably about 90° C., to form the racemic trans-dibromide XVI. Alternatively, in Step E1, a solution of compound XVIII in hexane is treated with Br 2 at 40° C. to 100° C., preferably at reflux temperature, to form the racemic trans-dibromide XVI. In Step E2, the dibromide XVI is combined with a mixture of acetone, water and a base, preferably NaHCO 3 , and heated at 40° to 100° C., preferably at reflux temperature, for 1 to 6 h, preferably about 3 h, to form the racemic trans-alcohol XVII. In Step E3, the alcohol XVII is reacted with a 40% solution of CH 3 NH 2 in water at 0° to 50° C., preferably about 20° C., for 10 to 30 h, preferably about 16 h, to form the racemic trans-amine VII. The following examples illustrate the process of this invention: PREPARATION 1 ##STR36## Combine Mg turnings (1.30 g, 54.00 mmol) and 35 mL dry THF. Add a solution of 5-bromo-2-chloroanisole (11.78 g, 53.20 mmol) dissolved in 300 mL dry THF over a 10 min. period, maintaining the reaction temperature at 40°-45° C., and stir for 90 min. The resulting solution of Grignard reagent is used as is. PREPARATION 2 ##STR37## Combine hydroquinine 4-chlorobenzoate (5.00 g, 10.753 mmol), NMMO (7.57 g, 64.636 mmol) and 44 mL of a 10:1 acetone/water solution, stir vigorously and add OsO 4 (0.35 mL, 0.175 mmol, 0.5M in toluene). Cool to 0° C. and add 1,2-dihydronaphthalene (5.234 g, 40.205 mmol) via a syringe pump over a 10 h period. After 16 h more, add Na 2 S 2 O 5 (13 g), stir for 10 min at room temperature, then add 80 mL of CH 2 Cl 2 and filter. Wash the solids with 3×50 mL CH 2 Cl 2 , dry the combined filtrates over anhydrous MgSO 4 and concentrate in vacuo to a residue. Flash chromatograph the residue (silica gel, 10% to 100% EtOAc/hexanes) and then recrystallize (EtOAc/hexanes) to yield the chiral diol product. 1 H NMR (CDCl 3 ) δ: 7.40 (m, 1H); 7.23 (m, 2H); 7.12 (m, 1H); 4.72 (d, 1H, J=2 Hz); 3.94 (m, 1H); 3.92 (m, 1H); 3.78 (m, 3H); 1.95 (m, 2H). Chiral 1 H NMR using a Eu(hfc) 3 shift reagent indicated an enantiomeric excess of 24%. ##STR38## Combine the product of Step (a) (1.678 g, 10.224 mmol) and 50 mL of CH 3 CN. Add a slurry of (C 6 H 5 ) 3 PBr 2 (4.371 g, 10.354 mmol) in 10 mL CH 3 CN and stir for 30 min. Add a solution of Et 3 N (2.335 g, 23.073 mmol) in 10 mL CH 3 CN and stir for 20 h. Add the reaction mixture to a mixture of 25 mL saturated NaHCO 3 , 10 mL H 2 O and 50 mL TBME. Separate, extract the aqueous layer with 1×25 mL TBME, wash the combined organic layers with 1×25 mL brine, dry over anhydrous MgSO 4 and concentrate in vacuo to a residue. Add 75 mL hexanes to the residue, decant from the resulting precipitate, concentrate the hexanes layer and flash chromatograph (silica gel, 5% to 50% EtOAc/hexanes) to afford the title epoxide. 1 H NMR was identical to the racemic material prepared in Example 2, Step (a). PREPARATION 3 ##STR39## Combine 1,2-dihydronaphthalene (1.000 g, 7.690 mmol), 4-phenylpyridine N-oxide (0.263 g, 1.538 mmol), the (S,S)-isomer of the Mn(III) salen catalyst (0.196 g, 0.310 mmol) and 8 mL of CH 2 Cl 2 , and cool to 0° C. Add a cooled solution (0° C.) of NaOCl* (27 mL, 1.105 g, 14.850 mmol, ≈4% NaOCl in water) and stir for 45 min at 0° C. Then extract with 100 mL of hexanes, wash the organic layer with 2×100 mL water and 1×75 mL brine. Extract the combined aqueous washes with 2×30 mL hexanes, and dry the combined organic layers over anhydrous MgSO 4 . Concentrate in vacuo to a residue, then flash chromatograph (as described in Preparation 2) to afford the chiral epoxide. 1 H NMR was identical to the racemic material prepared in step C. Chiral HPLC (Daicel OB® column) indicated the product to have an e.e. of 91%. *Prepare a stock solution of NaOCl by adjusting the pH of 500 mL of NaOCl (Clorox®) to pH 11.3 using 0.05M NaHPO 4 and 1M NaOH solutions. EXAMPLE 1 ##STR40## Combine the aziridinium tetrafluoroborate salt of Example 4 (13.70 g, 40.90 mmol) and 70 mL dry THF to form a suspension. Cool to -20 to -30° C. and add the Grignard reagent of Preparation 1 (335 mL, 53.20 mmol, 0.159M in THF) over a 30 min. period. Stir the reaction mixture at -20° C. for 5 h, warm to room temperature, and stir for 15 h more. Cool to 0° to 10° C. and add 8.6% aqueous NaHCO 3 to adjust the mixture to pH 11. Extract with 3×100 mL EtOAc, wash the combined organic layers with 1×100 mL water and concentrate to a residue. Purify by flash chromatography (silica gel, 2.5-10% MeOH/CH 2 Cl 2 ) to give the (+)-enantiomer of the title compound. 1 H NMR (CDCl 3 ) δ: 6.65-7.30 (m, 7H); 4.12 (t, 1H, J=5.6 Hz); 4.09 (d, 1H, J=11.3 Hz); 3.82 (s, 3H); 3.21 (s, 3H); 3.12 (s, 3H); 2.95 (m, 3H); 2.60 (dd, 2H, J=5.6, 11.3 Hz); 2.31 (s, 3H); 2.08 (m, 1H); 1.70-1.80 (m, 1H). ##STR41## Combine methanesulfonic acid (7.40 g, 77.003 mmol) and 15 mL CH 2 Cl 2 and cool to 0° to 5° C. Dissolve the product of Step (a) (2.34 g, 6.001 mmol) in 15 mL CH 2 Cl 2 and add the resulting solution to the acid solution over a 5 min period. Heat the mixture at 40° C. for 2 h, then concentrate (50° C./20 Torr) to a residue. Dissolve the residue in 10 mL CH 2 Cl 2 , cool to 10° to 15° C., and add a solution of NaBH 4 (0.280 g, 7.402 mmol) in 15 mL i-PrOH over a 10 min period. Stir for 2 h, then add a solution of Na 2 CO 3 (6.70 g, 63.208 mmol) in 34 mL water to adjust to pH 7. Extract the aqueous layer with 2×10 mL CH 2 Cl 2 , wash the combined organic layers with 2×10 mL water, then dry over anhydrous MgSO 4 and concentrate in vacuo to yield the (-)-enantiomer of the title compound. Purify by flash chromatography (silica gel, 2.5-10% MeOH/CH 2 Cl 2 ). 1 H NMR (CDCl 3 ) δ: 6.95-7.19 (m, 5H); 5.88 (s, 1H); 4.78 (d, 1H, J=7.5 Hz); 3.5-3.62 (m, 1H); 3.49 (s, 3H); 3.2 (dd, 1H, J=3.75, 11.3 Hz); 2.65-2.86 (m, 4H); 2.51 (s, 3H); 2.41 (dd, 1H, J=5.6, 11.3 Hz); 1.98-2.18 (m, 1H); 1.6-1.8 (dq, 1H, J=5.6, 11.3 Hz). EXAMPLE 1A ##STR42## Combine sulfuric acid (11.4 g, 116 mmol) and 200 mL of CH 2 Cl 2 and cool the mixture to 0° C. Dissolve the product of Example 1, Step (a), (9.08 g, 23.3 mmol) in 200 mL of CH 2 Cl 2 and add the resulting solution to the acid mixture. Warm to room temperature, stir for 24 h., then cool to 0° C. and add BH 3 .tBuNH 2 (2.43 g, 27.9 mmol) in portions. Warm to room temperature and stir for 4.5 h, then cool to 0° C. and extract with 150 mL of 1.5M Na 2 CO 3 (aqueous). Wash the organic layer with brine, dry over Na 2 SO 4 , then concentrate in vacuo to give the (-)-enantiomer of the title compound. 1 H NMR matches material prepared in Example 1. EXAMPLE 2 ##STR43## Combine 1,2-dihydronaphthalene (24.20 g, 0.186 mol), 70 mL MeOH and 60 mL CH 3 CN. Add KHCO 3 (2.00 g, 0.020 mol), stir 5 min and then add 30% H 2 O 2 (45.00 g, 0.400 mol, 30% solution in H 20 ) at a rate such that the reaction temperature is maintained at 25° to 30° C. Stir for 17 h at room temperature, then quench the reaction with 40% NaHSO 3 (50 g). Concentrate (40-45° C./60 Torr) the resulting mixture to a residue, partition the residue in 50 mL CH 2 Cl 2 and 150 mL H 2 O and wash the organic layer with 2×50 mL H 2 O. Dry over anhydrous Na 2 SO 4 and concentrate in vacuo to a residue. Distill the residue (70° to 76° C./0.05 Torr) to afford the epoxide product (racemic). 1 H NMR (CDCl 3 ) δ: 7.42 (dd, 1H, J=1,5 Hz); 7.24 (m, 2H), 7.10 (d, 1H, J=5 Hz); 3.85 (d, 1H, J=3 Hz); 3.72 (m, 1H); 2.80 (m, 1H); 2.56 (dd, 1 J=6, 11 Hz); 2.42 (m, 1H); 1.86 (m, 1H). ##STR44## Charge a 120 mL Teflon® acid digestion bomb with the product of Step (a) (20.09 g, 0.1374 mol) and a stirring bar. Add liquid MeNH 2 (≈25 mL), seal the bomb and stir while heating at 100° C. for 22 h. Cool the bomb and then allow excess MeNH 2 to boil off. Distill the residue (kugelrohr at 160°-175° C./1 Torr) to afford the trans-amino alcohol product (racemic). 1 H NMR (CDCl 3 ) δ: 7.30 (m, 4H); 3.86 (m, 1H); 3.64 (d, 1H, J=8 Hz); 2.89 (dd, 2H, J=5.4, 7.9 Hz); 2.42 (s, 3H); 2.25 (m, 3H); 1.86 (m, 1H). Alternatively, the product of Step (a) is converted to the trans-amino alcohol product by treating with CH 3 NH 2 via the procedure described in Crabb, et al., Mag. Res. in Chem., 24, 798 (1986). ##STR45## Combine the product of Step (b) (85.8 g, 0.484 mol), 484 mL anhydrous CH 3 CN, K 2 CO 3 (133.8 g, 0.968 mol) and bromoacetaldehyde dimethylacetal (123 g, 0.726 mol), and heat the mixture at reflux for 6 days. Cool to room temperature, decant the mixture and concentrate in vacuo to give a residue. Dissolve the residue in 350 mL of EtOAc and wash with 750 mL of water, then with 2×160 mL of 2.5% HCl (aqueous). Combine the acidic washes, adjust to pH 8.8 by adding saturated Na 2 CO 3 (aqueous) and extract with EtOAc. Wash the organic extract with brine, dry over MgSO 4 and concentrate in vacuo to give the product. 1 H NMR (CDCl 3 ) δ: 7.65 (d, 1H, J=7.5 Hz); 7.05-7.30 (m, 3H); 4.65 (d, 1H, J=11.3 Hz); 4.55 (br m, 1H); 4.10 (br s, 1H); 3.45 (s, 3H); 3.10 (s, 3H); 2.53-3.00 (m, 5H); 2.47 (s, 3H); 2.05 (m, 1H); 1.61 (m, 1H). ##STR46## Combine the product of Step (c) (81.0 g, 0.305 mol), 1, 10-phenanthroline (0.040 g, 0.222 mmol) and 305 mL anhydrous THF, cool the mixture to about 0° C., and add n-butyllithium (191 mL, 0.306 mmol, 1.6M solution in hexanes). Stir for 20 minutes, then add a solution of tosyl chloride (63.7 g, 0.334 mmol) in 200 mL of anhydrous THF. Stir the mixture for 1 h to form the aziridinium salt intermediate. Cool the mixture to about -30° C., then add the Grignard reagent from Preparation 1 (654 mL, 0.641 mmol, 0.98M in THF) and stir for 24 h at room temperature. Add 250 mL saturated NH 4 Cl (aqueous), filter, then concentrate the filtrate in vacuo to a residue. Dissolve the residue in 230 mL of TBME, wash with 100 mL of water, then with 5% HCl (aqueous) (1×200 mL and 3×100 mL). Combine the acidic washes and extract with 230 mL of TBME. Adjust the acidic washes to pH 4.9 by adding saturated Na 2 CO 3 (aqueous) and extract with 300 mL of TBME. Wash the organic layer with brine, dry over Na 2 SO 4 and concentrate in vacuo to yield the title compound (racemic). 1 H NMR spectra is identical to material prepared in Example 1. EXAMPLE 3 ##STR47## Combine (+)-α-aminobenzenebutanoic acid (100.14 g, 0.559 mol), NaOH (1.12 L, 1.12 mol, 1N aqueous solution) and Na 2 CO 3 (88.61 g, 0.836 mol), and cool the mixture to about 0° C. Add methyl chloroformate (90 mL, 1.17 mol) dropwise over 15 min and stir at room temperature for 3 h. Add 500 mL 5% HCl then enough 50% HCl to bring to pH 2 (about 400 mL). Add 1 L of CH 2 Cl 2 , separate the layers, wash the aqueous layer with 3×150 mL CH 2 Cl 2 , then wash the combined organic layers with 1×250 mL brine. Dry over anhydrous MgSO 4 and concentrate in vacuo to yield the S-enantiomer of the carbamate product. 1 H NMR (CDCl 3 ) δ: 7.10-7.30 (m, 5H); 5.25 (br d, 1H); 4.42 (br s, 1H); 3.70 (s, 3H); 2.70 (m, 2H); 2.20 (m, 1H) 2.01 (m, 1H). ##STR48## Combine the carbamate of Step (a) (124.9 g, 0.526 mol), 1 L of CH 2 Cl 2 and SOCl 2 (39.0 mL, 0.535 mol) and heat the mixture to reflux for 3 h, then cool to room temperature to form a solution of the S-enantiomer of the acid chloride intermediate. Add the acid chloride solution dropwise to a mixture of AlCl 3 (211.22 g, 1.584 mol) and 750 mL CH 2 Cl 2 over 2 h period, then stir for 1 h more. Add the reaction mixture gradually to 1 L of a saturated NH 4 Cl/ice mixture. Filter the mixture and slurry the solids obtained in 1.5 L CH 2 Cl 2 and 1 L water overnight, filter, combine the filtrates and separate the layers. Wash the aqueous layer with 2×200 mL of CH 2 Cl 2 , then wash the combined organic layers with 1×250 mL of brine. Dry over anhydrous MgSO 4 and concentrate in vacuo to yield the S-enantiomer of the ketone product, mp 119-121.5° C. 1 H NMR (CDCl 3 ) δ: 8.01 (d, 1H, J=7.5 Hz); 7.62 (t, 1H, J=7.5 Hz); 7.22-7.35 (m, 2H); 5.90 (br s, 1H); 4.40-4.50 (m, 1H); 3.72 (s, 3H); 3.25 (dt, 1H, J=11.2 Hz); 3.02 (m, 1H, J=15 Hz); 2.78 (br m, 1H); 1.95 (dd, 1H, J=3.7, 15 Hz). ##STR49## Combine the ketone of Step (b) (4.999 g, 22.802 mmol) and 50 mL anhydrous THF and cool to about 0° C. Add a solution of LiAlH 4 in Et 2 O (46.0 mL, 46.0 mmol, 1M in Et 2 O) gradually over 50 min, then heat at reflux for 2 h. Cool to about 0° C., then add 50 mL 5% HCl and 100 mL Et 2 O and warm the mixture to room temperature. Filter, then wash solids with 25 mL water/10 mL 5% HCl, separate the layers and wash the organic layer with 1×20 mL 5% HCl. Combine the aqueous layers and add 15 mL saturated NaHCO 3 , then add 100 mL EtOAc and separate the layers. Wash the aqueous layer with 3×50 mL EtOAc, dry the combined organic layers over anhydrous MgSO 4 and concentrate in vacuo to yield the trans-1S,2S-isomer of the amino alcohol product. 1 H NMR (CDCl 3 ) δ: 7.68 (d, 1H, J=7.5 Hz); 7.10-7.30 (m, 3H); 4.50 (d, 1H, J=7.5 Hz); 2.90 (m, 2H); 2.67 (m, 1H); 2.55 (s, 3H); 2.27 (m, 1H); 2.00 (br s, 2H); 1.60 (m, 1H). A small amount of the cis diasteriomer ##STR50## was also obtained. 1 H NMR (CDCl 3 ) δ: 7.48 (m, 1H); 7.10-7.30 (m, 3H); 4.71 (d, 1H, J=3.8 Hz); 2.75-3.00 (m, 3H); 2.55 (br s, 5H); 1.95 (m, 1H); 1.75 (m, 1H), ##STR51## Combine the trans-amino alcohol of Step (c) (1.010 g, 5 5.698 mmol), 10 mL anhydrous CH 3 CN and KF over alumina (3.050 g, 19.06 mmol) and stir for 5 min. Add bromo acetaldehyde dimethylacetal (1.4 mL, 11.8 mmol) and heat the mixture at reflux for 2 days. Cool to room temperature, add 25 mL EtOAc and filter though Celite®. Wash the solids with 10 mL EtOAc and 10 mL CH 2 Cl 2 , filter, then concentrate the combined filtrates in vacuo to yield the 1S,2S-isomer of the product. Purify by flash chromatography (silica gel, 30-100% EtOAc/hexanes and then to 60% MeOH saturated with ammonia/EtOAc). 1 H NMR (CDCl 3 ) δ: 7.65 (d, 1H, J=7.5 Hz); 7.05-7.30 (m, 3H); 4.65 (d, 1H, J=11.3 Hz); 4.55 (br m, 1H); 4.10 (br s, 1H); 3.45 (s, 3H); 3.10 (s, 3H); 2.53-3.00 (m, 5H); 2.47 (s, 3H); 2.05 (m, 1H); 1.61 (m, 1H). ##STR52## Combine the product of Step (d) (633.3 mg, 2.3867 mmol) and 2 mL THF and cool to about 0° C. Add a solution of n-butyllithium (1.20 mL, 2.45 mmol, 2.04M in hexane), stir for 10 min, then add tosyl chloride (456.4 mg, 2.3939 mmol) and stir for 15 min more to form the aziridinium salt intermediate. Add a solution of the Grignard reagent of Preparation 1 (5.8 mL, 4.8 mmol, 0.83M in THF) and stir at room temperature for 17 h. Add 10 mL saturated NH 4 Cl and 25 mL EtOAc, then filter and wash the solids with 10 mL EtOAc. Combine the filtrates, separate the layers, wash the organic layer with 1×10 mL of brine, dry over anhydrous MgSO 4 and concentrate in vacuo to a residue. Flash chromatograph (silica gel, 5% to 100% EtOAc/hexane) to yield the named compound. 1 H NMR (CDCl 3 ) δ: 6.65-7.30 (m, 7H); 4.12 (t, 1H, J=5.6 Hz); 4.09 (d, 1H, J=11.3 Hz); 3.82 (s, 3H); 3.21 (s, 3H); 3.12 (s, 3H); 2.95 (m, 3H); 2.60 (dd, 2H, J=5.6, 11.3 Hz); 2.31 (s, 3H); 2.08 (m, 1H); 1.70-1.80 (m, 1H). EXAMPLE 4 ##STR53## Charge a 30-mL Teflon® acid digestion bomb with the chiral epoxide (see Preparations 2 and 3) (1.00 g, 6.866 mmol) and amino acetaldehyde dimethyl acetal (2.171 g, 20.651 mmol). Seal and heat to 95° C. for 23 h. Cool and flash chromatograph (silica gel, 1% to 10% MeOH/CH 2 Cl 2 ) to yield the amino alcohol product. 1 H NMR (DMSO-d 6 ) δ: 7.38 (d, 1H, J=8 Hz); 7.10 (m, 3H); 4.72 (d, 1H, J=2 Hz); 4.42 (t, 1H, J=6.8 Hz); 3.82 (m, 1H); 3.52 (d, 1H, J=7 Hz); 3.42 (s, 3H); 3.40 (s, 3H); 2.73 (m, 3H); 2.54 (m, 1H); 2.00 (m, 1H); 1.78 (br s, 1H); 1.68 (m, 1H). ##STR54## Combine the product of Step (a) (3.647 g, 14.512 mmol), 75 mL of CH 3 CN and (C 6 H 5 ) 3 PBr 2 (9.472 g, 22.439 mmol) and cool to 0° C. Add a solution of Et 3 N (6.50 mL, 46.600 mmol) in 5.5 mL CH 3 CN dropwise over 10 min, stir for 90 min, then filter and concentrate. Slurry the filtrate with 20 mL n-hexane, filter and concentrate in vacuo to a residue. Flash chromatograph the residue (silica gel, 20-60% EtOAc/hexanes) to yield the aziridine product. 1 H NMR (CDCl 3 ) δ: 7.10-7.35 (m, 4H); 4.51 (t, 1H, J=6.8 Hz); 3.40 (2s, 6H); 2.65-2.87 (m, 2H); 2.42-2.55 (m, 3H); 2.21-2.31 (m, 2H); 1.53 (dd, 1H J=6.8, 11.3 Hz). The aziridine can also be formed by treating the product of Step (a) with mesyl chloride and Et 3 N instead of (C 6 H 5 ) 3 PBr 2 and Et 3 N. ##STR55## Combine the product of Step (b) (12.60 g, 51.30 mmol) and 200 mL dry CH 2 Cl 2 , and cool to -20° C. Add purified (CH 3 ) 3 OBF 4 (12.00 g, 81.00 mmol) and stir for 20 h at -20° C. Filter off the excess (CH 3 ) 3 OBF 4 , while excluding moisture, then treat the filtrate with Et 20 at -20° C. Collect the resulting precipitate under argon, wash with cold Et 2 O and dry under vacuum at room temperature to give the chiral aziridinium tetrafluoroborate salt. 1 H NMR (CDCl 3 ) δ: 7.60 (dd, 1H); 7.30 (m, 3H); 4.80 (t, 1H); 4.45 (d, 1H); 4.00 (m, 1H); 3.80 (dd, 1H); 3.50 (d, 6H); 3.35 (dd, 1H); 2.80-3.05 (m, 1H); 2.55-2.75 (m, 2H); 2.50 (s, 3H); 2.10-2.40 (m, 1H). Purified (CH 3 ) 3 OBF 4 is prepared from commercially available (CH 3 ) 3 OBF 4 as follows. Slurry under argon in dry CH 2 Cl 2 (two volumes) at 0° C. and stirred for 30 min. Filter the mixture under argon, wash with dry CH 2 Cl 2 , dry Et 2 O and then dry in vacuo at room temperature for 3 h. The solid is stored at 5° C. in a desiccator over P 4 O 10 under argon. EXAMPLE 5 ##STR56## Charge a 30 mL Teflon® acid digestion bomb with the epoxide of Preparation 2 (or Preparation 3) (2.613 g, 17.872 mmol) and N-methylamino acetaldehyde dimethyl acetal (2.747 g, 23.055 mmol). Seal and heat to 95° C. for 20 h. Cool and flash chromatograph (silica gel, 2% to 5% MeOH/CH 2 Cl 2 ) to give the title compound. 1 H NMR (CDCl 3 ) δ=7.12 (m, 4H); 4.50 (t, 1H, J=7 Hz); 4.13 (s, 1H); 3.72 (m, 2H); 3.40 (s, 6H); 3.08 (d, 2H, J=7 Hz); 3.86 (m, 2H); 2.48 (S, 3H); 2.22 (m, 1H); 1.80 (m, 1H). EXAMPLE 6 ##STR57## Combine the chiral aziridine of Example 4, Step (b) (0.50 g, 2.144 mmol) and 4 mL anhydrous THF. Add methyl triflate (0.363 g, 2.209 mmol), stir for 20 rain, then add the Grignard reagent of Preparation 1 (1.50 mmol) and stir at room temperature for 17 h. Add 50 mL H 2 O and 50 mL EtOAc, separate, extract the aqueous layer with 1×50 mL EtOAc, and wash the combined organic layers with 1×25 mL brine. Dry over anhydrous MgSO 4 and concentrate in vacuo to a residue. Flash chromatograph the residue (silica gel, 20-40% EtOAc/hexanes) to the title compound. 1 H NMR was identical to the material prepared in Example 3. EXAMPLE 7 ##STR58## Combine the racemic amino alcohol from Example 2, Step (b) (160 g) and 1 L of MeOH. Add a hot solution of L-(+)-tartaric acid (68 g) in 300 mL of MeOH. Seed the mixture with a few crystals of the L-(+)-tartrate salt of 1R,2R-isomer of the title compound and stir while cooling the mixture to -5° C. Filter and wash the solid with cold MeOH to give the tartrate salt. Dissolve the tartrate salt in hot MeOH and concentrate until crystals begin to form. Stir the resulting mixture while cooling to -5° C. Filter and wash with cold MeOH to obtain the purified tartrate salt. m.p.=214°-216° C. α! D 20 ° C. =+28.1 ° (water). Elemental Analysis: calculated for C 26 H 36 N 2 O 8 --C, 61.92; H, 7.15; N, 5.55; found --C, 61.89; H, 7.12; N, 5.59. Add the purified tartrate salt (61.33 g, 0.122 mol) to 10% NH 4 OH (183 mL), then extract with TBME (3×250 mL). Combine the extracts, dry over MgSO 4 and concentrate in vacuo to give the chiral amino alcohol. α! D 20 ° C. =+15.3° (MeOH). 1 H NMR using a chiral shift reagent of the formula ##STR59## indicates >99% e.e. for the chiral amino alcohol.
Disclosed are a process and intermediates of the formulae ##STR1## wherein X - is halide, BF 4 - , R 3 SO 3 - , wherein R 3 is C 1 -C 6 alkyl, CF 3 , C 1 -C 6 alkylphenyl or phenyl, and Q is a group of the formula ##STR2## wherein R is C 1 -C 6 alkyl; useful for preparing benzazepine intermediates of the formula ##STR3## These benzazepine intermediates are useful for preparing benzazepines having activity as selective D1 receptor antagonists.
2
TECHNICAL FIELD [0001] This invention relates to resistance seam welding and, more particularly, to a resistance seam welding apparatus and method. BACKGROUND OF THE INVENTION [0002] Resistance seam welding is known in the art for joining metal workpieces. The workpieces may be stacked or otherwise held in temporary assembly. The workpieces are then clamped between a pair of roller electrodes, which locally compress the workpieces. The electrodes are energized, causing electrical current flow through the workpieces to locally heat the workpieces between the electrodes and thereby form a weld. During this time the workpieces and the rollers are moved relative to one another to elongate the weld and thereby form a seam weld between the workpieces. [0003] Roller electrodes commonly have a larger contact area than conventional electrodes, which distributes welding current over a larger workpiece area. Thus a greater flow of electric current is required than with conventional electrodes to heat the larger area and form a weld. The larger contact area of a roller electrode also creates welding limitations when the workpieces to be joined are contoured or non-planar. In addition, roller wheels must be turned as they are moved relative to the workpieces to create a curved or angled seam weld. [0004] Thus, it is desirable to provide a resistance seam welding electrode which provides a smaller contact area than conventional rollers to reduce electric current requirements. It is also desirable to provide an apparatus for resistance seam welding having electrodes adapted for universal directional motion to conform to any desired weld pattern or part shape. SUMMARY OF THE INVENTION [0005] The present invention provides a resistance seam welding apparatus having a pair of universally programmable movable positioners each preferably carrying a ball electrode. The positioners are programmed to move the ball electrodes simultaneously along a seam line so that the electrodes clamp on opposite sides of a pair of workpieces as current is passed through the workpieces, between the electrodes, to form a resistance seam weld. [0006] In an exemplary embodiment, the resistance seam welding apparatus may include a suitable holding fixture or support adapted to carry a structural assembly formed of stacked workpieces. [0007] The resistance seam welding apparatus may further include a first programmable positioner in the form of a programmable robot. The positioner includes an end effector or holder carrying a coupler shank with a part-spherical socket for carrying a ball electrode therein. A retainer ring is attached to the shank, to retain the ball electrode in the socket. If desired, a cooling passage may extend within the jointed arm and into the coupler shank to provide liquid coolant flow to remove heat from the coupler shank and the ball electrode. [0008] The resistance seam welding apparatus may also include a second programmable positioner located beneath the support. The second positioner includes a holder mounting a coupler shank with a part-spherical socket carrying a ball electrode therein. A retainer ring is attached to the end of the shank to retain the ball electrode within the socket. If desired, a cooling passage may extend within the lower coupler shank to provide liquid coolant flow to remove heat from the coupler shank and the electrode. [0009] An electric current source, such as a transformer is attached to the base of the robot and supplies welding current to the upper and lower electrodes through the positioners. [0010] The first and second positioners of the invention may be used with workpieces having differing configurations, which may be accommodated by merely programming the positioners. The ball electrodes provide smaller welding contact points than do conventional roller wheels. These reduce the amount of contacting surface area between the electrodes and the surfaces of the workpieces, which reduces the amount of welding current required to form a weld. The ball electrodes allow the positioners to move the ball electrodes over curves and bends in the workpieces without loosing contact. The ball electrodes also allow the positioners to freely move the electrodes in any direction without having to steer the electrodes. [0011] These and other features and advantages of the invention will be more fully understood from the following description of certain specific embodiments of the invention taken together with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0012] FIG. 1 is a schematic pictorial view of a resistance seam welding apparatus according to the invention; [0013] FIG. 2 is a schematic cross-sectional view through a ball electrode assembly for the resistance seam welding apparatus of FIG. 1 ; and [0014] FIG. 3 is a schematic cross-sectional view through an alternative ball electrode assembly for the resistance seam welding apparatus of FIG. 1 . DESCRIPTION OF THE PREFERRED EMBODIMENT [0015] Referring first to FIG. 1 of the drawings, numeral 10 generally indicates a workstation containing an apparatus 11 configured for resistance seam welding of workpieces. A temporary assembly of workpieces, such as a tunneled floor pan 12 and a tunnel undershield 14 are supported in the apparatus for welding into a structural assembly 15 in the form of a floor pan assembly for a vehicle. The structural assembly 15 includes an upper side 16 of the floor pan 12 and a lower side 17 of the undershield 14 . [0016] The resistance seam welding apparatus 11 includes a suitable holding fixture or support 18 adapted to carry the temporary assembly of the structural floor pan 12 and undershield prior to and during welding of these workpieces into the structural assembly 15 . [0017] The resistance seam welding apparatus 11 further includes a first positioner in the form of a robot 20 . If appropriate, any other suitable form of programmable positioner may be substituted for the robot 20 within the scope of the invention. [0018] The robot 20 includes a base 22 supporting a jointed arm 24 with an end effector or holder 26 carrying an electrode assembly 28 , assembly 28 best shown in FIG. 2 . Assembly 28 includes a coupler shank 30 with an end 32 defining a part-spherical socket 34 receiving a ball electrode 35 , which acts as an upper electrode. A retainer ring 36 is attached to the end 32 to retain the ball electrode 35 within the socket 34 . The retainer ring 36 may be formed of any suitable material, for example it could be formed of graphite to provide heat resistant lubrication for the ball electrode 35 within the socket 34 . [0019] When the ball electrode 35 is retained in the socket 34 , the ball should be able to roll in any direction within the socket to allow the positioner 20 to move the upper electrode in any direction along the surface of the structural assembly 15 . A coolant passage 37 for circulating liquid coolant extends through the jointed arm 24 and into the coupler shank 30 to allow welding heat to be transferred from the upper electrode to the liquid coolant. [0020] The resistance seam welding apparatus 11 also includes a second programmable positioner 39 located beneath the support 18 . The positioner 39 includes a base 40 that is linearly movable along rails 41 extending about the length of the support 18 . A plurality of control arms 42 carry a positionable holder 43 mounting a coupler shank 44 which may be similar to coupler shank 30 . The positionable coupler shank 44 has an end 45 defining a part-spherical socket 46 adapted for receiving a ball electrode 47 , which acts as a lower electrode. A retainer ring 48 attaches to the end 45 to retain the ball electrode 47 within the socket 46 . The retainer ring 48 may be formed of graphite to provide lubrication for the ball electrode 47 within the socket 46 . The ring 48 could be made of other suitable materials, and lubrication, if needed, could be provided by other means. [0021] When the ball electrode 47 is retained in the socket 46 , the ball should be able to roll in any direction within the socket to allow the positioner 39 to move the lower electrode in any direction along the surface of the structural assembly 15 . A cooling passage 49 adapted for circulating liquid coolant extends through the holder 43 and into the coupler shank 44 to allow welding heat to be transferred from the lower electrode to the liquid coolant. [0022] A transformer 50 provides welding current for the ball electrodes 35 , 47 . [0023] Preferably the electrodes 35 , 47 are spherical and universally rotatable within their respective sockets 34 , 46 to create ball contact points for multidirectional seam welding. The ball electrodes should be of adequate size to move across the surfaces of the structural assembly while maintaining adequate contact with the structural assembly to form a continuous seam weld. [0024] In operation, the spatial coordinates of the structural assembly 15 are programmed into the positioners 20 , 39 . A structural assembly 15 comprising workpieces 12 , 14 in temporary assembly with opposing surfaces in contact along a seam line are placed onto the support 18 of the welding apparatus 11 . The first and second positioners 20 , 39 subsequently position the upper and lower ball electrodes 35 , 47 at a first selected location 52 along the seam line so that the electrodes engage opposite sides 16 , 17 of the structural assembly 15 . [0025] The transformer 50 then energizes the ball electrodes 35 , 47 to cause welding current to travel between the electrodes through the first selected location 52 to form a weld 54 between the electrodes. As the weld 54 forms between the ball electrodes 35 , 47 , the positioners 20 , 39 move the electrodes along the opposite surfaces of the structural assembly 15 to form a seam weld. As the positioners 20 , 39 move the ball electrodes along the surfaces 16 , 17 , the electrodes 35 , 47 roll within their respective sockets 34 , 46 similar to a ball point pen to maintain contact with the surfaces 16 , 17 of the workpieces 12 , 14 . During this time, the positioners 20 , 39 adjust positioning of the ball electrodes 35 , 47 , as needed, to maintain optimal electrode contact with the workpieces 12 , 14 for optimal weld quality. [0026] The ball electrodes 35 , 47 and their sockets should be made of suitable heat resistant high current (low resistance) materials, such as copper zirconium to maximize electric current through the workpieces and limit temperatures of the electrodes and excessive heat loss to the coolant in the coupler shanks 30 , 44 . Other suitable materials may also be used if desired. [0027] During the welding process, coolant is circulated through the cooling passages 37 , 49 to remove excess heat from the coupler shanks 30 , 44 and the ball electrodes 35 , 47 . [0028] The electrodes 35 , 47 , may be sequentially repositioned at subsequent selected locations 52 to allow the electrodes to form multiple seam welds 54 along multiple seam lines. Once all of the seam lines 52 are welded the structural assembly 15 is completed and removed from the support 18 . [0029] The ball shape of the electrodes 35 , 47 improves the versatility of the seam welding apparatus 11 by allowing the positioners 20 , 39 to move the electrodes over various contours on the surfaces of the workpieces to form non-planar or non-linear seam welds. In addition, the ball electrodes 35 , 47 allow the positioners 20 , 39 to move the electrodes in a 360 degree pattern along the surface of the structural assembly 15 to form continuous closed pattern seam welds. [0030] When the retaining rings are formed of a lubricating material, such as graphite, the retaining rings 36 , 48 provide lubrication for the ball electrodes 35 , 47 within the sockets 34 , 46 to allow the ball electrodes to roll freely over the surfaces 16 , 17 of the workpieces 12 , 14 . [0031] The ball shape of the electrodes 35 , 47 provide small surface area contacting the surfaces 16 , 17 of the structural assembly 15 . As a result, the amount of current required to form a weld between the ball electrodes 35 , 47 can be reduced, thereby increasing the efficiency of the welding apparatus 11 . [0032] FIG. 3 shows an alternative electrode assembly 60 similar to electrode assembly 28 where like numbers indicate like parts. Assembly 60 includes a coupler shank 62 with an end 64 defining a part-spherical socket, not shown, adapted to retain a ball electrode 35 . The socket is provided with a groove 68 adapted to retain a conductive leaf type spring 70 within the socket and engaging the ball electrode 35 . The spring 70 is preferably formed of a carbon material that provides lubrication between the ball electrode and the coupler shank. A retainer ring 72 is attached to the end 64 to retain the ball electrode 35 and the spring 70 within the socket. [0033] The spring 70 provides a large conductive contact with the ball electrode 35 to provide welding current to the ball electrode. The spring 70 also reduces friction by providing lubrication between the ball electrode 35 and the coupler shank 62 . In addition, the spring 70 may movably suspend the ball electrode 35 within the socket of the coupler shank 62 to allow the ball electrode to move axially within the socket. [0034] When the ball electrode 35 is retained in the socket, the ball electrode should be able to roll in any direction within the socket to allow a positioner to move the ball electrode in any direction along the surface of the structural assembly 15 . A coolant passage 74 for circulating liquid coolant extends into the coupler shank 62 to allow welding heat to be transferred from the ball electrode 35 to the liquid coolant. [0035] In operation, electrode assembly 60 operates similarly to electrode assembly 28 in that the ball electrode 35 rotates within the socket to allow a positioner to move the electrode assembly over the surfaces of a structural assembly 15 . [0036] It should be understood, that either one of the ball electrodes 35 , 47 may be replaced with any suitable electrode that will conduct current from the remaining ball electrode through the assembly opposite the locations of the remaining ball electrode. [0037] While the invention has been described by reference to certain preferred embodiments, it should be understood that numerous changes could be made within the spirit and scope of the inventive concepts described. Accordingly, it is intended that the invention not be limited to the disclosed embodiments, but that it have the full scope permitted by the language of the following claims. GP-304381 NUMBER SHEET 07002.266 [0000] 10 . workstation 11 . apparatus (welding) 12 . workpiece—floor pan 14 . workpiece—undershield 15 . structural assembly (floor pan) 16 . upper side 17 . lower side 18 . support 20 . robot (first positioner) 22 . base 24 . jointed arm 26 . end effector/holder 28 . electrode assembly 30 . coupler shank 32 . end 34 . socket 35 . ball electrode 36 . retainer ring 37 . coolant passage 38 . 39 . second positioner 40 . base 41 . rail 42 . control arms 43 . holder 44 . coupler shank 45 . end 46 . socket 47 . ball electrode 48 . retainer ring 49 . cooling passage 50 . transformer 52 . selected location 54 . weld 56 . 58 . 60 . electrode assembly 62 . coupler shank 64 . end 66 . 68 . groove 70 . spring 72 . retainer ring 74 . coolant passage 76 . 78 . 80 . 82 . 84 . 86 . 88 . 90 . 92 . 94 .
A resistance welding apparatus having a pair of programmable ball electrodes carried on universally movable positioners. The positioners are programmed to move the ball electrodes simultaneously along a seam line so that the ball electrodes clamp and support opposite sides of a pair of stacked workpieces and are electrically charged to form resistance seam welds along the seam lines to connect the workpieces.
1
BACKGROUND [0001] 1. Technical Field [0002] The following disclosure relates to an apparatus, system, and method for performing an electrosurgical procedure and, more particularly, to an apparatus, system and method that utilizes energy based sectioning to cut and/or section tissue as required by an electrosurgical procedure. [0003] 2. Description of Related Art [0004] It is well known in the art that electrosurgical generators are employed by surgeons in conjunction with electrosurgical instruments to perform a variety of electrosurgical surgical procedures (e.g., tonsillectomy, adenoidectomy, etc.). An electrosurgical generator generates and modulates electrosurgical energy which, in turn, is applied to the tissue by an electrosurgical instrument. Electrosurgical instruments may be either monopolar or bipolar and may be configured for open or endoscopic procedures. [0005] Electrosurgical instruments may be implemented to ablate, seal, cauterize, coagulate, and/or desiccate tissue and, if needed, cut and/or section tissue. Typically, cutting and/or sectioning tissue is performed with a knife blade movable within a longitudinal slot located on or within one or more seal plates associated with one or more jaw members configured to receive a knife blade, or portion thereof. The longitudinal slot is normally located on or within the seal plate within a treatment zone (e.g., seal and/or coagulation zone) associated therewith. Consequently, the knife blade cuts and/or sections through the seal and/or coagulation zone during longitudinal translation of the knife blade through the longitudinal slot. In some instances, it is not desirable to cut through the zone of sealed or coagulated tissue, but rather to the left or right of the zone of sealed or coagulated tissue such as, for example, during a tonsillectomy and/or adenoidectomy procedure. SUMMARY OF THE DISCLOSURE [0006] As noted above, after tissue is electrosurgically treated (e.g., sealed), it is sometimes desirable to cut tissue outside of the zone of treated tissue. With this purpose in mind, the present disclosure provides an electrosurgical apparatus that includes a housing having at least one shaft extending therefrom that operatively supports an end effector assembly at a distal end thereof. The end effector assembly includes first and second jaw members pivotably connected to each other and moveable from an open spaced apart position to a closed position. Each of the jaw members operatively couples to an electrically conductive seal plate. In an embodiment, one or both of the jaw members is configured to support one or more filaments thereon for selectively sectioning tissue. The electrically conductive seal plates and the filament each are adapted to connect to an electrical surgical energy source. In an embodiment, the electrosurgical apparatus is in operative communication with a control system having one or more control algorithms for independently controlling and/or monitoring the delivery of electrosurgical energy from the source of electrosurgical energy to the one or more filaments and the tissue sealing plate on each of the jaw members. [0007] The present disclosure also provides a method for performing an electrosurgical procedure. The method includes the initial step of providing an electrosurgical apparatus that includes a pair of jaw members configured to grasp tissue therebetween. In embodiments, one or both of the jaw members may include one or more filaments. The method also includes the steps of: directing electrosurgical energy from an electrosurgical generator through tissue held between the jaw members; directing electrosurgical energy from the electrosurgical generator to one or more filaments in contact with or adjacent to tissue; and applying a force to tissue adjacent a portion of the effected tissue site such that the portion of effected tissue is detachable from the rest of the effected tissue. [0008] The present disclosure further provides a system for performing an electrosurgical procedure. The system includes an electrosurgical apparatus adapted to connect to a source of electrosurgical energy. The electrosurgical apparatus includes a housing having at least one shaft extending therefrom that operatively supports an end effector assembly at a distal end thereof. The end effector assembly includes first and second jaw members pivotably connected to each other and moveable from an open spaced apart position to a closed position to grasp tissue. An electrically conductive tissue sealing plate operatively couples to each of the jaw members. In an embodiment, one or both of the jaw members is configured to support one or more filaments thereon for selectively sectioning tissue. The electrically conductive seal plates and the filament are adapted to connect to an electrical surgical energy source. In an embodiment, the electrosurgical apparatus is in operative communication with a control system. The control system includes one or more algorithms for independently controlling and monitoring the delivery of electrosurgical energy from the source of electrosurgical energy to the at least one filament and the tissue sealing plate on each of the jaw members. BRIEF DESCRIPTION OF THE DRAWING [0009] Various embodiments of the present disclosure are described hereinbelow with references to the drawings, wherein: [0010] FIG. 1 is a perspective view of an electrosurgical apparatus and electrosurgical generator adapted for use with an energy based sectioning (EBS) system intended for use during an electrosurgical procedure according to an embodiment of the present disclosure; [0011] FIG. 2 is a block diagram illustrating components of the system of FIG. 1 ; [0012] FIG. 3 is a schematic representation of an electrical configuration for connecting the electrosurgical apparatus to the electrosurgical generator depicted in FIG. 1 ; [0013] FIG. 4A is an enlarged, side perspective view of an end effector assembly including a filament configuration intended for use with the EBS system of FIG. 1 ; [0014] FIG. 4B is an enlarged view of the area of detail represented by 4 B depicted in FIG. 4A ; [0015] FIGS. 5A-5C are enlarged, front perspective views of various filament configurations suitable for use with the end effector assembly of FIG. 4A ; [0016] FIGS. 6A-6B illustrate the electrosurgical apparatus depicted in FIG. 1 in use; [0017] FIG. 7 is an enlarged, side view of an end effector assembly including a filament configuration intended for use with the EBS system of FIG. 1 according to another embodiment of the present disclosure; and [0018] FIG. 8 is a flowchart of a method for performing an electrosurgical procedure according to an embodiment of the present disclosure. DETAILED DESCRIPTION [0019] Detailed embodiments of the present disclosure are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the disclosure, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present disclosure in virtually any appropriately detailed structure. [0020] The present disclosure includes an electrosurgical apparatus that is adapted to connect to an electrosurgical generator that includes a control system configured for energy based sectioning (EBS). [0021] With reference to FIG. 1 an illustrative embodiment of an electrosurgical generator 200 (generator 200 ) is shown. Generator 200 is operatively and selectively connected to bipolar forceps 10 for performing an electrosurgical procedure. As noted above, an electrosurgical procedure may include sealing, cutting, coagulating, desiccating, and fulgurating tissue all of which may employ RF energy. Generator 200 may be configured for monopolar and/or bipolar modes of operation. Generator 200 includes all necessary components, parts, and/or members needed for a control system 300 (system 300 ) to function as intended. Generator 200 generates electrosurgical energy, which may be RF (radio frequency), microwave, ultrasound, infrared, ultraviolet, laser, thermal energy or other electrosurgical energy. An electrosurgical module 220 generates RF energy and includes a power supply 250 for generating energy and an output stage 252 which modulates the energy that is provided to the delivery device(s), such as an end effector assembly 100 , for delivery of the modulated energy to a patient. Power supply 250 may be a high voltage DC or AC power supply for producing electrosurgical current, where control signals generated by the system 300 adjust parameters of the voltage and current output, such as magnitude and frequency. The output stage 252 may modulate the output energy (e.g., via a waveform generator) based on signals generated by the system 300 to adjust waveform parameters, e.g., waveform shape, pulse width, duty cycle, crest factor, and/or repetition rate. System 300 may be coupled to the generator module 220 by connections that may include wired and/or wireless connections for providing the control signals to the generator module 220 . [0022] With continued reference to FIG. 1 , a system 300 for performing an electrosurgical procedure (e.g., RF tissue procedure) is shown. System 300 is configured to, among other things, analyze parameters such as, for example, power, tissue and filament temperature, current, voltage, power, impedance, etc., such that a proper tissue effect can be achieved. [0023] With reference to FIG. 2 , system 300 includes one or more processors 302 in operative communication with a control module 304 executable on the processor 302 , and is configured to, among other things, quantify electrical and thermal parameters during tissue sectioning such that when a threshold value for electrical and thermal parameters is met, the control system 300 provides a signal to a user to apply a force to tissue. Control module 304 instructs one or more modules (e.g., an EBS module 306 ) to transmit electrosurgical energy, which may be in the form of a wave or signal/pulse, via one or more cables (e.g., cable 410 ) to one or both of the seal plates 118 , 128 and/or one or more filaments 122 . Electrosurgical energy may be transmitted to the seal plates 118 , 128 and the filaments 122 simultaneously or consecutively. [0024] The control module 304 processes information and/or signals (e.g., tissue and/or filament temperature data from sensors 316 ) input to the processor 302 and generates control signals for modulating the electrosurgical energy in accordance with the input information and/or signals. Information may include pre-surgical data (e.g., tissue and/or filament temperature threshold values) entered prior to the electrosurgical procedure or information entered and/or obtained during the electrosurgical procedure through one or more modules (e.g., EBS module 306 ) and/or other suitable device(s). The information may include requests, instructions, ideal mapping(s) (e.g., look-up-tables, continuous mappings, etc.), sensed information and/or mode selection. [0025] The control module 304 regulates the generator 200 (e.g., the power supply 250 and/or the output stage 252 ) which adjusts various parameters of the electrosurgical energy delivered to the patient (via one or both of the seal plates and/or one or more filaments) during the electrosurgical procedure. Parameters of the delivered electrosurgical energy that may be regulated include voltage, current, resistance, intensity, power, frequency, amplitude, and/or waveform parameters, e.g., waveform shape, pulse width, duty cycle, crest factor, and/or repetition rate of the output and/or effective energy. [0026] The control module 304 includes software instructions executable by the processor 302 for processing algorithms and/or data received by sensors 316 , and for outputting control signals to the generator module 220 and/or other modules. The software instructions may be stored in a storage medium such as a memory internal to the processor 302 and/or a memory accessible by the processor 302 , such as an external memory, e.g., an external hard drive, floppy diskette, CD-ROM, etc. [0027] In embodiments, an audio or visual feedback monitor or indicator (not explicitly shown) may be employed to convey information to the surgeon regarding the status of a component of the electrosurgical system or the electrosurgical procedure. Control signals provided to the generator module 220 are determined by processing (e.g., performing algorithms), which may include using information and/or signals provided by sensors 316 . [0028] The control module 304 regulates the electrosurgical energy in response to feedback information, e.g., information related to tissue condition at or proximate the surgical site. Processing of the feedback information may include determining: changes in the feedback information; rate of change of the feedback information; and/or relativity of the feedback information to corresponding values sensed prior to starting the procedure (pre-surgical values) in accordance with the mode, control variable(s) and ideal curve(s) selected. The control module 304 then sends control signals to the generator module 220 such as for regulating the power supply 250 and/or the output stage 252 . [0029] Regulation of certain parameters of the electrosurgical energy may be based on a tissue response such as recognition of when a proper seal is achieved and/or when a predetermined threshold temperature value is achieved. Recognition of the event may automatically switch the generator 200 to a different mode of operation (e.g., EBS mode or “RF output mode”) and subsequently switch the generator 200 back to an original mode after the event has occurred. In embodiments, recognition of the event may automatically switch the generator 200 to a different mode of operation and subsequently shutoff the generator 200 . [0030] EBS module 306 (shown as two modules for illustrative purposes) may be digital and/or analog circuitry that can receive instructions from and provide status to a processor 302 (via, for example, a digital-to-analog or analog-to-digital converter). EBS module 306 is also coupled to control module 304 to receive one or more electrosurgical energy waves at a frequency and amplitude specified by the processor 302 , and/or transmit the electrosurgical energy waves along the cable 410 to one or both of the seal plates, one or more filaments 122 and/or sensors 316 . EBS module 306 can also amplify, filter, and digitally sample return signals received by sensors 316 and transmitted along cable 410 . [0031] A sensor module 308 senses electromagnetic, electrical, and/or physical parameters or properties at the operating site and communicates with the control module 304 and/or EBS module 306 to regulate the output electrosurgical energy. The sensor module 308 may be configured to measure, i.e., “sense”, various electromagnetic, electrical, physical, and/or electromechanical conditions, such as at or proximate the operating site, including: tissue impedance, tissue temperature, and so on. For example, sensors of the sensor module 308 may include sensors 316 , such as, for example, optical sensor(s), proximity sensor(s), pressure sensor(s), tissue moisture sensor(s), temperature sensor(s), and/or real-time and RMS current and voltage sensing systems. The sensor module 308 measures one or more of these conditions continuously or in real-time such that the control module 304 can continually modulate the electrosurgical output in real-time. [0032] In embodiments, sensors 316 may include a smart sensor assembly (e.g., a smart sensor, smart circuit, computer, and/or feedback loop, etc. (not explicitly shown)). For example, the smart sensor may include a feedback loop which indicates when a tissue seal is complete based upon one or more of the following parameters: tissue temperature, tissue impedance at the seal, change in impedance of the tissue over time and/or changes in the power or current applied to the tissue over time. An audible or visual feedback monitor may be employed to convey information to the surgeon regarding the overall seal quality or the completion of an effective tissue seal. [0033] With reference again to FIG. 1 , electrosurgical apparatus 10 can be any type of electrosurgical apparatus known in the available art, including but not limited to electrosurgical apparatuses that can grasp and/or perform any of the above mentioned electrosurgical procedures. One type of electrosurgical apparatus 10 may include bipolar forceps as disclosed in United States Patent Publication No. 2007/0173814 entitled “Vessel Sealer and Divider For Large Tissue Structures”. A brief discussion of bipolar forceps 10 and components, parts, and members associated therewith is included herein to provide further detail and to aid in the understanding of the present disclosure. [0034] With continued reference to FIG. 1 , bipolar forceps 10 is shown for use with various electrosurgical procedures and generally includes a housing 20 , a handle assembly 30 , a rotating assembly 80 , a trigger assembly 70 , a shaft 12 , a drive assembly (not explicitly shown), and an end effector assembly 100 , which mutually cooperate to grasp, seal and divide large tubular vessels and large vascular tissues. Although the majority of the figure drawings depict a bipolar forceps 10 for use in connection with endoscopic surgical procedures, the present disclosure may be used for more traditional open surgical procedures. [0035] Shaft 12 has a distal end 16 dimensioned to mechanically engage the end effector assembly 100 and a proximal end 14 which mechanically engages the housing 20 . In the drawings and in the descriptions which follow, the term “proximal,” as is traditional, will refer to the end of the forceps 10 which is closer to the user, while the term “distal” will refer to the end which is farther from the user. [0036] Forceps 10 includes an electrosurgical cable 410 that connects the forceps 10 to a source of electrosurgical energy, e.g., generator 200 , shown schematically in FIG. 1 . As shown in FIG. 3 , cable 410 is internally divided into cable leads 410 a , 410 b and 425 b which are designed to transmit electrical potentials through their respective feed paths through the forceps 10 to the end effector assembly 100 . [0037] For a more detailed description of handle assembly 30 , movable handle 40 , rotating assembly 80 , electrosurgical cable 410 (including line-feed configurations and/or connections), and the drive assembly reference is made to commonly owned Patent Publication No., 2003-0229344, filed on Feb. 20, 2003, entitled VESSEL SEALER AND DIVIDER AND METHOD OF MANUFACTURING THE SAME. [0038] With reference now to FIGS. 4A , 5 A- 5 C, and initially with reference to FIG. 4A , end effector assembly 100 is shown attached at the distal end 16 of shaft 12 and includes a pair of opposing jaw members 110 and 120 . As noted above, movable handle 40 of handle assembly 30 operatively couples to a drive assembly which, together, mechanically cooperate to impart movement of the jaw members 110 and 120 from an open position wherein the jaw members 110 and 120 are disposed in spaced relation relative to one another, to a clamping or closed position wherein the jaw members 110 and 120 cooperate to grasp tissue therebetween. [0039] Jaw members 110 and 120 are generally symmetrical and include similar component features which cooperate to effect the sealing and dividing of tissue. As a result, and unless otherwise noted, only jaw member 110 and the operative features associated therewith are described in detail herein, but as can be appreciated many of these features, if not all, apply to equally jaw member 120 as well. [0040] Jaw member 110 includes an insulative jaw housing 117 and an electrically conductive seal plate 118 (seal plate 118 ). Insulator 117 is configured to securely engage the electrically conductive seal plate 118 . Seal plate 118 may be manufactured from stamped steel. This may be accomplished by stamping, by overmolding, by overmolding a stamped electrically conductive sealing plate and/or by overmolding a metal injection molded seal plate. All of these manufacturing techniques produce an electrode having a seal plate 118 that is substantially surrounded by the insulating substrate. Within the purview of the present disclosure, jaw member 110 may include a jaw housing 117 that is integrally formed with a seal plate 118 . [0041] Jaw member 120 includes a similar structure having an outer insulative housing 127 that is overmolded (to capture seal plate 128 ). [0042] End effector assembly 100 is configured for energy based sectioning (EBS). To this end, end effector assembly 100 is provided with one or more electrodes or filaments 122 . Filament 122 may be configured to operate in monopolar or bipolar modes of operation, and may operate alone or in conjunction with control system 300 (mentioned and described above). With this purpose in mind, filament 122 is in operative communication with one or more sensors 316 operatively connected to one or more modules of control system 300 by way of one or more optical fibers or a cable (e.g., cable 410 ). [0043] Filament 122 functions to convert electrosurgical energy into thermal energy such that tissue in contact therewith (or adjacent thereto) may be heated and subsequently cut or severed. With this purpose in mind, filament 122 may manufactured from any suitable material capable of converting electrosurgical energy into thermal energy and/or capable of being heated, including but not limited to metal, metal alloy, ceramic and the like. Metal and/or metal alloy suitable for the manufacture of filament 122 may include Tungsten, or derivatives thereof. Ceramic suitable for the manufacture of filament 122 may include those of the non-crystalline (e.g., glass-ceramic) or crystalline type. [0044] Filament 122 is configured to contact tissue during or after application of electrosurgical energy that is intended to treat tissue (e.g., seal tissue). To this end, filament 122 is disposed at predetermined locations on one or both of the jaw members 110 , 120 , see FIG. 4A for example. As shown, filament 122 extends from and along seal plate 118 of jaw member 110 . Filaments 122 disposed on the jaw members 110 , 120 may be in vertical registration with each other. [0045] The top portion of filament 122 may have any suitable geometric configuration. For example, FIG. 4A illustrates filament 122 having a top portion that is curved, while FIGS. 5A and 5 B illustrate, respectively, one or more filaments 122 each having top portions that are flat and one or more filaments 122 each having top portions that are curved, flat, and pointed. [0046] To prevent short-circuiting from occurring between the filament 122 and the seal plate (e.g., seal plate 118 ) from which it extends or is adjacent thereto, filament 122 is provided with an insulative material 126 , as best seen in FIG. 4B . The insulative material 126 may be disposed between the portion of the filament 122 that extends from or that is adjacent to the seal plate. Alternatively, or in addition thereto, the portion of the filament 122 that extends from or that is adjacent to the seal plate may be made from a non-conductive material. In embodiments, one or more filaments 122 may have portions that are insulated and/or separated from each other (see FIGS. 5A-5C , for example). [0047] Filament 122 may be active prior, during, or subsequent to the application of electrosurgical energy used for performing an electrosurgical procedure (e.g., sealing). Filament 122 , or portions thereof, may be activated and/or controlled individually and/or collectively. [0048] In embodiments, filament 122 may be coated with a conductive non-stick material 124 , such as, for example, a conductive non-stick mesh, as best seen in FIG. 4B . Filament 122 coated with a conductive non-stick material 124 or conductive non-stick mesh may prevent and/or impede sticking and/or charring of tissue during the application of electrosurgical energy for performing the electrosurgical procedure or EBS. [0049] One or both of the jaw members 110 , 120 may include one or more sensors 316 . Sensors 316 are placed at predetermined locations on, in, or along surfaces of the jaw members 110 , 120 (FIGS. 4 A and 5 A- 5 C). In embodiments, end effector assembly 100 and/or jaw members 110 and 120 may have sensors 316 placed near a proximal end and/or near a distal end of jaw members 110 and 120 , as well as along the length of jaw members 110 and 120 . [0050] With reference now to FIGS. 6A and 6B , operation of bipolar forceps 10 under the control of system 300 is now described. For illustrative purposes, EBS is described subsequent to the application of electrosurgical energy for achieving a desired tissue effect (e.g., tissue sealing). Processor 302 instructs EBS module 306 to generate electrosurgical energy in response to the processor instructions, the EBS module 306 can access a pulse rate frequency clock associated with a time source (not explicitly shown) to form an electrosurgical pulse/signal exhibiting the attributes (e.g., amplitude and frequency) specified by the processor 302 and can transmit such pulse/signal on one or more cables (e.g., cable 410 ) to filament 122 and/or sensors 316 . In another embodiment, the processor does not specify attributes of the electrosurgical pulse/signal, but rather instructs/triggers other circuitry to form the electrosurgical pulse/signal and/or performs timing measurements on signals conditioned and/or filtered by other circuitry. [0051] The transmitted electrosurgical pulse/signal travels along cable 410 to one or more filaments 122 that is/are in contact with, and/or otherwise adjacent to tissue. Filament 122 converts the electrosurgical energy to thermal energy and heats the tissue in contact therewith or adjacent thereto. Data, such as, for example, temperature, pressure, impedance and so forth is sensed by sensors 316 and transmitted to and sampled by the EBS module 306 and/or sensor module 224 . [0052] The data can be processed by the processor 302 and/or EBS module 306 to determine, for example, when a tissue and/or filament threshold temperature has been achieved. The processor 302 can subsequently transmit and/or otherwise communicate the data to the control module 304 such that output power from generator 200 may be adjusted accordingly. The processor 302 can also subsequently transmit and/or otherwise communicate the data to a local digital data processing device, a remote digital data processing device, an LED display, a computer program, and/or to any other type of entity (none of which being explicitly shown) capable of receiving the data. [0053] Upon reaching a desired tissue and/or filament 122 threshold temperature, control system 300 may indicate (by way of an audio or visual feedback monitor or indicator, previously mentioned and described above) to a user that tissue is ready for sectioning. A user may then grasp tissue (for example, with a surgical implement or bipolar forceps 10 ) adjacent to the operating site and outside the seal zone ( FIG. 6A ) and apply a pulling force “F” generally normal and along the same plane as the sectioning line which facilitates the separation of tissue ( FIG. 6B ). Application of the pulling force “F” separates the unwanted tissue from the operating site with minimal impact on the seal zone. The remaining tissue at the operating site is effectively sealed and the separated tissue may be easily discarded. [0054] From the foregoing and with reference to the various figure drawings, those skilled in the art will appreciate that certain modifications can also be made to the present disclosure without departing from the scope of the same. For example, as best seen in FIG. 7 , it may be preferable to include a channel or cavity 122 a (shown phantomly) on one or both of the seal plates (e.g., seal plate 118 ) that is in vertical registration with a filament 122 on an opposing seal surface (e.g., seal plate 128 ). Here, the cavity 122 a and the filament 122 are configured to matingly engage with each other when the jaw members are in a closed configuration such that effective heating of tissue at the tissue site may be achieved. As can be appreciated by one skilled in the art, a filament 122 of a given structure configured to matingly engage with a corresponding cavity 122 a may allow the filament 122 to contact a greater tissue area which, in turn, may enable a user to heat more tissue for a given EBS procedure. [0055] While a majority of the drawings depict a filament 122 that is disposed on one or both of the seal plates of one or both of the jaw members 110 , 120 , it is within the purview of the present disclosure to have one or more filaments 122 disposed on and/or along an outside and/or inside edge of one or both of the jaw members 110 , 120 , or any combination thereof. For example, filament 122 may extend partially along an outside edge of jaw member 110 (see FIG. 7 , for example). Alternatively, filament 122 may extend along the entire length of a periphery of jaw member 110 . In either instance, filament 122 may be configured as described above and/or may include the same, similar and/or different structures to facilitate separating tissue. [0056] FIG. 8 shows a method 500 for performing an electrosurgical procedure. At step 502 , an electrosurgical apparatus including a pair of jaw members configured to grasp tissue therebetween and including one or more filaments is provided. At step 504 , electrosurgical energy from an electrosurgical generator is directed through tissue held between the jaw members. At step 506 , electrosurgical energy from the electrosurgical generator is transmitted to one or more filaments in contact with or adjacent to tissue such that tissue may be severed. And at step 508 , a force is applied to tissue adjacent the effected tissue site generally in a normal or transverse direction to facilitate separation of the tissue. [0057] In embodiments, the step of delivering electrosurgical energy to the at least one filament may include the step of system 300 quantifying one of electrical and thermal parameter associated with tissue and the filament. [0058] In embodiments, the step of applying a force may include the step of applying the force simultaneously with delivering electrosurgical energy from the source of electrosurgical energy to the at least one filament. [0059] In embodiments, the step of applying a force may include the step of applying the force consecutively after audible or visible indication (e.g., an LED located on generator 200 displays “Apply Pulling Force”). [0060] While several embodiments of the disclosure have been shown in the drawings, it is not intended that the disclosure be limited thereto, as it is intended that the disclosure be as broad in scope as the art will allow and that the specification be read likewise. Therefore, the above description should not be construed as limiting, but merely as exemplifications of particular embodiments. Those skilled in the art will envision other modifications within the scope and spirit of the claims appended hereto.
An electrosurgical apparatus that includes a housing having at least one shaft extending therefrom that operatively supports an end effector assembly at a distal end thereof is provided. The end effector assembly includes first and second jaw members pivotably connected to each other and moveable from an open spaced apart position to a closed position. Each of the jaw members operatively couples to an electrically conductive seal plate. One or both of the jaw members is configured to support one or more filaments thereon for selectively sectioning tissue. The electrically conductive seal plates and the filament are adapted to connect to an electrical surgical energy source. The electrosurgical apparatus is in operative communication with a control system having one or more control algorithms for independently controlling and monitoring the delivery of electrosurgical energy from the source of electrosurgical energy to the one or more filaments and the tissue sealing plate.
0
CROSS REFERENCE TO RELATED APPLICATION This is a division of application Ser. No. 07/286,567 filed on Dec. 16, 1988 by Bruce Cowger entitled VOLUMETRICALLY EFFICIENT INK JET PEN CAPABLE OF EXTREME ALTITUDE AND TEMPERATURE EXCURSIONS, now U.S. Pat. No. 4,920,362. FIELD OF THE INVENTION The present invention relates to ink jet printing systems, and more particularly to volumetrically efficient ink jet pens that can undergo arbitrarily large altitude and temperature excursions without leaking ink. BACKGROUND AND SUMMARY OF THE INVENTION Ink jet printers have become very popular due to their quiet and fast operation and their high print quality on plain paper. A variety of ink jet printing methods have been developed. In one ink jet printing method, termed continuous jet printing, ink is delivered under pressure to nozzles in a print head to produce continuous jets of ink. Each jet is separated by vibration into a stream of droplets which are charged and electrostatically deflected, either to a printing medium or to a collection gutter for subsequent recirculation. U.S. Pat. No. 3,596,275 is illustrative of this method. In another ink jet printing method, termed electrostatic pull printing, the ink in the printing nozzles is under zero pressure or low positive pressure and is electrostatically pulled into a stream of droplets. The droplets fly between two pairs of deflecting electrodes that are arranged to control the droplets' direction of flight and their deposition in desired positions on the printing medium. U.S. Pat. No. 3,060,429 is illustrative of this method. A third class of methods, more popular than the foregoing, is known as drop-on-demand printing. In this technique, ink is held in the pen at below atmospheric pressure and is ejected by a drop generator, one drop at a time, on demand. Two principal ejection mechanisms are used: thermal bubble and piezoelectric pressure wave. In the thermal bubble systems, a thin film resistor in the drop generator is heated and causes sudden vaporization of a small portion of the ink. The rapidly expanding ink vapor displaces ink from the nozzle causing drop ejection. U.S. Pat. No. 4,490,728 is exemplary of such thermal bubble drop-on-demand systems. In the piezoelectric pressure wave systems, a piezoelectric element is used to abruptly compress a volume of ink in the drop generator, thereby producing a pressure wave which causes ejection of a drop at the nozzle. U.S. Pat. No. 3,832,579 is exemplary of such piezoelectric pressure wave drop-on-demand systems. The drop-on-demand techniques require that under quiescent conditions the pressure in the ink reservoir be below ambient so that ink is retained in the pen until it is to be ejected. The amount of this "underpressure" (or "partial vacuum") is critical. If the underpressure is too small, or if the reservoir pressure is positive, ink tends to escape through the drop generators. If the underpressure is too large, air may be sucked in through the drop generators under quiescent conditions. (Air is not normally sucked in through the drop generators because their high capillarity retains the air-ink meniscus against the partial vacuum of the reservoir.) The underpressure required in drop-on-demand systems can be obtained in a variety of ways. In one system, the underpressure is obtained gravitationally by lowering the ink reservoir so that the surface of the ink is slightly below the level of the nozzles. However, such positioning of the ink reservoir is not always easily achieved and places severe constraints on print head design. Exemplary of this gravitational underpressure technique is U.S. Pat. No. 3,452,361. Alternative techniques for achieving the required underpressure are shown in U.S. Pat. No. 4,509,062 and in copending application Ser. No. 07/115,013 filed Oct. 28, 1987, both assigned to the present assignee. In the former patent, the underpressure is achieved by using a bladder type ink reservoir which progressively collapses as ink is drawn therefrom. The restorative force of the flexible bladder keeps the pressure of the ink in the reservoir slightly below ambient. In the system disclosed in the latter patent application, the underpressure is achieved by using a capillary reservoir vent tube, or bubble generator, that is immersed in ink in the ink reservoir at one end and coupled to an overflow catchbasin open to atmospheric pressure at the other. As the printhead, which is also connected to the reservoir, draws ink from the reservoir, the internal pressure of the reservoir falls. This underpressure increases as ink is ejected from the reservoir. When the underpressure reaches a threshold value, it draws a small volume of air in through the capillary tube and into the reservoir, thereby preventing the underpressure from exceeding the threshold value. While the foregoing two approaches for maintaining reservoir underpressure have proven highly satisfactory and unique in many respects, they nonetheless have certain drawbacks. For example, in the pen described in the above-referenced patent, as the flexible bladder reaches its fully collapsed state, the underpressure increases to the point that the drop generator can no longer draw ink therefrom and printing ceases with unused ink left in the bladder. The pen described in the above-referenced application is limited in the temperature and altitude extremes to which it can function properly. For example, if such a pen is transported in an aircraft cabin that is pressurized to an 8000 foot elevation, any air in the ink reservoir will expand in volume by a factor of approximately one third. If the volume of air in the reservoir is more than three times the volume of the catchbasin to which overflow from the capillary reservoir vent tube is routed, the air's expansion will drive more ink into the catchbasin than it can contain and the catchbasin will overflow. This problem can be solved by making the catchbasin large enough to contain the ink in any possible altitude or temperature circumstance, for example, by making the size of the catchbasin fully 35 percent the size of the ink reservoir. However, this solution is volumetrically inefficient and limits the amount of ink that a pen of a given volume can contain. It is an object of the present invention to provide an ink jet pen that overcomes these problems. It is a more particular object of the present invention to provide a volumetrically efficient ink jet pen that can undergo arbitrarily large altitude or temperature excursions with an arbitrarily small catchbasin. According to one embodiment of the present invention, an ink jet pen is constructed with a plurality of ink chambers serially coupled together by small coupling orifices. An ink well extends downwardly from the first chamber and supplies ink to a drop generator positioned at the bottom thereof. A catchbasin extends beneath all of the chambers and is coupled to the last chamber in the series by a drop tube with a bubble generator on the top thereof. In operation, the plurality of serially coupled chambers that comprises the pen's ink reservoir are initially all filled with ink. As ink is ejected from the first chamber by operation of the pen's drop generator, the partial vacuum induced therein is relieved by ink drawn into the first chamber from the second, which in turn draws ink from the third. The resulting partial vacuum in the third chamber is relieved by the introduction of air bubbles by the bubble generator. As printing continues, the third reservoir eventually becomes depleted of ink and is filled instead with air introduced from the catchbasin. Thereafter, further printing draws ink from the second chamber into the first and draws bubbles of air from the third chamber into the second. Finally, when the second chamber becomes depleted of ink, further printing simply draws air bubbles into the first chamber from the second. By the foregoing arrangement, only one chamber contains both air and ink at any given time. The others are filled either with ink or air. Consequently, altitude or pressure changes that cause air in the pen to expand operate on only one of the three chambers to drive ink therefrom, since the others either have no air that can expand or no ink that can be driven. The volume of ink driven to the catchbasin in the illustrated three chamber pen is thus just one third of that in a comparable single chamber pen for any given environmental excursion. Accordingly, the pen of the present invention can be manufactured with a catchbasin only one third the size as required in the prior art, thereby increasing the pen's volumetric efficiency and permitting more of the pen's volume to be used for the initial load of ink. The principles of the present invention can be applied to pens with an arbitrarily high number of chambers, by which the requisite size of the catchbasin can be reduced to an arbitrarily small volume. The foregoing and additional objects, features and advantages of the present invention will be more readily apparent from the following detailed description, which proceeds with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view of an ink jet pen according to one embodiment of the present invention. FIG. 2 is sectional view of the pen of FIG. 1 in a partially depleted condition. FIG. 3 is a sectional view of the pen of FIG. 2 after a temperature increase has expelled some of the ink in the second chamber to the catchbasin. FIG. 4 is a sectional view of the pen of FIG. 3 after a temperature decrease has caused the ink formerly in the catchbasin to be drawn back into the second chamber. FIG. 5 shows a different, "cluster of grapes," embodiment of an ink reservoir usable with the pen of the present invention. FIG. 6 shows another chamber interconnection arrangement wherein coupling conduits extend beneath the ink chambers. DETAILED DESCRIPTION Referring to FIGS. 1-4, an ink jet pen 10 according to one embodiment of the present invention includes a multi-chambered ink reservoir 12, here comprised of first, second and third chambers 14, 16 and 18, respectively. The first chamber 14 is coupled to the second chamber 16 by a small coupling orifice 20 positioned near the bottoms of said chambers in a lower portion of a first dividing wall 22. The second chamber 16 is similarly coupled to the third chamber 18 by a small coupling orifice 24 in a lower portion of a second dividing wall 26. Extending downwardly from the first chamber 14 is an ink well 28 that supplies ink to a drop generator 30 disposed at the bottom thereof. Drop generator 30 is conventional in design and may comprise, for example, a thermal bubble type ink jet or a piezoelectric pressure wave type ink jet. Ink well 28 may have a filter 32 disposed thereon to prevent clogging of the printing orifices by foreign matter. Extending beneath the chambers 14-18 is a catchbasin 34 that is coupled to the third chamber by a drop tube 36 that has a bubble generating orifice 38 on its top. The catchbasin is vented to ambient pressure by a chimney 40 extending upwardly therein from the base of the pen. In operation, the three chambers 14-18 are initially all filled with ink. In this filled condition, altitude or temperature excursions have substantially no effect on the pen because there is no air in any of the chambers that can expand and drive ink therefrom. The ink volume itself does not change with altitude or temperature. The one element of the pen that does contain air, the catchbasin, is vented to ambient, so any expansion of the air therein is easily relieved. During printing, air is introduced sequentially into the three chambers. When printing begins, the ejection of ink by the drop generator 30 causes a partial vacuum in the first chamber 14. This partial vacuum is relieved by the drawing of replacement ink into the first chamber from the second chamber 16 through the orifice 20. (Since the orifice 20 is wetted on both sides, it acts only as a fluid restriction. This restriction can be made arbitrarily small by the use of multiple orifices in parallel.) This drawing of ink from the second chamber likewise causes the second chamber to draw a corresponding volume of ink from the third chamber 18 through orifice 24. When the partial vacuum in the third chamber 18 reaches a threshold value (about one and a half inches of water in the illustrated embodiment), it is sufficient to draw an air bubble through the bubble generator orifice 38. This pressure is termed the "bubble pressure" and is principally dependent on the diameter of orifice and the viscosity of the ink. In the illustrative embodiment, the bubble generator orifice 38 has a diameter of 0.012 inches. (Partial vacuums smaller than the bubble pressure are insufficient to overcome the surface tension at the ink/air interface and thus are unable to draw bubbles through the bubble generator.) The introduction of an air bubble through the bubble generator 38 and into the third chamber 18 lowers the partial vacuum in that chamber below the threshold value momentarily, until continued ejection of ink again brings it to the bubble pressure and another bubble is introduced. Continued printing results in the periodic introduction of bubbles, causing the volume of air in the third chamber to increase. During this "steady state" printing condition, the underpressure in the third chamber oscillates in a closely bounded range about the bubble pressure. The first and second chambers are likewise regulated at this pressure since there is no pressure drop across the coupling orifices 20, 24. (A pressure drop only occurs at these orifices if there is ink on one side and air on the other.) As printing continues, the third chamber 18 eventually becomes filled with air and exhausted of ink. Thereafter, it cannot replace the ink drawn from the second chamber by the first with ink, as was earlier the case. Instead, continued printing causes the introduction of bubbles of air into the second chamber from the third. (The third chamber is now at atmospheric pressure since there is no air/ink interface at bubble generator orifice 38.) With the third chamber filled with air, the coupling orifice 24 between the second and third chambers acts as a bubble generator. This orifice 24 is sized to produce the same pressure differential (or bubble pressure) as the bubble generator orifice 38 did earlier (i.e. about one and a half inches of water) so that the partial vacuum in the ink chambers 14, 16 does not change. Continued operation of the pen likewise drains the second chamber 16 and fills it with air so that only the first chamber contains ink. Thereafter, air bubbles, rather than ink, are drawn into the first chamber to replace the volume lost due to printing. Again, the coupling orifice 20 serves as a bubble generator and maintains the pressure in the first chamber at the desired value below ambient. Finally, the ink becomes exhausted from the first chamber and the pen must be replaced or refilled. As noted earlier, when all of the chambers are filled with ink, altitude and temperature excursions have no effect since there is no air in the pen that can expand and drive ink to the catchbasin. During the pen's first phase of printing, when the first and second chambers are filled with ink and there is some air in the third chamber, environmental changes which cause the air to expand will drive ink from the third chamber 18, through the bubble generator orifice 38 and into the catchbasin 34. In the illustrated example, the pen is designed to perform at altitude excursions of up to 8000 feet. At that altitude, air pressure is approximately three quarters of that at sea level, so the air trapped in the third chamber expands by an inversely proportional amount, or by a factor of one third. If the catchbasin volume is one third the volume of the third chamber, it will be more than sufficient to contain the expelled ink. (The only situation in which the volume required by the third chamber would fully increase by a factor of one third is if it is completely filled with air. In this case, there would be no ink to be driven into the catchbasin. To the extent that the third chamber does contain ink, it does not contain expandable air, so a catchbasin sized one third the volume of the third chamber is more than adequate to contain the anticipated ink overflow.) When the environmental factors subsequently change and the volume of air trapped in the third chamber 18 contracts and returns to its original volume, a partial vacuum is formed in the third chamber that draws ink from the catchbasin 34, up the drop tube 36 and back into the third chamber through the bubble generator orifice 38. The situation during the second phase of operation, in which the first chamber is full of ink, the third chamber is full of air, and the second chamber contains both, is similar. An environmental change that causes the volume of air in the second chamber to expand drives ink out of the second chamber, through the coupling orifice 24 and into the empty third chamber. A small volume of ink can be received in the third chamber without any being driven into the catchbasin 34. However, once the volume of ink driven into the third chamber is sufficient to cover the bubble generator orifice 38, the third chamber's link to atmospheric pressure is cut off and the chamber is effectively sealed. Further ink driven into the third chamber from the second causes a corresponding volume to be driven from the third chamber through the bubble generator orifice into the catchbasin. If a corresponding volume of ink was not driven into the catchbasin, the additional ink in the third chamber would have to work to compress the air trapped in that now-sealed chamber. The path of least resistance is for ink instead to leave the third chamber for the vented catchbasin. Consequently, substantially all of the ink driven from the second chamber 16 by the expansion of the air therein flows into the catchbasin. Only a small amount pools on the floor of the third chamber. When the environmental conditions thereafter change and the air trapped in the second chamber 16 contracts in volume, a partial vacuum is formed in the second chamber that draws ink from the catchbasin 34, through the drop tube 36, the bubble generator orifice 38, the small pool on the floor of the third chamber and finally through the coupling orifice 24 and into the second chamber. This sequence of events is illustrated in FIGS. 2-4. FIG. 2 shows a pen according to the present invention in the second phase of its operation, i.e. with the first chamber 14 filled with ink, the third chamber 18 filled with air, and the second chamber 16 containing both. As the temperature rises, the air in the second chamber expands and drives ink through the third chamber 18 and into the catchbasin 34, as shown in FIG. 3. When the temperature thereafter falls, the ink in the catchbasin is drawn up and through the third chamber and back into the second chamber, as shown in FIG. 4. A similar sequence of events occurs when both the second and third chambers are depleted of ink. A rise in temperature causes the air in the first chamber to expand, driving the ink therein through the orifice 20 to the second chamber 16, which is at atmospheric pressure due to open orifices 24 and 38. The ink driven from the first chamber collects in the second until the orifice 24 venting the second chamber is blocked by the expelled ink. Thereafter, continued expulsion of ink from the first chamber 14 forces ink from the pool on the floor of the second chamber 16 through the orifice 24 and into the third chamber 18. This ink again pools until it blocks the drop generator orifice 38, at which time ink is driven through it into the catchbasin 34. When the environmental conditions thereafter change and the air trapped in the first chamber 14 contracts in volume, the ink retraces its path up out of the catchbasin, through the drop generator 38, the third chamber 18, the orifice 24, the second chamber 16, the orifice 20 and finally back into the first chamber 14. It will be recognized that the volume of the catchbasin is dependent on the altitude and temperature extremes to which the pen should function, and the volume of the largest ink chamber. In the simplest two chamber embodiment of the invention, assuming equal chamber volumes, the volume of air that can drive ink from the reservoir to the catchbasin is always less than half the volume of the reservoir. (Similarly, the volume of ink that can be driven from the reservoir to the catchbasin is always less than half the volume of the reservoir.) Consequently, the catchbasin can be one-half its usual size. The catchbasin size can be further reduced to an arbitrarily small volume by segregating the ink reservoir into an correspondingly large number of commensurately small chambers. While the foregoing description has illustrated one embodiment of the invention, the principles thereof are equally applicable to a variety of other constructions. Exemplary is the ink chamber arrangement shown in FIG. 5. While in the FIG. 1 embodiment the reservoir was divided into a plurality of chambers by dividing walls defining coupling orifices, in FIG. 5 the chambers are in a "cluster of grapes" configuration and are coupled by coupling tubes 42 and 44 extending therebetween. Similarly, while the FIG. 1 embodiment shows the coupling orifices as positioned in the side walls of the chambers, they need not be so located. FIG. 6 shows an arrangement in which coupling orifices 20', 24' open to flow channels 46, 48 that extend beneath the walls dividing the chambers 14-18. Having described and illustrated the principles of my invention with reference to a preferred embodiment and several variations thereof, it should be apparent that the invention can be further modified in arrangement and detail without departing from such principles. For example, while the invention has been described with reference to an ink reservoir comprised of serially connected ink chambers, a variety of other chamber interconnection topologies may advantageously be used. Similarly, while the invention has been illustrated as having only a single orifice coupling adjacent ink chambers, a plurality of coupling orifices can advantageously be used. (If only a single orifice is used, any foreign matter that becomes lodged in the orifice would critically impair operation of the pen. By using several orifices operated in parallel, the reliability of the pen is improved.) Similarly, while the invention has been described in the context of a single ink pen, the invention is equally applicable in multiple ink pens, such as pens in which cyan, yellow and magenta inks are delivered to one printhead. Finally, while the invention has been described as having a catchbasin for collecting expelled ink, a variety of other ink accumulation techniques may be adopted for this function, such as a flexible bladder. In view of the wide range of embodiments to which the principles of the present invention can be applied, it should be understood that the embodiments described and illustrated should be considered illustrative only and not as limiting the scope of the invention. Instead, my invention is to include all such embodiments as may come within the scope and spirit of the following claims and equivalents thereto.
An ink jet pen is disclosed having a drop generator, a catchbasin and a plurality of interconnected ink chambers comprising an ink reservoir coupled therebetween. The ink is distributed among the chambers so that, at any given time, only one contains both air and ink. The others contain either all ink or all air. Consequently, environmental excursions that cause expansion of air in the reservoir act to drive ink from only one of the chambers to the catchbasin. (The other chambers either have no air that can expand or no ink that can be driven therefrom.) The pen can thus be constructed with a smaller catchbasin than prior art pens, thereby increasing its volumetric efficiency. The catchbasin size can be reduced to an arbitrarily small volume by segregating the ink reservoir into an correspondingly large number of commensurately small chambers.
1
BACKGROUND [0001] There is a need for a demolition shear having a piercing tip insert and nose configuration to reduce nose wear and to resist retract forces exerted on the piercing tip insert in jamming situations and in the event of snagging of the piercing tip insert. DESCRIPTION OF THE DRAWINGS [0002] FIG. 1 is a right side perspective view (from the position of the operator) of one embodiment of a demolition shear attachment. [0003] FIG. 2 is a left side perspective view of the demolition shear attachment of FIG. 1 . [0004] FIG. 3 illustrates the shear attachment of FIG. 1 in a typical operating position showing the movement of the upper jaw with respect to the lower jaw during a shearing operation. [0005] FIG. 4 is an exploded perspective view of the jaw pivot shaft of the shear attachment of FIG. 1 [0006] FIG. 5 is an enlarged view of FIG. 1 showing the jaws of the shear attachment. [0007] FIG. 6 is the same view as FIG. 5 but with the blade inserts and piercing tip inserts removed. [0008] FIG. 7 is an enlarged view of FIG. 2 showing the jaws of the shear attachment. [0009] FIG. 8 is a perspective view of the lower jaw of FIG. 1 with the upper jaw removed to better show the blade-side shear blade inserts and guide blade insert. [0010] FIG. 9 is another perspective view of the lower jaw of FIG. 1 with the upper jaw removed to show guide-side guide blade insert and cross-blade insert. [0011] FIG. 10 is the same view as FIG. 7 with the blade inserts and piercing tip insert removed. [0012] FIG. 11 is the same view of the lower jaw as FIG. 9 with the blade inserts removed. [0013] FIG. 12 shows different views of an embodiment of a shear blade insert, wherein 12 A is a front perspective view, 12 B is a front elevation view, 12 C is an end elevation view and 12 D is rear elevation view. [0014] FIG. 13 shows different views of an embodiment of a guide blade insert, wherein 13 A is a front perspective view, 13 B is a front elevation view, 13 C is an end elevation view and 13 D is rear elevation view. [0015] FIG. 14 shows different views of an embodiment of a cross-blade insert, wherein 14 A is a front perspective view, 14 B is a rear perspective view, 14 C is an end elevation view, 14 D is a front elevation view and 14 E is rear elevation view. [0016] FIG. 15 shows different views of an embodiment of a blade-side piercing tip half, wherein 15 A is a front perspective view, 15 B is a rear perspective view, 15 C is a front end elevation view, 15 D is an outer side elevation view and 15 E is an inner side elevation view. [0017] FIG. 16 shows different views of an embodiment of a guide-side piercing tip half, wherein 16 A is a front perspective view, 16 B is a rear perspective view, 16 C is a front end elevation view, 16 D is a inner side elevation view and 16 E is outer side elevation view. [0018] FIG. 17 is a perspective view of the upper jaw of the shear attachment of FIG. 1 in isolation with the piercing tip inserts shown exploded with respect to the nose seat. [0019] FIG. 18 is an enlarged side elevation view of the upper and lower jaws of the shear attachment of FIG. 1 with the upper jaw in the fully open position. [0020] FIG. 19 is an enlarged side elevation view of the upper and lower jaws of the shear attachment of FIG. 1 with the upper jaw in a partially closed position. [0021] FIG. 20 is an enlarged side elevation view of the upper and lower jaws of the shear attachment of FIG. 1 with the upper jaw about to enter the slot in the lower jaw. [0022] FIG. 21 is an enlarged side elevation view of the upper and lower jaws of the shear attachment of FIG. 1 with the upper jaw fully closed and extending into the slot of the lower jaw. [0023] FIG. 22 is an enlarged side elevation view of the upper and lower jaw illustrating forces acting on the piercing tip in a jamming situation. [0024] FIG. 23 is an enlarged side elevation view of the upper and lower jaw illustrating forces acting on the piercing tip in another type of jamming situation. [0025] FIG. 24 is an enlarged side elevation view of the upper and lower jaw illustrating forces acting on the piercing tip in the event of snagging of the upper end of the piercing tip due to wear of the parent material from the nose of the upper jaw. DESCRIPTION [0026] Referring to the drawings wherein like reference numerals designate the same or corresponding parts throughout the several views, FIGS. 1 and 2 are perspective views from right and left sides, respectively (from the position of the operator), of one embodiment of a demolition shear attachment 10 . The shear attachment 10 has a main body 12 with a forward end 14 and a rearward end 16 . The rearward end 16 is adapted to be operably mounted to the boom or stick 18 ( FIG. 3A ) of an excavator such as by a swivel attachment 19 or other suitable mounting attachment as recognized and understood by those of skill in the art. At the forward end 14 of the main body 12 is a movable upper jaw 40 and a fixed lower 42 (discussed in detail later). [0027] FIGS. 3A-3C show the shear attachment 10 mounted to the boom or stick of an excavator 18 of an excavator, and positioned in a typical operating position, and illustrating the movement of the upper jaw 40 closing with respect to the lower jaw 42 over an object 11 to be sheared. The object 11 to be sheared may be any structural member, such as a steel I-beam or channel, steel plate, pipe or some other material, such as scrap metal, sheet metal or any other object or material for which a demolition shear is suited for handling or processing. [0028] Referring to FIGS. 1-4 , the main body 12 is typically constructed of steel side plates 20 , 22 , a top plate 24 and a bottom plate 26 which together define a substantially enclosed area within which a hydraulic actuator 30 ( FIGS. 3A-3C ) and other hydraulic components of the shear attachment 10 are substantially enclosed and protected. The hydraulic actuator 30 is pivotally secured at a rearward end within the main body 12 by an actuator pivot pin 32 extending through the side plates 20 , 22 , internal gussets (not shown) and the cylinder rod clevis 34 . The forward end of the hydraulic actuator 30 is pivotally attached to the movable upper jaw 40 by a cylinder pin 36 extending through the cylinder body clevis 38 and cylinder pin bore 42 (see also FIG. 16 ) in a rearward lobe of the upper jaw 40 . Thus, it should also be appreciated, that as the hydraulic actuator 30 extends and retracts as illustrated in FIGS. 3A-3C , the upper jaw 40 rotates about the longitudinal axis of the jaw pivot shaft 60 (discussed below) to open and close the upper jaw 40 with respect to the lower jaw 42 . An access opening with an access cover 25 ( FIG. 2 ) may be provided in the top plate to gain access to the interior of the body 12 for installation, maintenance, servicing and repair of the hydraulic actuator and other components of the hydraulic system. [0029] As best illustrated in FIGS. 4 , 8 and 9 , jaw bosses 44 , 46 on each side of the forward end 14 of the main body 12 include hub bores 48 , 50 . A jaw pivot shaft assembly 60 received within the hub bores 48 , 50 and through a pivot shaft bore 54 (see FIG. 17 ) pivotally supports the upper jaw 40 . [0030] The jaw pivot shaft assembly 60 comprises flanged bushings 56 , 58 fitted within the hub bores 48 , 50 . A main shaft 62 is press-fit into the pivot shaft bore 54 for rotation with the upper jaw 40 . The main shaft 62 includes a central bore 64 which receives a tie rod 66 having threaded ends 68 . End caps 70 , 72 are secured to the flanged bushings 56 , 58 by threaded connectors extending through aligned holes in the flange bushings 56 , 58 and are threadably received by aligned internally threaded holes in the hubs 44 , 46 . Tie rod nuts 74 threadably receive the threaded ends 68 of the tie rods 66 . The tie rod nuts 74 are secured to the end caps 70 , 72 by threaded connectors threadably received into internally threaded aligned holes in the flange bushings 56 , 58 . It should be appreciated that the tie rod 66 and tie rod nuts 74 laterally restrain the hubs 48 , 50 against lateral forces exerted on the jaws during the shearing operation. [0031] As best viewed in FIGS. 4 and 8 , lateral jaw stabilizing puck assemblies 80 , such as disclosed in U.S. Pat. No. 7,216,575, may be provided along with corresponding wear plates or wear surfaces 82 ( FIG. 17 ) on the adjacent side or sides of the upper jaw 40 to resist lateral movement of the upper jaw 40 during the shearing operation until the upper jaw enters the slot 96 of the lower jaw 42 (discussed below). [0032] Referring to FIGS. 5-11 , the lower jaw 42 includes forwardly extending, laterally spaced and substantially parallel jaw beams 90 , 92 and a cross-beam 94 extending transversely between the forward ends of the laterally spaced jaw beams 90 , 92 . The laterally spaced jaw beams 90 , 92 and the cross beam 94 together define a slot 96 into which the upper jaw 40 is received during the shearing process (see FIG. 3C and FIG. 4 ). As discussed in more detail below, the forwardly extending jaw beam 90 is adapted to receive shear blade inserts and guide blade inserts and is hereinafter referred to as the blade-side jaw beam 90 . The other forwardly extending jaw beam 92 serves to provide structural rigidity to the lower jaw and also serves to laterally restrain and guide the upper jaw into the slot 96 during the shearing process and is hereinafter referred to as the guide-side jaw beam 92 . [0033] As best viewed in FIG. 10 , the inner side of the blade-side jaw beam 90 includes a shear blade seat 100 which is adapted to receive a set of hardened steel shear blade inserts 110 ( FIGS. 7 and 8 ). An embodiment of the shear blade inserts 110 is illustrated in FIG. 12 . The shear blade inserts 110 each have generally planar vertical wear surfaces 114 , 116 and generally planar horizontal wear surfaces 118 , 120 . The intersection of the vertical and horizontal wear surfaces define four shearing edges 122 . The shear blade inserts 110 have parallel sloping end surfaces 124 , 126 creating a parallelogram configuration so that when the shear blade inserts 110 are positioned and oriented in the shear blade seat 100 the adjacent end surfaces bear against each another in a downward apex (see FIGS. 7 and 8 ). It should be appreciated, that because the shear blade inserts 110 are in the shape of identical parallelepiped, they may be rotated and oriented with respect to one another within the shear blade seat 100 so that all four shearing edges 122 may be used as the shearing edges wear during use. The planar vertical wear surfaces 114 , 116 include counterbore holes 130 for receiving threaded connectors 132 (preferably socket headed cap screws) to removably attach the shear blade inserts 110 within the shear blade seat 100 . The counterbore holes 130 permit the heads of the threaded connectors 132 to be seated within the counterbore. The threaded ends of the threaded connectors 132 extend through the counterbore holes 130 and through aligned holes 134 ( FIG. 10 ) in the shear blade seat 100 and are secured by nuts 136 ( FIGS. 5 and 9 ), received within counterbore holes 138 on the outer side of the blade-side jaw beam 90 . [0034] As best viewed in FIG. 10 , the inner side of the blade-side jaw beam 90 also includes a guide blade seat 200 which is adapted to receive a hardened steel guide blade insert 210 (best viewed in FIG. 8 ). An embodiment of the guide blade insert 210 is illustrated in FIG. 13 . The guide blade insert 210 has generally planar vertical wear surfaces 214 , 216 and generally planar horizontal wear surfaces 218 , 220 . The intersections of the vertical and horizontal wear surfaces define four shearing edges 222 . The guide blade insert 210 has parallel sloping end surfaces 224 , 226 creating a parallelogram configurations. The sloping end surfaces 224 , 226 of the guide blade insert 210 are complimentary to the sloping end surfaces 124 , 126 of the shear blade inserts 110 so that when the guide blade insert 210 is positioned and oriented in the guide blade seat 200 one of its end surfaces 224 , 226 will bear against one of the end surfaces 124 , 126 of the adjacently positioned shear blade insert 110 (as best illustrated in FIG. 8 ). It should be appreciated, that because the guide blade insert 210 is in the shape of a parallelepiped, it may be rotated and oriented within the guide blade seat 200 (and switched with the guide-side guide blade seat 300 discussed below) so that all four shearing edges 222 may be used as the shearing edges wear during use. The vertical wear surfaces 214 , 216 include tapped internally threaded holes 230 for receiving threaded connectors 232 (e.g., bolts) to removably attach the guide blade insert 210 within the guide blade seat 200 . The threaded ends of the threaded connectors 232 extend through aligned counterbore holes 234 ( FIGS. 5 and 9 ) on the outer side of the blade-side beam 90 and are threadably received by the tapped internally threaded holes 230 in the guide blade insert 210 . [0035] As best viewed in FIGS. 9 and 11 , the guide-side beam 92 also includes a guide-blade seat 300 ( FIG. 11 ) which is adapted to receive the same guide blade insert 210 as received in the blade-side guide blade seat 200 so that the guide blade inserts 210 are interchangeable between the guide-side guide blade seat 300 and the blade-side guide blade seat 200 . Accordingly, the guide blade insert 210 is retained and secured in the guide-side guide blade seat 300 in substantially the same manner as the blade-side guide blade seat 200 in that the same threaded connectors 232 (e.g., bolts) extend through aligned counterbore holes 334 ( FIGS. 7 , 8 , 10 ) on the outer side of the guide-side jaw beam 92 and are threadably received by the tapped holes 230 in the guide blade insert 210 . [0036] As best viewed in FIGS. 9 and 11 , the cross-beam 94 includes a cross-blade seat 400 ( FIG. 11 ) which is adapted to receive a hardened steel cross-blade insert 410 ( FIG. 9 ). An embodiment of the cross-blade insert 410 is illustrated in FIG. 14 . The cross-blade insert 410 has a generally planar front wear surface 414 , generally planar top and bottom wear surfaces 418 , 420 , generally planar end surfaces 424 , 426 and a back side 428 . The back side 428 includes four equally radially spaced internally threaded holes 430 . The back side 428 is also keyed with a projection 432 which seats within a recess 434 ( FIG. 11 ) in the cross-blade seat 400 . The intersection of the front vertical wear surface 414 with the top and bottom wear surfaces 418 , 420 and end surfaces define four cutting edges 422 . The cross-blade insert 410 is preferably square with four radially spaced holes 430 so that it may be rotated 90 degrees four times within the cross-blade seat 400 so that all four cutting edges 422 may be used as the shearing edges wear during use. The cross-blade insert 410 is secured within the cross-blade seat 400 by threaded connectors 436 (such as bolts) extending through counterbore holes 438 ( FIGS. 5 and 7 ) in the cross-beam 94 . The ends of the threaded connectors 436 are received within the aligned internally threaded holes 430 in the back side surface 428 of cross-blade insert 410 . [0037] The upper jaw 40 has a blade-side and a guide-side which correspond to the adjacent blade-side jaw beam 90 and guide-side beam 92 of the lower jaw 42 . The blade-side of the upper jaw 40 includes a shear blade seat 500 ( FIG. 6 ) which is adapted to receive the same shear blade inserts 110 ( FIG. 5 ) as used in the shear blade seat 100 of the lower jaw 42 so that the shear blade inserts 110 are interchangeable between the upper and lower jaws, thereby reducing the number of different blade configurations needed for the shear attachment 10 . However, in the upper jaw, the shear blade inserts 110 are oriented in an upward apex as opposed to the downward apex in the lower jaw (compare FIGS. 5 and 7 ). The shear blade inserts 110 are secured in the upper jaw in substantially the same manner as the lower jaw. The threaded ends of the threaded connectors 132 extend through the counterbore holes 130 and through aligned holes 534 in the upper shear blade seat 500 and are secured by nuts 136 received within counterbores 538 ( FIG. 7 ) on the guide-side of the upper jaw 40 . [0038] Referring to FIGS. 6 , 10 and 17 , the forward most end of the upper jaw 40 or nose 601 includes a nose seat 600 adapted to receive a hardened steel piercing tip insert 610 ( FIGS. 5 , 7 , 17 ) to protect the parent material of the upper jaw nose from wear during use. The nose seat 600 includes a blade-side nose seat 602 ( FIGS. 6 and 17 ), a guide-side nose seat 604 ( FIG. 10 ), and a front nose seat 606 ( FIGS. 6 , 10 , 17 ) which results in a narrowed nose portion 608 . The forward most nose tip 609 of the nose seat 600 is preferably radiused to minimize stress concentrations on the nose portion 608 , both during the manufacturing process and during use. The piercing tip insert 610 is comprised of two halves 620 , 622 which are substantially mirror images of each other except for the connector holes in each half (discussed later). The half which extends over the blade-side of the nose is hereinafter referred to as the blade-side half 620 , and the half which extends over the guide-side of the nose is hereinafter referred to as the guide-side half 622 . [0039] FIG. 15 shows various views of an embodiment of the blade-side half 620 . FIG. 16 shows similar views of an embodiment of the guide-side half 622 . Each of the piercing tip halves 620 , 622 includes an outer sidewall 630 having a substantially planar vertical wear surface 632 and a substantially planar vertical inner bearing surface 634 . Each half 620 , 622 also includes a laterally inward projecting front wall 636 having an outer curved wear surface 638 and an inner bearing surface 640 . Each piercing tip half 620 , 622 also includes a laterally inward projecting bottom leg 642 having a bottom planar wear surface 644 and an upper leg bearing surface 646 . Each of the piercing tip halves 620 , 622 further includes an end bearing surface 648 and an ear 650 having upper ear bearing surface 651 and a lower ear bearing surface 653 . The ear 650 may have a radiused periphery to reduce stress concentrations. The lower ear bearing surface 653 extends rearwardly of the end bearing surface 648 , the purpose of which is discussed later in connection with FIGS. 22 and 23 . The intersection of the planar vertical wear surface 632 and the bottom planar wear surface 644 defines a shearing edge 652 . The intersection of the curved wear surface 638 of the front wall 636 and the bottom planar wear surface 644 defines a front piercing edge 654 (the front piercing edge may be chamfered). [0040] As best viewed in FIGS. 6 , 10 and 17 , the nose seats 602 , 604 , 606 define peripheral bearing edge surfaces 656 which complimentarily receive the outer peripheries of the piercing tip halves 620 , 622 . It should be appreciated that the inner surface 640 of the laterally inward projecting front wall 636 and the upper surface 646 of the laterally inward projecting bottom leg 642 of each piercing tip half 620 , 622 is approximately half the width of the narrowed nose portion 608 so that when the piercing tip halves 620 , 622 are mounted in the nose seat 600 , the inner bearing surfaces 640 of the sidewalls 630 and the upper leg bearing surfaces 646 of the bottom legs 642 of the piercing tip halves 620 , 622 bear against the respective bearing surfaces of the blade-side nose seat 602 , the guide-side nose seat 604 and the front nose seat 606 . Additionally, the upper ear bearing surface 651 and the lower ear bearing surface 653 of the tip halves 620 , 622 bear against peripheral bearing edge surfaces 656 of the nose seat 600 . On the blade-side of the nose 601 , one of the sloping ends 124 , 126 (depending on orientation) of the upper shear blade insert 110 abuts and bears against the back end bearing surface 648 of the blade-side half 620 . As such, the blade-side piercing tip half 620 is rotationally restrained from outward rotation (as discussed later) by both the blade insert 110 and the peripheral bearing edge surfaces 656 which mateably receive of the upper ear bearing surface 651 and the lower ear bearing surface 653 of the blade-side nose seat. The guide-side piercing tip half 622 is rotationally restrained from movement by the peripheral bearing edge surfaces 656 which mateably receive of the upper ear bearing surface 651 and the lower ear bearing surface 653 of the guide-side nose seat 604 . [0041] It should be appreciated that when the two piercing tip halves 620 , 622 are mounted in the nose seat 600 , the narrowed nose portion 608 is completely surrounded by the hardened steel piercing tip insert 610 thereby protecting the parent material of the nose 601 from wear during use. [0042] In addition to being rotationally restrained by the peripheral bearing edge surfaces 656 , the two piercing tip halves 620 , 622 are secured to the narrowed nose tip 608 with threaded connectors 670 . In a preferred embodiment, the threaded connectors are socket headed cap screws. The two halves 620 , 622 include aligned holes 660 through their respective outer sidewalls 632 . Corresponding aligned holes 664 are provided through the narrowed nose tip 608 . Concentric counterbores 668 are provided over the holes 660 in the outer wall 632 of the blade-side half 620 . The aligned holes 660 in the outer wall 632 of the guide-side half 622 are tapped with internal threads. The counterbores 668 permit the heads of the threaded connectors 670 to be seated within the counterbores 668 . The threaded ends of the threaded connectors 670 extend through the holes 660 in blade-side half 620 and through the aligned holes 664 in the narrow nose tip 608 and are threadably received by the internally threaded aligned holes 660 of the guide-side tip half 622 . Obviously, the counterbores 668 and the internal threaded holes 660 in the two tip halves 620 , 622 could be reversed if desired. Alternatively, counterbores 668 could be provided in outer walls 632 of both tip halves 620 , 622 for receiving the heads of the threaded connectors 670 and to receive a nut (not shown) on the opposing tip half rather than tapping the holes 660 of one of the halves. As discussed in more detail later in connection with FIGS. 18 and 22 , the holes 660 , 664 are aligned along an arc concentric with the front edge of the piercing tip 610 (i.e., the outer curved wear surface 638 ) to ensure a more uniform loading across the threaded connectors 670 . [0043] It should be appreciated that when mounted to the upper jaw 40 , the planar vertical wear surfaces 114 , 116 (depending on orientation) of the shear blade inserts 110 are substantially co-planar with the vertical wear surface 632 of the blade-side tip half 620 and the shearing edges 122 , 652 of the shear blade inserts 110 and piercing tip insert 610 are substantially aligned. Similarly, on the lower jaw 42 , the planar vertical wear surfaces 114 , 116 (depending on orientation) of the shear blade inserts 110 are substantially coplanar with the vertical wear surface 214 of the blade-side guide blade insert 210 and their respective shearing edges 122 , 222 are substantially aligned. It should also be appreciated that the substantially coplanar vertical wear surfaces 114 , 116 , 632 and shearing edges 122 , 652 of the upper shear blade inserts and piercing tip insert 610 are slightly laterally, inwardly offset from the shearing edges 122 , 232 of the shear blade inserts 110 and blade-side guide blade insert 210 of the lower jaw (preferably between a range of about 0.01 inches and 0.05 inches), to permit the upper shearing edges to pass by the shearing edges of the lower jaw as the upper jaw moves through its range of motion and into the slot 96 of the lower jaw 42 . Likewise, the shearing edge 652 of the guide-side piercing tip half 622 is laterally inwardly offset from the shearing edge 222 of the guide-side guide blade insert 210 preferably between a range of about 0.01 inches and 0.05 inches. Accordingly, the width of the piercing tip insert 610 is less than the width between the opposing shearing edges 222 of the blade-side and guide-side guide blades 210 (preferably between a range of about 0.02 and 0.1 inches), such that the piercing tip insert 610 can pass between the lower dual guide blades 210 as the upper jaw closes into the slot 96 of the lower jaw 42 . Shims may be inserted between the various inserts 110 , 210 , 610 and their respective seats 100 , 200 , 300 , 500 , 600 to maintain the close tolerances between the respective shearing edges. [0044] FIGS. 18-22 are enlarged side elevation views of the jaws 40 , 42 to better illustrate the relationship of the blade inserts 110 , 210 and piercing tip insert 610 cross-blade insert 410 during movement of the upper jaw—i.e., from the fully open position ( FIG. 18 ), to the fully closed position ( FIG. 21 ) in which the upper jaw reaches full depth into the slot 96 of the lower jaw 42 . FIG. 19 , shows the upper jaw partially closed wherein the front piercing edge 654 of the piercing tip insert 610 is perpendicular or normal to the ground surface. FIG. 20 , shows the upper jaw in a position where the front piercing edge 654 intersects the lower jaw 42 . [0045] A nose wear shoe 700 is secured (such as by welding) to the nose 601 of the upper jaw 40 above the piercing tip insert 610 to protect the parent material of the upper jaw from wear during use. As the nose wear shoe 700 wears down, it may be removed and replaced with another wear shoe 700 . The wear shoe 700 may be fabricated from the same material as the parent material or it may be fabricated from hardened steel. Referring to FIG. 20 , the nose wear shoe preferably extends along the nose a sufficient distance to ensure that the parent material of the nose is protected to at least the full depth of entry of the upper jaw 40 into the lower jaw 42 . In an alternative embodiment, the piercing tip insert 610 may be extended along the nose 601 to the full dept of entry of the upper jaw into the lower jaw. In such an embodiment, the nose seat 600 would likewise be extended and additional holes 660 may be necessary to adequately restrain the longer piercing tip insert 610 to the narrowed nose 608 . [0046] It should be appreciated that the parent material of the nose 601 above the piercing tip insert 610 is more susceptible to wear than the hardened steel piercing tip insert 610 . Accordingly, without a wear shoe 700 , the nose 601 could wear down to the point that the upper edge of the piercing tip insert 610 projects above the nose. If the upper edge of the piercing tip insert 610 projects outwardly from the nose 601 , the projection could potentially snag on material caught in the jaws as the upper jaw re-opens or is retracted from the lower jaw. If sufficient retract force is exerted on the upper jaw, the piercing tip insert could be pulled away from the nose by the snagged material, shearing the threaded connectors in the process or breaking the piercing tip insert. Accordingly, as hereinafter described, the nose 601 of the upper jaw is configured to minimize the risk of snagging, even when a wear shoe 700 is not mounted to the nose 601 or where the wear shoe itself is worn down such that the parent material of the nose is no longer protected by the wear shoe. [0047] FIGS. 18 and 21 illustrate a preferred configuration of the nose 601 to avoid or minimize occurrences of snagging. The phantom line designated by reference numeral 800 identifies the arc created by the forward most front piercing tip edge 654 of the piercing tip insert 610 as the upper jaw moves through its range of motion. The arc 800 has a radius R 1 to the center axis of the jaw pivot shaft 60 . The outermost periphery of the nose 601 from the forward piercing edge 654 of the piercing tip 610 to the end of the nose wear shoe 700 or to the point on the nose which corresponds to the maximum depth that the nose 601 penetrates the lower jaw is configured to transitions away from the front piercing tip edge arc 800 in a substantially smooth nose arc 802 . The nose arc 802 has a radius R 2 which is less than the radius R 1 , such that radial distances from the central axis of the jaw pivot shaft 60 to points along the nose 601 or nose arc 802 continually decrease relative to the front piercing tip edge arc 800 . Stated another way, the distance between the piercing tip front edge arc 800 and the nose arc 802 continually increases along the nose 601 or nose arc 802 from the piercing tip front edge 654 . This configuration allows the nose 601 to only make contact at the piercing tip front edge 654 , thereby avoiding or reducing the likelihood of the nose 601 scraping along objects being pierced by the piercing tip 610 , thereby minimizing wear along the nose. Additionally, because the nose increasingly transitions away from the piercing tip edge arc 800 , it reduces the likelihood of snagging of material caught in the jaws even if the parent material of the nose becomes worn down to where the upper edge of the piercing tip insert 610 projects outwardly from the worn parent material of the nose. [0048] Furthermore, the piercing tip seat 600 and piercing tip insert 610 are configured to ensure retention of the piercing tip if a projecting edge of the piercing tip becomes snagged or if the upper jaw becomes jammed by material trapped in the jaws. For example, in FIG. 22 the hatched area 900 is intended to represent trapped or lodged material caught between the wear surfaces of the piercing tip insert 610 and the guide shear blade inserts 210 causing the upper jaw to become jammed within the slot 96 of the lower jaw 42 such that the upper jaw 40 cannot retract or re-open. The retract force F of the upper jaw 40 (exerted by the hydraulic actuator 30 pulling on the upper jaw) attempts to pull the piercing tip insert 610 in the direction perpendicular to the radial line 806 extending from the center axis of the jaw pivot shaft 60 to the midpoint of the trapped material 900 . It should therefore be appreciated that any bearing surface which is less than 90 degrees to the radial line 806 , will resist the retract force F. Accordingly, the rearwardly projecting ears 650 of the piercing tip insert 610 ensure that a bearing surface is provided to resist the retract force F. [0049] Referring to FIG. 22 , the lower ear bearing surface 653 is at an angle less than 90 degrees to the radial line 806 and therefore provides a bearing surface designated by arrows R against which the peripheral bearing edge surfaces 656 of the nose seat 600 engage to resist the retract force F. Similarly, the inner bearing surface 640 of the front wall 636 bears against the nose seat 606 as designated by arrows R to resist the retract force F. Thus, the resistance or reactionary forces R will reduce the shearing forces being exerted on the connectors 670 by the retract force F, thereby preventing or minimizing the piercing tip insert 610 from being pulled off the nose or otherwise fracturing. [0050] Furthermore, because the holes 660 in the piercing tip insert 610 are aligned along an arc 804 having a radius R 3 which is less than the radius R 2 but which is concentric with the nose arc 802 , a more uniform load is applied across all of the connectors 670 thereby further reducing the shearing stresses exerted on any one connector or causing stress concentrations which could shear the connectors or cause the piercing tip insert to fracture. [0051] FIG. 23 illustrates another example wherein the hatched area 902 is intended to represent material trapped between the piercing tip insert 610 and the cross-blade insert 410 . In this example, the retract force F again pulls the piercing tip in the direction perpendicular to the radial line from 806 extending from the center axis of the jaw pivot shaft 60 to the center point the trapped material, which, in this example, is assumed to be at the piercing tip front edge 654 . The retract force F will cause the piercing tip insert 610 to attempt to roll outwardly or away from the nose 601 as indicated by arrow 810 . However, the upper ear bearing surface 651 engages with the peripheral bearing edge surfaces 656 of the nose seat 600 as designated by reactionary forces R to resist the outward rotation of the piercing tip insert 610 thereby reducing shearing forces on the connectors 670 and preventing or reducing stress fracturing of the piercing tip insert 610 . [0052] FIG. 24 illustrates an example of the retract force F acting on the upper edge of the piercing tip insert 610 in the unlikely event that the nose 601 is worn down to create a ridge upon which material could snag as described above. Such an occurrence is unlikely in view of the configuration of the nose 601 having a continually increasing distance between the nose arc 802 and the piercing tip front edge arc 800 for the reasons explained above, but nevertheless, if the nose is worn down to create a ridge on which material could snag, the upper ear bearing surface 651 would engage against the peripheral bearing edge surfaces 656 of the nose seat 600 as indicated by reaction forces R to resist the retract force F attempting to roll the piercing tip edge outwardly as indicated by arrow 810 thereby reducing shearing forces on the connectors 670 and preventing or reducing stress fracturing of the piercing tip insert 610 . [0053] The foregoing description is presented to enable one of ordinary skill in the art to make and use the invention and is provided in the context of a patent application and its requirements. Various modifications to the embodiments described herein, and the general principles and features of the embodiments described herein will be readily apparent to those of skill in the art. Thus, the present invention is not to be limited to the embodiments described herein and illustrated in the drawing figures, but is to be accorded the widest scope consistent with the spirit and scope of the appended claims.
A demolition shear and a piercing tip insert and nose configuration for a demolition shear which resists nose wear and resists retract forces exerted on the piercing tip insert in jamming situations and in the event of snagging of the piercing tip insert. There is a need for a demolition shear having a piercing tip insert and nose configuration to reduce nose wear and to resist retract forces exerted on the piercing tip insert in jamming situations and in the event of snagging of the piercing tip insert.
1
FIELD OF THE INVENTION [0001] The present invention relates to a holder for holding an object which melts or drips or leaves imprints on one's fingers comprising a handle and a protrusion section. BACKGROUND OF THE INVENTION [0002] U.S. Pat. No. 6,182,854 relates to an ice cream cone and popsicle holder. The device catches dripping ice cream or popsicles. The holder has a container with a closed bottom and side walls. The side walls support a shelf which extends outwardly from the container and has an outer peripheral wall. The shelf also has an inner cone holding wall with drain holes located either in the shelf or cone holding wall. The popsicle holder preferably has a pair of aligned slots for popsicles with two sticks. [0003] U.S. Pat. No. 4,992,283 relates to a frozen confection holder for toddlers. The invention is a combination of a mouth and lip conforming confection that is mounted on a drip catching, stylistically shaped biodegradable handle that can be grasped by a toddler. The drip catch device may either be of a consumable composition and secured to the handle by a musilage or formed integrally with the handle. [0004] U.S. Design Pats. D382,085 and D442,764 relate to designs for ice cream holders. [0005] U.S. Design Pat. D286,700 relates to the ornamental design for an ice-cream sandwich. [0006] U.S. Pat. No. 6,941,982 relates to a food holder attachable to the outside of the food such as an ice cream cone for capturing liquid, the liquid to be captured by an absorbent material and in a plurality of channels and interconnections, for maximizing the surface of the absorbent material. The channels have openings to allow the liquid to enter via gravity. [0007] U.S. Pat. No. 6,571,979 relates to a holder for an ice cream having a stick which includes a handle having a drip receiving cavity. A drip catchment member is attached to or formed integrally with the handle and includes a catchment surface for receiving drips from the ice cream. A stick receiving aperture receives the stick to support the ice cream above the catchment surface. A drain enables any drips caught by the catchment surface to migrate into the cavity. [0008] U.S. Patent Publ. No. 2003/0129280 relates to a supported comestible comprising a frozen comestible or a non-frozen comestible that is supported by an edible support. The edible support has sufficient surface area inside the comestible to support the comestible. Protective, edible mess guards for the hands and fingers, protective, edible drip guards, free standing edible supports, and moisture proof barriers/coatings and sealants are included. [0009] There are plenty of foods that when eaten stick to the fingers and hands of the person holding the food. Such food includes ice cream products, cakes, or any other finger foods. In the prior art there has been no way to make these foods pleasant to eat without creating a mess to the person trying to eat such foods. SUMMARY OF THE INVENTION [0010] The present invention comprises a device which has a handle that can be held by a user, a protrusion section which is placed inside an object to hold the object on the device. [0011] It is an object of the present invention for the device to further comprise a platform or opening for catching drippings. [0012] It is an object of the present invention for the device to be made of biodegradable material. [0013] It is an object of the present invention for the device to be made out of plastic. [0014] It is an object of the present invention for the device to be made out of wood. [0015] It is an object of the present invention for the device to be made out of metal. [0016] It is an object of the present invention for the device to be approximately 2-10 inches tall. [0017] It is an object of the present invention for the device to comprise a slip prevention disk. [0018] It is an object of the present invention for the protrusion to be separated from the rest of the device by a round disk. [0019] It is an object of the present invention for the round disk to be approximately ¼ inch to 2 inches from the rest of the device. [0020] It is an object of the present invention for the protrusion about the disk to be flat. [0021] It is an object of the present invention for the protrusion to measure approximately 1/16 inch to approximately ½ inches in thickness. [0022] It is an object of the present invention for the device to be placed into the center of the object for which it will be holding. [0023] It is an object of the present invention for the handle to be approximately ¼ to 3 inches in thickness. [0024] It is an object of the present invention for the handle to have a logo printed on it. [0025] It is an object of the present invention for the handle to be round or flat. [0026] It is an object of the present invention for the protrusion to be ¼ inch or longer. [0027] It is an object of the present invention for the handle to be hollow. [0028] It is an object of the present invention for the handle to contain an object inside. [0029] It is an object of the present invention for the hollow handle to have a prize or toy inside of it. [0030] It is an object of the present invention to have the prize or toy inside covered by a wrapping around the handle, so that the user cannot see what is inside. [0031] It is an object of the present invention for the handles to have holes in it to allow ones hand to breathe and not conduct heat. [0032] It is an object of the present invention for the disk to be in the form of a rectangle or circle. [0033] It is an object of the present invention for the disk to have on it protrusions to assist in holding the object. [0034] It is an object of the present invention for the item to be held to be an ice cream sandwich, chipwich, flying saucer or other type of ice cream which is normally held in a person's hands. [0035] It is an object of the present invention for the item to be held to be a cake, sandwich, pizza or any other type of finger food. [0036] It is an object of the present invention for the device to be inserted into the ice cream or other food item prior to the item being frozen. [0037] It is an object of the present invention for the device to be made of a single piece. [0038] It is an object of the present invention for the device to be made of multiple pieces. [0039] It is an object of the present invention for the protrusion to have a single point or screw at the end of it for being inserted into the object to be held. [0040] It is an object of the present invention for the device to have multiple protrusions to be inserted into the object. [0041] It is an object of the present invention for the protrusion to be able to pass through the center of the object to the outside. [0042] It is an object of the present invention for a separate novelty to be added on to the end of the protrusion once it has passed through the object. [0043] It is an object of the present invention for the device to be used multiple times. [0044] It is an object of the present invention for the device to be thrown away after a single use. [0045] It is an object of the present invention for multiple types of handles to be used with multiple types of protrusions so that the tops and bottoms can be used interchangeably. BRIEF DESCRIPTION OF THE DRAWINGS [0046] FIG. 1 illustrates a view of the device being attached to an object held by a user. [0047] FIG. 2 shows how the device is inserted into an object having two separate halves. [0048] FIG. 3 shows a cross section of the device in FIG. 1 inserted into an object. [0049] FIG. 4 shows the device prior to being assembled. [0050] FIG. 5 shows the device prior to being assembled. [0051] FIG. 6 shows the device and how it can be inserted into an object having a pre-cut center area. [0052] FIG. 7 shows an embodiment of the present invention. [0053] FIG. 8 shows a cross section of the embodiment shown in FIG. 7 . [0054] FIG. 9 shows an embodiment of the present invention. [0055] FIG. 10 shows a cross section of the embodiment of FIG. 9 . [0056] FIG. 11 shows an unassembled embodiment of the present invention. [0057] FIG. 12 illustrates how the device is inserted into the object. [0058] FIG. 13 illustrates how the device is inserted into the object. [0059] FIG. 14 shows an embodiment of the present invention. [0060] FIG. 15 shows an embodiment of the present invention. [0061] FIG. 16 shows an unassembled view of the device of the present invention. [0062] FIG. 17 shows a cross section of the device shown in FIG. 16 . [0063] FIG. 18 shows an unassembled view of the device of the present invention. [0064] FIG. 19 shows the device including an embodiment of a handle. [0065] FIG. 20 shows the device including an embodiment of a handle. [0066] FIG. 21 shows the device including an embodiment of a handle. DETAILED DESCRIPTION [0067] FIG. 1 shows a person holding the device 10 by the handle 12 holding an object 14 . As shown in FIG. 1 , the object is a flying saucer or chipwich. [0068] FIG. 2 shows the device 10 having a handle 12 . Above the handle 12 is a slip prevention disk 16 which allows the object 14 to rest on it so the object does not fall off or slide off the device 10 . Above the slip preventive disk 16 is a protrusion 18 which goes through the center 20 of the object 14 . As shown in FIG. 2 , the object 14 is broken up into two halves. [0069] FIG. 3 is a cross section of the device 10 shown in FIG. 1 . FIG. 3 shows the handle 12 , the slip prevention disk 16 , and the protrusion 18 placed in the center 20 of object 14 . [0070] FIG. 4 shows the device 10 broken up into a piece 30 and a piece 40 . Piece 30 comprises the handle 32 and the protrusion 34 , the piece 40 comprises the slip prevention disk 40 . As shown in FIG. 4 , the slip disk prevention 40 has a hole 42 which is placed over the protrusion 34 and it sits on top of the handle 32 . [0071] FIG. 5 shows an alternative embodiment of the device 50 . The device 50 has a handle 52 which has a larger surface area for putting on a logo 54 . The device 50 further has the protrusion 56 and the slip prevention disk 58 . [0072] FIG. 6 shows an embodiment of the device 60 having the handle 62 , a top portion 64 is made up of the protrusion 66 and the slip prevention disk 68 . The top portion 64 is then attached to the handle 62 . The protrusion 66 fits inside the center 70 of object 72 . [0073] FIG. 7 shows an embodiment of the device 80 having a handle portion 82 a slip prevention disk 84 and a protrusion 86 . The slip prevention disk 84 can also be used to catch drippings. FIG. 8 shows a cross section of FIG. 7 . FIG. 8 shows how the top piece 88 made up of the protrusion 86 and the slip prevention disk 84 is attached to the handle 82 . [0074] FIG. 9 shows an alternative embodiment 90 having a handle 92 , the top portion 98 comprises the protrusion 94 and the slip prevention disk 96 . The top portion 98 is placed onto the handle section 92 where it attaches to section 100 . [0075] FIG. 10 shows a cross section of FIG. 9 . [0076] FIG. 11 shows an embodiment of device 110 having a top portion 112 , and a handle portion 114 . The top portion 112 comprises protrusion 116 and slip prevention disk 118 . The top portion 112 is slipped onto the handle 114 . [0077] FIG. 12 shows the device 120 having handle section 122 , a slip prevention disk 124 and a protrusion 126 . In this embodiment, the protrusion 126 is formed like a screw and is turned such as shown by arrow 128 to screw into the center of object 130 . [0078] FIG. 13 shows an embodiment of the device 140 having a handle section 142 and a protrusion 144 . In the device 140 the protrusion 144 is made up of three prongs 146 which are placed into the object 148 . [0079] FIG. 14 shows an embodiment of the device 150 having a handle section 152 , a slip prevention disk 154 and a protrusion 156 . The protrusion 156 is long enough to go through the entire center of the object 158 . The protrusion 156 has a hole 160 in it for receiving a further novelty item 162 . [0080] FIG. 15 shows an embodiment of the device 170 having a handle 172 , a slip prevention disk 174 , a protrusion 176 which goes into the object 178 . The device 170 further has a drip catching disk 180 which catches drippings from the object 178 . [0081] FIG. 16 shows an embodiment of the device 190 having a handle portion 192 and a protrusion 194 . Attached to the handle portion is a disk 196 having further protrusions 198 for securing an object to it. [0082] FIG. 17 is a cross section of the device 190 shown in FIG. 16 . [0083] FIG. 18 shows an embodiment of the device 200 having a handle section 202 and a protrusion 204 . A disk 206 having further protrusions 208 is attached to the handle 202 allowing the protrusion 204 to go through the center of the disk 206 . [0084] FIG. 19 shows a further embodiment of the device 210 having a handle 212 and a top portion 214 comprising a slip prevention disk 216 and a protrusion portion 218 . In this embodiment, the handle 212 is hollow so that objects 220 such as candy or other objects can be placed within the hollow handle 212 . [0085] FIG. 20 shows an embodiment of the device 230 having a handle section 232 , a slip prevention disk 234 and a protrusion 236 . The handle 232 can have objects such as balls 238 placed on it. [0086] FIG. 21 shows an embodiment 240 having a handle section 242 , a slip prevention disk 244 and a protrusion 246 . The handle 242 is hollow and can receive a prize or novelty item 248 . The novelty item 248 can be placed in the handle and the handle sealed with cap 250 .
A holder for holding an object which melts or drips or leaves imprints on one's fingers comprising a handle and a protrusion section. The device can further comprise a slip prevention disk with is located between said handle and said protrusion section.
0
This application is a continuation of Ser. No. 07/124,120, filed 11/16/87, now abandoned. BACKGROUND OF THE INVENTION The present invention pertains to automatically positioning a patient, who lies on a rest, such that the patient can assume an exactly predetermined posture and position particularly as far as certain body parts are concerned and in relation to particular equipment. In particular, the invention relates to the automatic positioning of a patient so that a concrement in his/her body is placed into the focal point of a device provided for the comminution of such a concrement. U.S. Pat. No. 3,942,531 corresponding to German printed patent application 23 51 247 describes a device including a focusing chamber for the comminution of concrements in the body of human beings. The focusing chamber is a portion of and pertains to a rotational ellipsoid that outlines and delineates the interior chamber wall. Such an ellipsoid has two focal points. Shock waves are produced through spark discharge at one of the focal points, and these shock waves are focused by the device in the second focal point. The chamber is filled with a liquid serving also as a coupling fluid to couple the body of the patient to the focusing chamber. The construction is chosen so that the concrement to be comminuted is situated in that second focal point of the ellipsoid. The shock waves are produced through an underwater arc discharge having two electrodes across which a capacitor discharges. As the discharge is ignited, shock waves are produced in the first mentioned focal point of the rotational ellipsoid. The ellipsoid is carefully constructed to permit a high concentration i.e. near pointlike concentration of shock waves in the second focal point. The pressure amplitudes may exceed 1 kbar and the duration of a shockwave pulse is less than 1 microsecond. A high concentration of shockwave energy is made possible on account of the high degree of focusing produced by the ellipsoid while on the other hand the shock waves as they converge towards the concrement and pass through normal tissue, affect that tissue only insignificantly. Following the destruction of the concrement and its pulverization or breaking up the concrement e.g. into grit, that grit will be discharged from the body by normal physiological process. This is particularly true in case of kidney stones. It is of course apparent that the aforementioned method will function properly only if one knows exactly where that concrement is situated, so that in fact the device can be positioned such that the above mentioned second focal point coincides with that point in the interior of the body of the living being in which a concrement appears to have lodged. It is, therefore, necessary to determine the position of such a stone ahead of time i.e. prior to launching comminuting shockwaves. In the past one has used X-rays, particularly two separate X-ray beams, for obtaining spatial coordinate values of the concrement once the patient has assumed a particular position. German patent 34 26 398 (see U.S. Pat. No. 4,936,291) describes a system by means of which a concrement is located, and the patient is positioned under utilization of a combination and, particularly, correlation of an X-ray locating system and an ultrasonic locating system. Here particularly the ultrasonic locating system will continuously monitor the position of the kidney stone, even after it has originally been located, and signals are provided and steps are taken to fix the location of the stone as far as external equipment is concerned. It should be observed that when the patient is breathing the stone undergoes a certain movement and, therefore, may oscillate around a particular point at the rate of breathing. The second focal point of the rotational ellipsoid can be made to coincide with that particular zero point around which the kidney stone oscillates, and continuous observation of the stone as it moves and oscillates permits manual triggering of the shock waves right when the stone passes through the focal point. This is done through the ultrasonic system and only occasionally is the X-ray system used to determine the resolution and the extent any comminution of a kidney stone was successful. The automated or quasiautomated tracking and following of the equipment in relation to the kidney stone must require that it occurs in the ultrasonic section plane. Another locating device may be provided and shifting within the ultrasonic section plane may be made visible on a screen. One may locate and identify on a monitoring screen a kidney stone. The screen may simulate the ultrasonic section plane. Next, a light pen may be used on the screen to identify a particular point namely the point where the stone is located, and now computer operated functions may ensue. The Munich Medical Weekly (Muenchner Medizinischen Wochenschrift, 125, 1983, No. 8, pages 151-155) describes a device for comminuting kidney stones through shock waves. The concrement is to be placed in the focal area of a bundled and focused shock wave. This position is obtained through a motor driven positioning device which is manually operated and controlled by the attending physician. Moreover, this device as described shows that the location of the stone is monitored by the physician through two independent X-ray systems. German printed patent application 32 20 751 discloses a similar device which includes either two independent X-ray systems or two independent ultrasonic systems used in conjunction with a positioning device being independent from the foregoing equipment and operated by the physician. Further patents of interest are U.S. Pat. Nos. 4,669,483, 4,552,348, 4,938,232, Ser. No. 942,251 and U.S. Pat. No. 4,705,026. DESCRIPTION OF THE INVENTION It is an object of the present invention to improve recognition and acquistion of locating a concrement to be comminuted as fast as possible, bypassing any operating personnel and to obtain representation in four axial directions, ultimately to place the second focal point of a lithotripter that includes rotational ellipsoid, such that this second focal point is made to coincide with the concrement to be comminuted; the principal goal in mind is that the patient as well as the personnel must not be exposed excessively to X-rays, at the very least the X-ray must be held very low. Another object and purpose of the invention is to ensure a transition and interface between water and the patient without the inclusion of bubbles or the like and it must be ensured that this connection is maintained throughout. In accordance with the preferred embodiment of the present invention a lithotripter is suggested which includes a positioning device which moves the located concrement by moving the rest on which the patient lies together with the patient, in at least three axes; the first one extends along the body and this movement is from feet to head or vice versa. The second direction is taken in regard to the normal position and posture of the patient described, that being a movement to the left and to the right; and the third coordinate is a direction transverse to both these aforementioned directions. Moreover, an automatic follow-up is provided for the water cushion level to ensure air bubblefree coupling of that cushion to the patient's body. The cushion is established by the water generally and is placed between the skin of the patient and the shock wave generator/focusing device; the water serves as a coupler fluid between the lithotripter itself and a membrane that closes off the submerged spark generator of the lithotripter by means of which the shock wave production is initiated. The patient can be assumed to have been placed on a rest which in turn can be placed either onto a vehicle, a cart or the like to wheel the patient into the treatment room. The rest with the patient lying on it, can also be placed on a treatment table, whereby, so to speak the position of the patient as such and particularly of the concrement in him has the same position in relation to the vehicle as it has now in relation to the treatment table. Patient movement on the rest and through the vehicle is thus equivalent to a movement of coordinate system. Thus, even though there is physical relocation of the patient his/her position are such that upon the aforedescribed movement the concrement is merely being relocated in a known fashion without displacement in relation to the translated coordinate system. In other words, the particular positions are indicated by LED-s which indicate specifically the instantaneous position of the equipment. Involved is a movement along the three axes mentioned earlier and a fourth motion is provided along a tilting axis. The purpose of that tilting is to avoid "shading" of the concrement by ribs or the spine. In addition the X-ray coordinates, horizontal as well as vertical are ascertained whereby particularly any horizontal movement of the concrement actually moves only within the plane of one of the monitors or the other. In treatment position the patient rests with his back on a water cushion (see e.g. application Ser. No. 942,251). Between the cushion and the patient there is an ultrasonic coupling layer which is a pasty gel and which couples the casing of the cushion directly to the skin of the patient to avoid the forming of cavities, bubbles or the like (see also U.S. Pat. No. 4,805,600). If bubbles are present a wiper may remove them (see e.g. U.S. patent application Ser. No. 942,259). This method is preferred because it can be practiced in a simple fashion, and there is no negative influence exerted on the equipment; particularly, nothing impedes the propagation of shock waves. The level of the water cushion can be raised or lowered by key operation from control panel if such is desired. In order to visualize later the concrement on an X-ray screen the positioning table is manually moved, i.e. through manually operated servo motors, until the concrement is visible on both screens. The level of the water cushion is manually or automatically caused to follow, through computer operation to maintain coupling of the lithotripter to the patient, and in dependence upon the movement of the positioning table. This way the shockwave generation is ensured. The contact necessary for shock wave treatment as between the patient and the cushion will not be interrupted on account of the positioning procedure and the ensuing movement. Subsequent to the foregoing a locating procedure is carried for finding the concrement. This procedure is computer operated, and is provided for ascertaining specifically the position of the concrement. The locating operation is carried out through crossing X-ray systems, i.e. under utilization of two, intersecting X-ray systems. Each of these systems is oriented in an angle to the respective other one, in that the two projection planes have an angle in relation to each other one. These angles can vary but they can be held fixed. The required projection coordinates, as far as X-ray projection is concerned, are ascertained by means of a monitor and video image device pertaining to the X-ray equipment. First, an X-ray image is taken to ascertain the condition of the concrement and an image of concrement is made visible on both monitors. Next, a light pen (wand) system is activated. The concrement is positioned somewhere in the projected area on the screen. Next, the second monitor is turned off and the user will mark the position of the concrement through the light pen. If the ascertained values are correct within particular equipment limits this monitor is also turned off, and the user-technician will enter the position into the second monitor. In an alternative version one may dispense with the initial turn-on of both monitors, and one starts out with having only one X-ray system turned on for a little and the other by itself thereafter. The light pen has a pressure responsive feeler at its tip and is operated with the pen touching the image on one of the screens i.e. the respective screen itself. The resulting feeler response starts an electronic positioning device provided for acquiring positional data, here the location of the light pen. A period of time is ascertained which the electron beam has available to move in accordance with a regular video, scan beginning e.g. at a corner of the monitor, until reaching the particular location where the light pen touches the screen. This scanning usually follows the conventional television line raster. The electron beam's position will accordingly be located through the position of the light pen, particularly by means of a photodiode in the tip of that pen a threshold discriminator is connected to that diode. One or two counters are used for ascertaining the time. In the one counter version, that counter just tracks the time from the beginning of a field (frame) scan. However, the two counter version permits operation at a larger accuracy. One of the counters acquires the line number and the other one just cumulatively counts from the beginning of a line until a line pen signal is detected on that line. The accuracy can be improved further through measuring, on a running basis, the entire line length which is then used for normalizing any in-line period. This procedure compensates any variations in line frequencies. The thus acquired virtual coordinates in terms of line number and line scan time, and counting from the beginning of a line up to the location of the light point are values which in a computer and using conventional algorithm, can readily be used to ascertain a coordinate value in relation to a point of origin which for example is located or situated in the center of the monitoring screen. In other words, the attending physician uses the light pen to mark on one (or both) X-ray monitors a location that is expected to be the location of his diagnozed concrement, and now that location is referred to the equipment bearing in mind that the X-ray locating system with its center and center beam is a well defined system and in fact establishes coordinates in relation to which the light pen marking denotes the concrement. Having done that, the position inputting operation is completed. Coordinate inputting generally as described may be obtained with other means such as the so called tracking ball, a joystick or a mouse. Here it may be advisable to project a haircrossing onto the screen, or an arrow or a distinctive cursor or the like. Thereafter, i.e. after the concrement location has been illustrated on the screen and e.g. through manual key operation automatic positioning is initiated. The computing facility responds to the coordinates ascertained through the light pen (or any of the other inputting devices) and calculates the mathematical relationship between the position of the monitor and video screen coordinate system, on one hand, and the spatial coordinate system of the concrements of the patient on the rest on the other hand. The reference point or coordinate origin in this case is, as far as equipment is concerned, the known geometric second focus of the rotational ellipsoid as defined above. The first focus, within the present context, is always the focus of the reflector in which the shock waves are generated by means of spark discharge, and the second focus of that reflector is exactly that, a second focus of the rotational ellipsoid serving as the reflector and into which shock waves are focussed when generated by and in the first focus. Now, the geometric parameters of the second focal point are used as reference coordinates. That second focal point has a definite position vis-a-vis the patient or the rest. The master computer will provide control signals such that the concrement in the patient and through motion of the positioning table on which the patient lies and control table is made to coincide with the coordinates of the this second focal point for the shock wave. Each of the coordinate axes indicated above is associated with an indexer that is a servo computer which signals back to the master computer the respective state, namely the position of the equipment such as the rest vis-a-vis the respective axis. This indexing computer will ultimately control the movement of the patient and of the rest on that axis. The coordinates of tracking transducers are monitored and ascertained; as the device homes-in on any desired coordinate as for the specific axis is concerned, the motion is slowed down or stopped. Accuracy should permit that after all three (or more, infra) axis-movements have been completed, indeed the concrement is situated and located in the second focal point F 2 . Three commands can be executed with regard to each axis and by the respective indexing motions. (i) Movement at constant speed generally; (ii) motion towards a predetermined coordinate point and stopping therein; (iii) interrogating the equipment status. The motion of the patient rest is speed controlled with a max speed of about 10 mm/s whereby acceleration and deceleration occur preferably along graduated slopes and ramps. Through coordination of the various drives operating in relation to the various axes, one can in fact carry out any kind of movement, of course within practical limit, and along any kind of trajectory. For example it may be of advantage to use an isocentric motion pattern to home in, in the above defined sense. The various inputs and operations will be indicated to be observed by the user and operator, using for this purpose a separate monitor for the computer. The instantaneous input may be highlighted on the screen so that the operating person knows where the positioning actually is in any given moment. The master computer runs through the individual steps for positioning by means of the indexing motors but the individual operating modes may be selected by the user from within a menu as it appears on the screen. In addition protective functions for the positioning operations are provided, such as responding to touching of the ellipsoid edge by the patient so that any kind of patient can be treated. Moreover, desired coordinate value will be displayed on the screen as part of the menu in addition to the actual patient-table coordinates as well as the actual water cushion level. DESCRIPTION OF THE DRAWINGS While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter which is regarded as the invention, it is believed that the invention, the objects and features of the invention and further objects, features and advantages thereof will be better understood from the following description taken in connection with the accompanying drawings in which: FIG. 1 illustrates a block diagram for a positioning control device in accordance with the preferred embodiment of the present invention for practicing the best mode thereof; FIG. 2 is an example of the operator's panel manual as can be seen on the monitor of the panel; FIG. 3 is a schematic illustration of a light pen measuring, indicating and inputting system showing additionally alternative input devices; and FIGS. 4 and 5 are modified drawings from U.S. Pat. No. 4,705,026 as modified background. Proceeding now to the detailed description of the drawings, FIG. 1 shows a first central and control computer 2 being a master controller to which are connected, as input-output units, an operator terminal 4 with the usual panel and monitor, a manual override control 6 that has a separate function but physically it may be a part of the panel 4; and a light pen-measuring and data acquisition system 8. The light pen system 8 is connected to two X-ray monitors 10 and 12 as well as the respective X-ray receiving systems 10" and 12". Reference numerals 10' and 12' denote the X-ray sources. A first interface circuit 16 provides for the transmission of commands from the master controller 2, to four independently operating indexing computers or controllers designated collectively by 18 and further identified by the axes x,y,z,w to indicate that motion is provided along axes x,y, z and in a tilting direction w around axis x. The respective motion is carried out by a group of motors 24 individually identified by Mx, My, Mz, Mw. The four controllers 18 provide the servo operation for position controlling each of the motors 24 separately and in feedback configuration. The master controller 2 provides a common control signal for indicating to each of the motors 24 a representation, to where to place the patient rest as far as motion on the respective axis (x,y,z,w) is concerned. The patient rest may be constructed as shown e.g. in U.S. Pat. No. 4,705,034 issued Nov. 10, 1987 or the other references mentioned above. The second interface 20 establishes a connection between the four indexing computers or controllers 18 with power output stages 22 (22x, 22y, 22z, 22w) which in turn operate and drive the motors 24 thereof; as already stated there are four motors Mx, My, Mz and Mw corresponding to the four axes (x,y,z,w). The motor shaft in each instance as far as providing turning operation is concerned and to be explained more fully below, is connected to a shaft encoder 26. There are four encoders being in each instance an optical encoder or any other path tracking device, a transducer, tachometer, or resolver, which, on an incremental, high resolution basis tracks the motion of the respective motor. The encoders 26 provide signals which are directly used for motor control in the power end stages 22 immediately as far as feedback is concerned, and also through the respective controllers 18 for determining tracking and indicating to the equipment the actual position of the motion devices as they are related to particular axes. These encoders 26 and particularly their motor shafts are connected in addition to absolute value yielding transducers 28, which give exact position values to the controllers 18. To the extent necessary the indexing computers will communicate that information to the master control computer 2. Mechanical limit switches 30 are provided along the axis and in end position of movement obtained by the motions along these axes (x,y,z,w). These switches indicate to the computers or controllers 18 and to the power stages 22 directly that further motion in the particular direction is no longer possible because what is being moved has reached an end position. These are actual physical limiters operating in addition to software limits which, independently from the physical limitation provide for limitations on attainable movement. Details will be explained more fully below. In each case the effect of a response is to turn off the respective power stage 22 completely and immediately to bring whatever motor is available to a full stop in order to avoid any damage. Such damage may be to the equipment but also to the patient. The calculating system as well as the X-ray system are electrically (potential) separated from the light pen system so that any potential transfer and voltage differences will not become effective anywhere. FIG. 2 illustrates an operator's menu as it may appear on the monitor of terminal 4 as shown in FIG. 1. The menu will be run through by the computer 2 automatically, line by line, and the respective relevant information of immediate actuality is highlighted. Moreover, the desired coordinates as far as the concrement position is concerned, as well as the coordinate system of the focal point F2 in concrement and, finally, the level of the water cushion are also indicated. The desired value coordinates as well as the actually existing coordinates have to agree at a particular point in time so that the concrement is in the right position when a shock wave is being released and generated. Through the coordinates one can also ascertain indirectly whether and where the positioning devices have reached its limit position anywhere. The positioning device as proposed here in fact shortens the needed time to locate a concrement in that locating and positioning in the automated control operation are in each instance one shot operations. The positioning is to a large degree independent from the operating personnel. The only genuine human input is actually a medical diagnosis; the physician has to identify on the X-ray screen 10, 12 the location of the concrement. That is to say, as the physician touches a point on the screen 10/12 with the light pen, the system "assumes" that this is the desired point of the concrement location, and the equipment homes in on it. This is an important safety feature because once that desired point is identified, the X-ray equipment can be turned off and that minimizes in fact the X-ray load on the patient but also on the operating personnel at large so that the overload safety aspects are increased. Moreover, erroneous positioning is in fact excluded once a concrement has been recognized by a trained person and within the prescribed limits (infra). From an overall point of view the treatment time can be shortened and the equipment can be used longer and for a larger number of patients. The water cushion automatically tracks any patient movement and that maintains coupling between the patient and the cushion membrane. Inputting the concrement position in the alternative can be carried out through a touch screen. A touch screen is a particular device placed in front of a video screen with an infrared lattice or a particular pressure sensitive foil. The position can be indicated simply by touching the screen i.e. the device with a finger. In order to meet of all the required and desired safety factors, including any demands made on account of safety rules, it may be required to minimize coupling between X-ray equipment and use calculator as well as the measuring system. For this purpose one needs the device of the invention in lieu of complete digitization of any X-ray image, the invention uses just the filtered out video synchronous and time synchronous pulses extracted from the X-ray image. FIG. 3 includes schematically the coordination of the light pen measuring system 8 for acquiring the coordinates of actual location of concrements such as 32. The two X-ray monitors 10 and 12 will image the concrements 32 as well as the kidneys 34. Monitor 10 and 12 are connected to the light pen system 8 via connectors 36. Another electrical connection 38 connects the light pen system 8 to the main computer 2. The light pen system 8 includes two counters 40 and 41 for determining screen coordinates where the pen has touched the screen. The light pen 42 itself is, of course, connected to and is a part of the system 8. The pen 42 has a tip which includes a pressure monitor and switch 44. In addition, there is a light receiver (not indicated). Alternatively one can use a tracking ball 46, a mouse 48 or a joystick 50. They all can be part of the same system and can be used alternatively. They are connected to and are a part of the measuring system 8 and provide corresponding coordinates values. In the case of a tracking ball, a mouse or a stick one needs also hairpin as well as a central cross hair 54 a monitor screen 10 or 12 has anyway. In order to guarantee safe and secure position of the patient a number of safety functions and precautions are integrated in the system. (a) Function tests on operational start up are carried out through the computer 2 in that a movement is introduced i.e. motors 24 are turned on and simulate and run through their ranges while automatically a comparison is made between actual and desired coordinates and any agreement or disagreement agreement is tested. If as a consequence of this test, agreement does not obtain, an appropriate positioning system defect will be displayed on the monitor 4. (b) All movements which are manually introduced as well as automatically obtained or obtainable positions, are triggered in accordance with the dead man principle i.e. it requires actuation of a particular key by an operator. If the key is not or no longer depressed i.e. released for any reason, the respective motion is stopped automatically. (c) Certain limits are introduced as far as the source is concerned and with respect to the motion as controlled by the various computers whereby a combined motion in several directions may lead to stopping if for some reason a software limit has been reached. (d) Analogously, there is a hardware limit (switches 30) as far as motion overrun is concerned. These limits that are provided at the end of the respective displacement paths. Whenever such a limit is reached then the appropriate calculator or even the power source of the equipment turns off the device of controls. (e) The current supply to a power stage is generally turned on by the calculator and computer 2 only during positioning, if there is no positioning the power simply is turned off. (f) Motion is triggered only when the respective motion control stages, i.e. controllers 18 do not only receive speed control signals but also an independent enabling signal. (g) Any signal transmission from and to the respective path transducer 26 is carried out through a wire pair i.e. without the reliance on any connection that is common or to ground. (h) For inputting the position of a concrement through the light pen system 18 one provides for a number of unique error signal situations. (h1) "No position input". This kind of error situation appears on the monitor 4 if within 30 seconds following a request made by the operator menu no input has been provided by the light pen system 8(42). This situation implies that there is nothing the user can indicate even though he should indicate. (h2) "Inaccurate positioning". This indication appears on monitor 4 if the inputted data scatter too widely. As the light pen 42 touches the screen (10 or 12) one will obtain about 10 coordinate pairs which are being ascertained by the counter tracking the light pen 42(8). The range between zero and the maximum value is subdivided into X-groups wherein X is the maximum permissible scatter value divided by 10. The values as ascertained are divided into groups wherein each group covers a certain number range. From the group which covers more than 5 values one will calculate standard deviation as well as the medium or average value. If the standard deviation exceeds 0.01 the above mentioned indication obtains. (h3) "Positioning input incorrect" is an indication which signifies that all of the coordinate values do not lead to a particular point in space within a sphere of 10 mm diameter. (h4) "Position not obtainable" will be indicated under the following conditions. The maximum freedom of motion on each axis is about +10 cm. If the respective calculated coordinate is outside of that range this error indication obtains. One can also indicate on the screen in what direction the patient has to be physically relocated on the rest e.g. after a particular limit of motion has been obtained so that the patient is shifted in the range covered by the equipment. (i) If the desired and the actual coordinate values do not agree with the limits as defined above during automated positioning and are caused e.g. by accidental release of the enabling key, then the following obtains. In order to increase safety after the positioning has been completed a, so to speak, cross check through an X-ray system may be carried out. The invention is not limited to the embodiments described above but all changes and modifications thereof, not constituting departures from the spirit and scope of the invention, are intended to be included.
Apparatus for positioning the body of a patient in relation to equipment for contactless comminution of concrements such that the focal point of equipment is made to coincide with a concrement; the patient who lies on a rest which is moved with the patient on it in a longitudinal direction, tilted about it, and moved also laterally and in a direction that is transverse to the longitudinal and lateral directions of movement; a water filled cushion with controlled water level is adapted for interpositioning between the equipment for comminution and focusing, and the patient, a plurality of differently oriented X-ray beams are provided for locating a concrement in the patient and images are marked through a light pen or the like on X-ray monitors; a control provides for homing-in the rest in relation to the comminution equipment such that its focal point coincides with the concrement as previously detected.
0
FIELD OF THE INVENTION [0001] The present invention generally relates to a device and process for removing contaminants from wastewater by electrolysis processes, and more particularly to an advanced electro-coagulation device that comprises electro-coagulation and electro-catalytic precipitation cells, and at least one electrode surface activator unit, and a process that removes the contaminants from wastewater using the advanced electro-coagulation device in a continuous and cost-effective manner. BACKGROUND OF THE INVENTION [0002] Wastewater in this application refers to any aqueous fluid that without prior treatment is not suitable for human consumption or industry application or discharge from any facility because of the existence of natural or artificial contaminants. The contaminants include organics, particulates, sub-micro particles, microorganisms such as viruses and bacteria, and dissolved metals. Wastewater is being continuously generated by nature (e.g., storm, mudslides, animals, and growth of microorganisms) and human activities (e.g., domestic consumption, and industry applications); it imposes a grave challenge to provide suitable water supply for human consumption and industry applications because of limited water reservoir on the Earth. Therefore, wastewater treatment is critical for provision of reusable water and limit of spreading of contamination from untreated discharge from wastewater-generating industries. [0003] Electrolysis process (often referred as electrocoagulation) has been proven to be able to treat a variety of wastewater including paper pulp mill waste, metal plating, tanneries, caning factories, steel mill effluent, slaughterhouses, chromate, lead and mercury-laden effluents, domestic sewage, and radioactive materials. It has the capability of removing a large range of contaminants under a variety of conditions ranging from: suspended solids, heavy metals; petroleum products, color from dye-containing solution, aquatic humus, and defluoridation of water. The treatment provides clear, clean, odorless and reusable water. [0004] Electrocoagulation is a complex process with a multitude of mechanisms operating synergistically to remove contaminants from wastewater. Electro-coagulation employs a pair of electrodes to neutralize small charged particles in colloidal suspension. The electrodes are usually made of aluminum or iron. When the electrodes (anode and cathode) are subjected to a specific current density, the anodes are oxidized and form metal ions (either Fe +2 , Fe + or Al +3 ) in solution that react with hydroxide (OH−) anions created in the electrocoagulation process. This leads to the formation of metal hydroxide ions, either cationic or anionic species depending on the pH of the wastewater. A combination of inert anodes and metal (titanium) cathodes can also be used. The inert electrodes accomplish contaminant destabilization utilizing the transfer of electrons within the electrolyte. The transfer of electrons and formation of protons (H + ) created in the electrocoagulation process can effectively destabilize a range of metal and organic contaminant species. [0005] For aluminum anode, various forms of charged hydroxyl (OH − ) and Al +3 species might be formed under appropriate conditions. These gelatinous hydroxyl cationic/anionic complexes can effectively destabilize contaminant particles by adsorption and charge neutralization, resulting agglomeration due to the attractive van der Wall forces and formation of stable precipitates that could then be separated by conventional separation technique. Typical chemical reactions at both the aluminium anode and cathode are shown below: [0006] Anode: [0007] Al (s) →Al 3+ (aq) +3e − (lose electrons) [0008] Al 3+ (aq) +3H 2 O→Al(OH) 3 +3H + [0009] nAl(OH) 3 →Al n (OH) 3n [0010] Cathode: [0011] 2H 2 O+2e − →H2 (g) +2OH − [0012] Al 3+ +3e − →Al (s) (gain electrons) [0013] The electrochemical dissolution of the aluminum anode produces Al 3+ ions which further react with OH − ions (from cathode), transforming Al 3+ ion initially into Al(OH) 3 and then into the gelatinous hydroxyl precipitate (Aln(OH) 3n ). Depending on the pH of the wastewater, different ionic species will also be formed in the medium such as: Al(OH) 2+ , Al 3 2(OH) 2 2+ , and Al(OH) 4 . At the cathode, hydrogen (H 2 ) gas and hydroxide (OH − ) ions are formed from the division of H 2 O and dissolved metals are reduced to their elemental state. (i.e. Al 3+ ). [0014] The electrochemical dissolution of the iron anode produces iron hydroxide, Fe(OH) n where n=2 or 3. There are two proposed mechanisms for the production of the iron hydroxide. Like the gelatinous aluminum hydroxyl precipitate (Aln(OH) 3n ), the iron hydroxide precipitate (Fe(OH) n ) formed remains in the aqueous medium (stream) as a gelatinous suspension. This suspension can also remove water and wastewater contaminants either by complexation or by electrostatic attraction, followed by coagulation. The cathode is subject to scale formation, which can impair the operation of the system. Typical chemical reactions at both the iron anode and cathode are shown below: [0015] Anode: [0016] 4Fe (s) →Fe 2+ (aq) +8e − (lose electrons) [0017] 4Fe 2+ (aq) +10H 2 O (I) +O 2(g) →4Fe(OH) 3(s) +8H + (aq) [0018] Cathode: [0019] 8H + (aq) +8e − →4H 2(g) [0020] Overall: [0021] 4Fe (s) +10H 2 O (I) +O 2(g) →4Fe(OH) 3(s) +4H 2(g) [0022] Anode: [0023] Fe (s) →Fe 2+ (aq) +2e − (lose electrons) [0024] Fe 2+ (aq) +2OH − (aq) →FeOH 2(s) [0025] Cathode: [0026] 2H 2 O (I) +2e − →H 2(g) +2OH − (aq) [0027] Overall: [0028] Fe (s) +2H 2 O (I) →Fe(OH) 2(s) +H 2(g) [0029] A typical electrocoagulation reactor contains a series of substantially parallel electrolytic plates or electrodes through which the wastewater to be treated travels in a serpentine path while being exposed to a strong electric field or voltage. For the past twenty over years, in order to try to find a more environmentally friendly way to treat wastewater, many electrocoagulation (EC) systems were designed and built for many wastewater treatment applications. For example, US 2002/0040855 A1 discloses an apparatus for electrocoagulation treatment of industrial wastewater. However, a broad use of the EC systems is limited by unsolved technical obstacles. [0030] The main technical obstacles affecting the efficiency and performance of EC devices include the corrosion and passivation of electrodes and the accumulation of gases in an EC device. Electrodes are easily coated with contaminants, corroded and oxidized by wastewater, thus unable to evenly distribute the ion density in wastewater. Therefore, regular cleaning and replacement of electrodes were normally required. In addition, the oxygen and hydrogen gases are gathered over time at the electrodes and not utilized fully for treating the wastewater, causing a reduction or stoppage of electrolysis action after some time. These result in higher electrical power consumption than expected, slower separation of flocculants from the water at the output, higher percentage of sludge and lower percentage of floating flocculants due to inefficient use of hydrogen gas, and required post-treatment of sludge. [0031] Attempts have been made to address the problem of passivation of electrodes during the electrocoagulation process by constructing self-cleaning electrolytic cells. For example, US 2003/0222030 A1 discloses an electro-coagulation treatment system with an electrolytic cell including an anode and a helical cathode. It claims that the provision of a helical cathode in the form of a helically wound coil of a wire or rod of circular cross section provides an arrangement in which the cell is automatically self-cleaning in that the coagulated precipitates are carried from the cell by the flow of the water. However, the construction of such a helical cathode is a challenge and increases its cost. In addition, CN 01108767.6 discloses an EC device with a wiper to remove any deposits from the surfaces of electrodes. However, the wiper is in firm contact with surfaces of electrodes, and this causes unnecessary wearing out of the electrodes. [0032] Attempts also have been made to reduce the sludge by increasing the flocculants. For example, U.S. Pat. No. 6,719,894 discloses an apparatus for treating organics, particulates and metal contaminates in a waste fluid. The apparatus has a pressurizing means for pressurizing waste fluid to be treated in the reactor vessel so that water, organics, particulates and metal contaminants form dissolved gases and form precipitate particles in the pressurized waste fluid. When the pressure of the treated waste fluid is reduced, dissolved gases evolve from the waste fluid causing said precipitate particles to float to a fluid surface for removal. However, the introduction of pressure complicates the system. SUMMARY OF THE INVENTION [0033] Therefore, there is an imperative need for an electrocoagulation device and method that can treat wastewater in a continuous and cost-effective manner. [0034] In one aspect, the present invention provides an electrocoagulation (EC) device for treating aqueous fluids with contaminants, where the EC device comprises a plurality of anode electrode plates and cathode electrode plates, wherein the anode and cathode electrode plates are arranged alternatively so that one anode plate and one cathode plate form an electrolytic cell with which the aqueous fluids undergo electrochemical reactions so that the contaminants will become gelatinous flocculants and sludge at the end of the reactions, and wherein the electrode plates are substantially parallel metallic electrolytic plates disposed substantially parallel to each other; at least two bus-bars, where one bus-bar is connected to the anodes, and another bus-bar to the cathodes; an electrode surface activator (ESA) unit with a plurality of wipers, wherein each wiper is disposed between two adjacent electrode plates, and wherein the wipers are lightly in touch or in close proximity of the surfaces of the electrode plates when the wipers are in motion, and wherein the wipers in motion keeps the surfaces of the electrode plates from passivation; and a sealed chamber within which the electrode plates and ESA unit are disposed. [0035] In one embodiment, in the EC device, the electrolytic plates are fabricated from material selected from the group consisting of iron, titanium, platinum, steel, aluminum, copper, carbon, metal-impregnated plastics, ceramics or a mixture thereof. In another embodiment; in the EC device, the electrolytic plates are made of aluminum. In another embodiment, in the EC device, the electrolytic plates are made of iron. In yet another embodiment, each of the electrolytic plates has a hole allowing the aqueous fluids to pass through from one cell to another; wherein the holes on two adjacent plates are opposite cross the center. In still another embodiment, all the anode electrode plates are connected to one bus-bar and connected to the positive terminal of a DC power supply; and wherein all the cathode electrode plates are connected to another bus-bar and connected to the negative terminal of the DC power supply. In yet another embodiment, the bus-bar is made of copper or copper coated or plated with tin, silver or gold. [0036] In another embodiment, the ESA unit further comprises a wiper driver shaft, a speed reduction gearbox, an electric motor for driving the wiper drive shaft via the speed reduction gearbox, a bearing with seal holding the wiper drive shaft in place and allowing smooth movement and water tight sealing, and a plurality of wiper spacers for insulating the wiper shaft from the electrode plates when it penetrates the plates; wherein the wiper drive shaft is disposed through the centers of the electrode plates. In yet another embodiment, the wiper blade has a cylindrical shape. In another embodiment, the wiper blade has a partial cylindrical shape with two straight sides. In another embodiment, the wiper blade has a thin blade protrusion throughout the length of the blade. In another embodiment, the wiper blade has brushes (toothbrush style) attached throughout the length of the blade; wherein the wiper blade further comprises a plurality of holes on its two surfaces facing the plate surfaces to accommodate fibers to form a brush on each side. [0037] In another embodiment, the sealed chamber is formed by two end bracket/stand, two end insulators, a plurality of electrode plates and a plurality of electrode spacers with O-rings so that the reactions can be carried in a sealed environment, preventing leakage of liquid and gases. In another embodiment, the EC device further comprises an inlet and an outlet for allowing the EC device to get the aqueous fluids for treatment and exit the treated aqueous fluids. [0038] In another embodiment, all anode electrode plates are sacrificial so as to form an electro-coagulation device. In another embodiment, all anode electrode plates are not sacrificial so as to form an electro-catalytic device. In another embodiment, the anode electrode plates are made of carbon. In another embodiment, at least one anode electrode plate is different from the rest (e.g., sacrificial vs non-sacrificial) so as to form a hybrid EC device. [0039] In another embodiment, the aqueous fluids with contaminants are any aqueous solution that needs to be treated before its use. In another embodiment, the contaminants include organics, metals, microorganisms, and sub-micro particles. [0040] In another aspect, the present invention provides an electrocogulation system for treating aqueous fluids with contaminants, where the system comprises a pre-treatment unit for receiving the aqueous fluids to be treated; a post-treatment unit for receiving the aqueous fluids being treated; and a plurality of anode electrode plates and cathode electrode plates, wherein the anode and cathode electrode plates are arranged alternatively so that one anode plate and one cathode plate form an electrolytic cell with which the aqueous fluids undergo electrochemical reactions so that the contaminants will become gelatinous flocculants and sludge at the end of the reactions, and wherein the electrode plates are substantially parallel metallic electrolytic plates disposed substantially parallel to each other; at least two bus-bars, where one bus-bar is connected to the anodes, and another bus-bar to the cathodes; an electrode surface activator (ESA) unit with a plurality of wipers, wherein each wiper is disposed between two adjacent electrode plates, and wherein the wipers are lightly in touch or in close proximity of the surfaces of the electrode plates when the wipers are in motion, and wherein the wipers in motion keeps the surfaces of the electrode plates from passivation; and a sealed chamber within which the electrode plates and ESA unit are disposed. [0041] In yet another aspect, the present invention provides a process for treating aqueous fluids with contaminants using the device and system provided herein. [0042] One advantage of the present invention is that the treatment of wastewater becomes continuous operation with high efficiency. [0043] Another advantage of the present invention is that both electro-coagulation and electro-catalytic precipitation cells can be built into one device, and cells can be configured to treat all types of pollutants in wastewater in one pass. [0044] Another advantage of the present invention is that electrodes are activated at all times by an electrode surface activator unit, ensuring high efficient electrochemical reaction. The electrode surface activator unit keeps the electrode surfaces clean, reduces metal depletion and controls the amount of passivation as required by the process. [0045] Another advantage of the present invention is that the processing speed of waste water is 2 to 5 times faster than EC machines made by others. [0046] Another advantage of the present invention is that the separation of flocculants from water is 2 to 5 times faster than EC machines made by others. [0047] Another advantage of the present invention is that flocculants floats due to efficient utilization of hydrogen and oxygen gas given off by the EC cell. [0048] Another advantage of the present invention is that very much lower electric power consumption than EC machine made by others. [0049] Another advantage of the present invention is that any odor and color of the processed water is removed or greatly reduced. [0050] Another advantage of the present invention is that pathogens (bacteria and micro-organisms) are killed or removed by up to 99.99%. [0051] The objectives and other advantages of the invention will become apparent from the following detailed description of preferred embodiments thereof in connection with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0052] Preferred embodiments according to the present invention will now be described with reference to the Figures, in which like reference numerals denote like elements. [0053] FIG. 1 is a block diagram illustrating the electrocoagulation system in accordance with one embodiment of the present invention. [0054] FIG. 2 shows an illustrative cross-section view of the electrocoagulation device in accordance with one embodiment of the present invention. [0055] FIG. 3 shows a plan view of the outlet end of the EC device in accordance with one embodiment of the present invention. [0056] FIG. 4 shows a plan view of the inlet end of the EC device in accordance with one embodiment of the present invention. [0057] FIG. 5 shows a schematic cross-section view of the configurations of the electrode plates 11 , and the wipers 20 and wiper drive shaft 21 of the ESA unit within the sealed chamber of the EC device in accordance with one embodiment of the present invention. [0058] FIG. 6 shows a schematic cross-section view of a first type of electrolytic cell (A-cell) in accordance with one embodiment of the present invention. [0059] FIG. 7 shows a schematic cross-section view of a second type of electrolytic cell (B-cell) in accordance with one embodiment of the present invention. [0060] FIG. 8 shows a partial schematic cross-section view of the configuration among the electrode plates and wiper in accordance with one embodiment of the present invention. [0061] FIG. 9 shows an illustrative view of a wiper with two blades in accordance with one embodiment of the present invention. [0062] FIG. 10 shows an illustrative view of a wiper with four blades in accordance with one embodiment of the present invention. [0063] FIG. 11A and FIG. 11B shows an illustrative cross-section view and plan view respectively of the wiper in accordance with one embodiment of the present invention. [0064] FIG. 12A and FIG. 12B shows an illustrative cross-section view and plan view respectively of the wiper in accordance with another embodiment of the present invention. [0065] FIG. 13A and FIG. 13B shows an illustrative cross-section view and plan view respectively of the wiper in accordance with one embodiment of the present invention. [0066] FIG. 14A and FIG. 14B shows an illustrative cross-section view and plan view respectively of the wiper in accordance with one embodiment of the present invention. [0067] FIG. 15 shows a schematic view of the basic electrical connections among the electrolytic plates, bus-bars, wiper motor and power supplies in accordance with one embodiment of the present invention. [0068] FIG. 16 shows an illustrative view of the process of wastewater flow through and within the EC device in accordance with one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0069] The present invention may be understood more readily by reference to the following detailed description of certain embodiments of the invention. [0070] Throughout this application, where publications are referenced, the disclosures of these publications are hereby incorporated by reference, in their entireties, into this application in order to more fully describe the state of art to which this invention pertains. [0071] While the description will relate to many specific elements and techniques in order to better illustrate the principles of the present invention, it is to be appreciated that the present invention is not limited to the specific descriptions. The present invention can be practiced with variations to any specific elements and techniques without departing from the principles of the present invention. At the same time, many details and specifics that their omissions will not affect the practices of the present invention will be omitted from the description in order not to obscure the principles of the present invention. [0072] Now referring to FIG. 1 , there is provided an electrocoagulation (EC) system in accordance with one embodiment of the present invention. The EC system 1 comprises a pretreatment unit 2 , an electrocoagulation (EC) device 3 , and a post-treatment unit 4 . The pre-treatment unit 2 includes at least one tank for receiving wastewater to be treated and input pipes and pumps and valves for controlling the speed and volume wastewater being introduced into the pre-treatment unit and being pumped out the pre-treatment unit and into the electrocoagulation device. The pre-treatment unit may pre-filter the wastewater to remove big particles and/or change the pH and compositions of the wastewater by adding the correct type and amount of chemicals so as to improve the efficiency. The EC device 3 performs the electrolytic treatment, where the device and its operation will be detailed hereinafter. The post-treatment unit 4 includes at least one tank for receiving the affluent from the EC device. The post-treatment unit separates the clean water from the flocculants and sludge so that the flocculants are collected from the surface and the sludge is collected at the bottom for further treatment. Dosing small amount of polymer will make the flocculants bind and float more effectively. The separation can employ any known methods including filtering and precipitating. The pre-treatment and post-treatment can be done using any known methods. Thus, no further details will be provided herein. [0073] In one aspect of the present invention, there is provided an EC device that comprises a plurality of electrolytic cells and an electrode surface activation (ESA) unit, where the EC device can treat a wide range of wastewater in a continuous and cost-effective manner. [0074] Now referring to FIG. 2 , there is provided an illustrative side view of the EC device in accordance with one embodiment of the present invention. The EC device 3 comprises a plurality of anode and cathode electrode plates 11 , two bus-bars 12 for electrical connections to anodes and cathodes, two end bracket/stand 13 , end insulators 23 , cell stack 14 , base frame 15 , inlet (inflow) 16 , outlet (outflow) 17 , and an ESA unit including a wiper motor 18 , a reduction gearbox 19 , a plurality of wipers 20 (first shown in FIG. 5 ), and wiper drive shaft 21 (first shown in FIG. 5 ). The cell stack 14 , the end insulators 23 and the two end bracket/stand 13 form a sealed chamber within which wastewater is being treated. The interior of the sealed chamber is of cylindrical shape for circular electrode plates in one embodiment. The interior may be in any other shapes that are suitable for specific applications. The exterior of the sealed chamber may be of polygon shapes for each handling. It is to be noted that the shapes are not critical for the practice of the present invention. The gap or space between the anode and cathode electrode plates depends on the type and capacity of wastewater to be treated; it should be easily determined by those skilled in the art. The sealed chamber is disposed onto the base frame 15 . The cell stack, end bracket/stand, and base frame may be made of any suitable material by any known techniques. In certain embodiments, the suitable materials include stainless steel, iron, engineering grade plastics, or ceramics. [0075] The plurality of anode and cathode electrode plates 11 are substantially parallel metallic electrolytic plates disposed substantially parallel to each other alternatively within the sealed chamber. The electrolytic plates may be fabricated from material that may sacrifice or donate ions in an electrolysis process. Preferably, the plates may be fabricated from iron, titanium, platinum, steel, aluminum, copper, carbon, metal-impregnated plastics, ceramics or the like. In one embodiment, the electrolytic plates are made of aluminum. In another embodiment, the electrolytic plates are made of iron. The two bus-bars 12 connect the electrolytic plates alternatively so that every two adjacent electrolytic plates form an electrolytic cell. All the anode electrode plates are connected to one bus-bar and connected to the positive terminal of a DC power supply. All the cathode electrode plates are connected to another bus-bar and connected to the negative terminal of the DC power supply. In one embodiment, the bus-bar is made of copper or copper coated or plated with tin, silver or gold. The bus-bar may be also made of other metals including gold, silver, or the like. As shown in FIG. 2 , in one preferred embodiment, the interlaced electrolytic cells with the electrode plates are mounted vertically and the EC device is mounted in a horizontal position. The horizontal orientation with vertical electrode plates reduces the accumulation of bubbles on the surfaces of the electrode plates. It is to be appreciated that other orientations like vertical one may also be used in the present invention. [0076] While there are thirty electrolytic cells shown in FIG. 2 , the number of electrolytic cells within one EC device will vary according to specific applications. In one embodiment, the EC device has sufficient numbers of cells to allow the wastewater to stay in the EC device for about 60 to 120 seconds. It is evident that the length of time for wastewater to stay in the EC will depend on multiple factors including the number of electrolytic cells and flow rate. In addition, the distance between two adjacent plates is determined by multiple factors such as power supply and the types of wastewater to be treated. It is in the theory of electrocoagulation that the closer the distance between the electrode plates, the lower the DC voltage is required for electrolysis reaction. In one preferred embodiment, when the DC power supply is in the range of 5 to 15 voltages, the distance between two plates is about 5 to 15 mm. [0077] The inlet (inflow) 16 takes wastewater from the pre-treatment unit 2 . The outlet (outflow) 17 vents the treated wastewater into the post-treatment unit 4 . Suitable pumps and valves can be used to control the flow. In one embodiment, the inlet pipe is at one end and the outlet pipe at the other end. It is evident that both the inlet and outlet can be configured at the same end as long as the inflow will not mix with the outflow before the inflow is fully treated within the EC device. In one embodiment, both of the inlet pipe and outlet pipe can have threaded or flanged connection, depending on the piping requirements. [0078] As for the ESA unit, the wiper motor is a small motor that drives the wiper drive shaft 21 via the speed reduction gearbox 19 . [0079] Now referring to FIG. 3 , there is provided a plan view of the outlet end of the EC device in accordance with one embodiment of the present invention. The electrode plates are fastened along their peripherals. The fastening means 22 include through-rods and nuts. In addition, the bus-bars 12 can be located within any suitable points on the electrode plates. FIG. 4 shows a plan view of the inlet end of the EC device in accordance with one embodiment of the present invention. [0080] Now referring to FIG. 5 , there is provided a schematic cross-section view of the configurations of the electrode plates 11 , and the wipers 20 and wiper drive shaft 21 of the ESA unit within the sealed chamber of the EC device in accordance with one embodiment of the present invention. The electrode plates 11 are insulated from each other by electrode plate spacers 26 and sealed with O-rings 25 . Both ends of the cell stack 14 are insulated from the two end bracket/stand 13 by the end insulators 23 . The end insulators and electrode plate spacers may be made of any suitable insulating materials. In one embodiment, they are made of plastics. Each electrode plate has a flow hole 28 (shown in FIG. 9 ) at its peripheral allowing the wastewater to flow. In one embodiment, in order to increase the travel distance of the wastewater within the EC device, the holes on two adjacent plates are opposite to each other. It is evident that the holes can be constructed in other shape, size or configuration according to specific requirements. In one embodiment, the flow holes 28 are round in shape. The wipers are disposed between every two adjacent electrode plates. All wipers 20 are connected to the wiper drive shaft 21 . In one embodiment, in order to obtain the best balance, the wiper drive shaft 21 is located within the center of the sealed chamber and the wipers. The wiper drive shaft 21 is insulated from the electrode plates by the wiper drive spacers. A bearing with seal 33 holds the wiper shaft in place, allowing smooth movement and water tight sealing. [0081] It is convenient to use identical electrolytic cells in one EC device, but it may not be able to treat as many contaminants as desired. The inventors of the present invention discovered that the inclusion of two kinds of electrolytic cells within one EC device broadened its capabilities of treating different contaminants. Therefore, in one aspect of the present invention, there is provided two kinds of electrolytic cells that can be employed in any EC devices, wherein the two kinds of electrolytic cells are based on two different operation principles. [0082] Now referring to FIG. 6 , there is provided a schematic cross-section view of a first type of electrolytic cell (A-cell) in accordance with one embodiment of the present invention. The A-cell is an electro-coagulation cell using principle of sacrificial anode to create flocculants to remove organic solids, minerals or metal from the wastewater. The anode 11 a is usually made of aluminum and is thicker than that of the cathode 11 b which is made of iron. In combination with the wipers (described in detail hereinafter) of the present invention, it has been demonstrated that the degree of surface passivation could be controlled and the electrode metal depletion was reduced by up to 80% as compared to other EC device. The small amount of metal content in the flocculants released by the sacrificial electrodes is processed by the B-cell (detailed next) into harmless compounds. [0083] Now referring to FIG. 7 , there is provided a schematic cross-section view of a second type of electrolytic cell (B-cell) in accordance with one embodiment of the present invention. B-cell is an electro-catalytic cell using electro-catalytic precipitation principles that do not cause electrode metal depletion. It uses electrolytic oxidation to reduce chemical compounds and oxidize metals in wastewater. This oxidation process reduces organic solids to a liquid, and a liquid into gas, usually to H 2 O and CO 2 . Precipitation is the oxidation/reduction of metals to form metal mineral compounds form into flocculants. Hydroxyl radicals (OH) and ozone (O 3 ) are produced in each cell. Both anode 11 c and cathode 11 d electrodes are of the same thickness, and have the same thickness as the cathode of the A-cell. The B-cell can treat some pollutants which the A-cell cannot and vice-versa. The anode 11 c is usually made of carbon and cathode 11 d made of iron, same as 11 b . The cathode 11 d can also be the shared cathode of an A-cell. By using different metal, electrically conductive material like carbon or coating the surfaces of the electrodes with metal oxides, it is possible to treat many impurities or pollutants that the A-cell cannot. [0084] Both types of cells have its own unique functions and are complementary to achieve a complete wastewater treatment process. Depending on the type of wastewater to be treated, the EC device can be configured with a combination of A-cells and B-cells. The two types of cell can be placed alternately with more of one type, but the last one should be a B-cell in order to remove any metal present in the output flocculants. [0085] As discussed above, electrode plate passivation during the electrocoagulation process causes many problems. Current designs by others for minimizing the plate passivation have their limitations one way or the other. Therefore, in another aspect of the present invention, there is provided an ESA unit with new wiper designs that overcome the shortcomings of the prior art. [0086] The ESA unit comprises a wiper motor 18 , a reduction gearbox 19 , a plurality of wipers 20 , a plurality of spacers 24 , wiper drive shaft 21 and bearing with seal 33 . Now the description is focused on the wipers. In reference to FIG. 8 , there is provided a partial schematic cross-section view of the configuration among the electrode plates and wiper in accordance with one embodiment of the present invention. In one embodiment, each wiper in a cell consists of two blades as shown in FIG. 9 . In another embodiment, each wiper in a cell consists of four blades as shown in FIG. 10 . The blades are designed and made in such a way that it only touch the electrode surfaces very lightly or do not touch at all. Using hydraulic operation principles, the rotating blades create hydraulic cleaning action of the electrode surfaces and turbulence of the liquid inside the cell. With the ESA unit, it has been demonstrated that the metal depletion of sacrificial electrodes was reduced by up to 90% of the prior art designs. The amount of passivation of the electrode surfaces can be reduced or controlled. [0087] The shape and configuration of the blades of the wiper can be varied with specific applications. It is to be appreciated that different blades to be discussed herein can be combined for use in one EC device. FIG. 11A and FIG. 11B shows an illustrative cross-section view and plan view respectively of the wiper in accordance with one embodiment of the present invention. The blade as shown in FIG. 11A and FIG. 11B has a cylindrical shape. The blade is inserted into the wiper center piece 27 and the wiper center piece has a wiper drive shaft hole 29 for accommodating the wiper drive shaft. FIG. 12A and FIG. 12B shows an illustrative cross-section view and plan view respectively of the wiper in accordance with another embodiment of the present invention. The blade as shown in FIG. 12A and FIG. 12B has a partial cylindrical shape with two straight sides. FIG. 13A and FIG. 13B shows an illustrative cross-section view and plan view respectively of the wiper in accordance with one embodiment of the present invention. The blade as shown in FIG. 13A and FIG. 13B has a thin blade protrusion throughout the length of the blade. FIG. 14A and FIG. 14B shows an illustrative cross-section view and plan view respectively of the wiper in accordance with one embodiment of the present invention. The blade as shown in FIG. 14A and FIG. 14B has brushes (toothbrush style) attached throughout the length of the blade. In this design, the blade has a plurality of holes 31 for accommodating suitable fibers to form a gentle or hard brush 30 . The brush can be made of material like those used on toothbrush or any suitable material. In one embodiment, the brush is made of nylon. Without wish to be bound by any specific theory or explanation, it is believed that the hydraulic cleaning and good turbulence effects result from the close proximity of the wipers to the surfaces of the electrode plates. In one preferred embodiment, the gap between the wiper and the surfaces of the electrode plates is 0.5 mm at maximum. [0088] Now referring to FIG. 15 , there is provided a schematic view of basis electrical connections in accordance with one embodiment of the present invention. The AC power supply is converted into adjustable 5 to 15 volts DC by a suitable DC power supply unit 32 for providing low voltage direct current electrical power to the electrolytic cells via the bus-bars. The wiper motor is also connected to the AC power supply. The necessary controls are not shown. [0089] Now referring to FIG. 1 and FIG. 16 , there is provided a brief description of a process of using the EC device for wastewater treatment in accordance with one embodiment of the present invention. The pre-treatment unit receives the contaminated water, allowing a pump to draw the liquid from the pre-treatment unit at the desired flow rate required by the EC device to function properly. After the wastewater is introduced into the sealed chamber of the EC device via the inlet 16 , the wastewater meanders through the electrolytic plates via the holes in the plates (as shown by the u-turn arrows) and is under the influence of the electromotive force from the electrical current supplied to the metallic electrolytic plates by the power supply. The wipers driven by the wiper motor will continuously clean the surfaces of the electrolytic plates, mix the ions thoroughly to enable efficient electrochemical reactions, and at the same time move the gases produced in the EC process to contact with the gelatinous precipitations so that the trapped gases within the precipitations will make the precipitations into floating flocculants, but not sludge when the wastewater exits the EC device. The treated wastewater exiting the reaction chamber flows directly into the post-treatment unit. The post-treatment unit is preferably to be dosed by small amount of suitable polymer to make the flocculants float faster so as to reduce cost in removable of the flocculants. The flocculants are also quite dry and required less efforts and cost in de-watering process. [0090] This invention may include a method further improving efficiency of the EC device. This method is to implement automatic dosing of one or more chemical compounds to adjust the pH and increase the ORP of some type wastewater in order to increase the treatment efficiency. A chemical compound such as poly aluminum chloride, ferrous sulfate and ferrite chloride can be added to the incoming wastewater at about 15 grams to one ton of wastewater. Other chemicals can be used provided they are not poisonous or give harmful residues in the processed water. It will also have the effect of reducing metal depletion of the electrodes. For processing of less polluted wastewater chemical dosing may not be required. [0091] Depending on the chemical nature of the wastewater it may be necessary to pre-treat the wastewater prior to its passing through the electrocoagulation process. Preferably, the pre-treatment processes involves removal of large sized suspended solids and adjusting the pH and/or ORP of the wastewater. [0092] This invention is the EC device with its associated DC power supply. For applications, it is built into a system that can consist of one or many (array) units connected in parallel in order to increase the processing flow/capacity. The system may consist of pumps, pre-treatment and post-treatment chemical dosing systems, automation control system and pipe-works. [0093] The amount of voltage and current required depends on the volume of wastewater to be processed, the type and concentration of contaminants, and the physical size of the EC device. [0094] While the foregoing has presented descriptions of certain preferred embodiments of the present invention, it is to be understood that these descriptions are presented by way of example only and are not intended to limit the scope of the present invention. It is expected that others skilled in the art will perceive variations which, while differing from the foregoing, do not depart from the spirit and scope of the invention as herein described and claimed.
The present invention provides an electrocoagulation device for drinking water and wastewater treatment by electro-coagulation and electro-catalytic precipitation principles. The invented device comprises a number of electrolysis cells formed by round-shaped electrode plates through which the raw water and waste water passes. A low DC voltage of 5 to 15 volts is applied to the cells. In addition, an electrode surface activator unit is provided to eliminate or minimize the passivation of the electrode plates. All types of impurities, including suspended solids, sub-micron particles, dissolved matters, dissolved minerals (including heavy metals and colloidal compounds), oil, grease, organic compounds and algae are converted to flocculants, water and carbon dioxide by the device. Micro-organisms and bacteria (pathogens) will be effectively killed at up to 99.99%. The invented device is capable of continuous operation.
2
BACKGROUND [0001] The present invention relates to conveyors and more particularly to an alignment system for use with conveyors to align conveyed product. [0002] In certain material handling industries, it is desirable to convey a procession of products on a conveyor system, stop flow of the procession and perform some operation on individual units in the procession. For example, in the concrete block manufacturing industry, blocks are typically conveyed in procession on a conveyor to a patterning station, where individual blocks are turned relative to other blocks in the procession. This is usually done to prepare a group of blocks in the procession for staggered stacking in multi-tiered shipping stacks. Typically, one or more blocks, also referred to as “groups,” are separated from the upstream procession of blocks for turning. [0003] A clamp, positioned at the end of a conveyor but upstream from the patterning station, is used to perform this separation. After a group of blocks to be turned passes the clamp, the clamp clamps against the next blocks in the procession. The passed group of blocks continues to the patterning station, where they are turned. After turning, the clamp releases the clamped blocks and the process is repeated. [0004] Frequently on conveyor systems, mis-aligned blocks jam in a clamp because they cannot be squarely clamped. The blocks become twisted or mis-aligned due to collision with other blocks or conveyor vibration. To un-jam the clamp, an operator must manually remove or re-orient the block in the clamp, resulting in production down time. Furthermore, efforts to reorient the blocks in the clamp are potentially dangerous. SUMMARY OF THE INVENTION [0005] The aforementioned problems are overcome in the present invention wherein a clamping guide is provided with a clamp and an alignment guide that are coupled to and actuated with each other. The clamp and alignment guide are configured so that as the clamp stops a conveyed procession of product, the alignment guide simultaneously aligns the procession upstream of the clamp. [0006] In the preferred embodiment, a pair of clamps are mounted across from one another on a conveyor that conveys a procession of blocks between the clamps. A drive ram extends and retracts the clamps against individual blocks on the conveyor to stop the upstream procession. A linkage couples each of the clamps to corresponding alignment guides positioned upstream from the clamps. The linkage is configured to actuate each of the guides with each of the clamps so that as the clamps extend to stop the procession, the guides align blocks upstream from the clamps. [0007] In a more preferred embodiment, the linkage couples the guides to the clamps so that as the clamps are retracted by the drive ram and fully withdrawn from the procession, the alignment guides remain closer to the procession than the clamps. Accordingly, the alignment guides protect edges of the clamps from the edges of passing blocks, thereby preventing corners of blocks snagging and twisting on the clamp edges. [0008] The present invention provides a simple and effective clamping guide to stop and simultaneously align a procession of product. The present invention preferably utilizes one drive system to extend and retract clamps and corresponding alignment guides, thereby eliminating the need for additional drive systems to operate each individually. Further, the retarded retraction of the alignment guides relative to the clamps allows the alignment guides to provide a secondary function of preventing clamp edges from snagging and turning passing product. [0009] These and other objects, advantages and features of the present invention will be more readily understood and appreciated by reference to the detailed description of the preferred embodiments and the drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0010] [0010]FIG. 1 is a perspective view showing the clamping guide of the present invention; [0011] [0011]FIG. 2 is a top plan view of the clamping guide; [0012] [0012]FIG. 3 is an enlarged top plan view of a linkage of the clamping guide in an extending position; [0013] [0013]FIG. 4 is an enlarged top plan view of the linkage in a retracting position; and [0014] [0014]FIG. 5 is a perspective view of the linkage. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0015] A clamping guide in accordance with a preferred embodiment of the present invention is shown in FIG. 1 and generally designated 10 . The clamping guide 10 generally includes a frame 12 , clamps 20 , alignment guides 30 , a linkage 40 , which couples the clamps 20 to corresponding alignment guides 30 , and actuators 50 for extending and retracting the clamps 20 toward and away from one another. By way of example, FIG. 1 also shows a power roller conveyor 100 , which is driven by a conventional roller conveyor drive 110 . The power roller conveyor 100 conveys a procession downstream in direction D through the clamping guide 10 . By way of further example, the clamping guide 10 is also shown upstream from patterning station 200 , which is shown in general detail. As will be appreciated, although a patterning station 200 is illustrated, the clamping guide 10 of the present invention is well suited for use with other product processing stations. In operation, the actuators 50 drive clamps 20 toward blocks in procession B until the clamps 20 clamp against one or more individual blocks. This prevents those clamped blocks from being conveyed or pushed downstream by upstream line pressure caused by blocks accumulating against the clamped blocks. As the clamps 20 are driven, the linkages 40 simultaneously actuate the alignment guides 30 to move toward the procession of blocks B with the corresponding clamps 20 . As the guides engage the procession of blocks B, the linkages allow the alignment guides to align blocks between the guides, thereby aligning the procession of blocks B immediately upstream from the clamps. Preferably, the guides 30 align, but do not clamp the blocks. [0016] Accordingly, when individual blocks in the procession B reach the clamping guide 20 , they are squarely aligned between the clamps so that they are not crushed by or mis-aligned within the clamps 20 . Preferably, when the clamps 20 are withdrawn by the actuator 50 , the corresponding alignment guides 30 are also withdrawn. When the clamps 20 are fully withdrawn, the alignment guides are positioned closer to procession B than the clamps 20 . In this configuration, the individual blocks in the procession B are unlikely to snag on edges of the clamps because the blocks are deflected from the clamps 20 by the alignment guides 30 . [0017] With reference to FIG. 1, the clamps 20 , clamping actuators 50 and alignment guides 30 are preferably mounted to frame 12 . The frame 12 generally includes base members 14 , which are connected to one another by transverse beams 15 located under the conveyor 100 and conveyor drive 110 . Alignment frame members 16 are mounted to the transverse beams 15 . Likewise, clamp frame members 18 are mounted to the transverse beams 15 near the clamps 20 . [0018] The configuration, size and location of the elements of the frame may vary from application to application depending on the desired configuration of the clamps 20 and clamping guides 30 . Power roller conveyor 100 and conveyor drive 110 also are mounted to the transverse beams. As will be appreciated, the clamping guides 10 of the present invention may be retrofitted over an existing conveyor system thereby eliminating the need for the conveyor 100 and associated drive 110 . Further, the power roller conveyor 100 may be substituted with a belt or other conventional conveyor system as the application requires. [0019] In the preferred embodiment shown in FIGS. 1 and 2, the clamps 20 are movable relative to the frame 12 . Preferably, the extender arms 25 are slidably interfit within the clamp slide members 19 . Similarly, the alignment guides 30 are moveable with respect to the frame 12 . More preferably, the alignment guides 30 are pivotally mounted with mounting pins 35 to the alignment guide slide members 17 . Optionally, the interfitting extender arm 25 and clamp slide members may be substituted with any conventional guiding system that allows the clamps 20 to move toward and away from the procession of blocks B, more preferably perpendicular to the procession's line of travel on the power conveyor 100 . [0020] The clamp slide members 19 are adjustably interfit within clamp frame members 18 . This configuration provides adjustability of the alignment guides to accommodate different sized product. A clamp width adjuster 70 is mounted to clamp frame members 18 . The adjuster 70 may be any screw, lasp, hook or other conventional mechanism capable of holding the clamp slide members 19 and clamp frame members 18 in fixed relation to one another, but when de-actuated, allow the clamps 20 to be moved closer to or away from the procession. [0021] The alignment slide members 17 may also be slidably interfit within alignment frame members 16 , and adjustable with actuation of alignment guide width adjusters 72 , which act on the same premise as the clamp width adjuster 70 explained above. [0022] The clamp actuators 50 are mounted in fixed relation to the frame 12 , preferably to the clamp frame members 18 . As illustrated, the clamp actuators are hydraulic cylinders 51 with rams 52 extendable and retractable therefrom in a conventional manner. As will be appreciated, the hydraulic cylinders may be replaced with any commercially available actuator system, such as a pneumatic drive, a gear drive, or other drive mechanism, capable of extending and retracting the clamps 20 . As the application requires, the actuator 50 may be controlled by a programmable logic control unit (not shown) to control the extension and retraction of the ram 52 and, therefore, movement of the clamps 20 . [0023] [0023]FIGS. 3 and 4 show the actuator 50 and clamps 20 in more detail. The yoke 53 of ram 52 is connected to the clamp 20 with drive arm 21 via yoke pin 59 . The clamp 20 is guided in its extension and retraction by interfitment of extender arm 25 in clamp slide member 19 . Each of the clamps 20 include a clamping plate 22 to which a wearing plate 23 is secured. The clamping plate 22 is preferably constructed of metal or synthetic material of high strength. The clamp wearing plate 23 preferably is constructed of a high density rubber or plastic material that is resistant to wear. The size and shape of the clamping plate 22 and clamp wearing plate 23 may vary depending on the block or product size. The clamp wearing plate 23 is secured to the clamping plate 22 with bolts, screws, tabs or other fasteners. In some applications, the clamp wearing plate 23 may be eliminated. [0024] As shown in FIGS. 1 and 3, the alignment guides 30 are generally rectangular plate elements constructed of metal or synthetic material of high strength. Preferably, a low-friction plate 32 is secured to the alignment guides 30 . This may be done with bolts, screws or other fasteners. The low-friction plate 32 is preferably of a high density polyethylene or other synthetic material. The low-friction plate 32 functions to reduce friction between the alignment guides and passing product, and/or facilitate alignment by allowing the product to easily shift into square between the guides 30 . As desired, the low-friction plate 32 may be absent. The alignment guides are generally guided toward one another in a consistent manner with the aid of the linkage 40 . Preferably, the guides 30 are pivotally mounted with mounting pin 35 to the alignment slide member 17 . As will be appreciated, other mechanisms for ensuring that the alignment guides 30 move toward each other in a consistent manner may be used. [0025] With particular reference to FIGS. 3 - 5 , the alignment guides 20 and clamping plate 22 are coupled together with linkage 40 , which generally includes clamp arm 24 , guide pin 26 , which interfits within journal 36 , and guide arm 34 . Preferably, the clamping plate 22 is mounted to clamp arm 24 , which is preferably mounted on the side of the clamping plate opposite the clamp wearing plate 23 . The clamp arm 24 may be secured to the clamping plate 22 by a weld or fasteners such as bolts or screws. Optionally, multiple clamp arms 24 may be secured to the clamping plate. Secured to the clamp arm 24 is guide pin 26 which may be a pin, bolt, shaft or other structure coupled to the clamp arm 24 . Although the cross section of guide pin 26 is shown annular, it may be elliptical, square or rectangular, or any other desired shape. [0026] With further reference to FIGS. 3 and 5, the guide arm 34 is secured to or integral with alignment guide 30 . Guide arm 34 includes journal 36 including opposing journal ends 36 a and 36 b . The journal 36 is preferably in the form of a slot, but may be any open channel or other guide mechanism that allows guide pin 26 to move relative to the guide arm 34 in certain positions and engage the guide arm 34 in other positions. Stabilizer arm 38 is secured to or integral with guide arm 34 . As will be appreciated, stabilizer arm 38 may be secured directly to the alignment guide 30 as well. The stabilizer arm 38 extends over the drive arm 21 . Preferably, friction block 39 is disposed between the stabilizer arm 38 and the drive arm 21 . The friction block is constructed of a low friction material to reduce abrasion and wear between the stabilizer arm 38 and the drive arm 21 . As will be appreciated, the friction block 39 may be secured to or integral with stabilizer arm 38 or the drive arm 21 as desired. [0027] With reference to FIGS. 3 - 5 , the clamping guide 10 may also include an adjuster 60 to fine-tune the spatial relationship between the alignment guides 30 , the clamping guides 20 , and their movement relative to procession B. As shown, the adjuster 60 includes bracket 64 to which set screw 62 is movably coupled. The bracket 64 is mounted in a stationary position relative to the alignment guides 30 , preferably to the clamping guide frame member 19 . The function of the set screw 62 is to adjust the positioning of the guide pin 26 within the guide journal 36 and, therefore, adjust the spatial relationship of the alignment guide 30 with respect to the clamp 20 . Locking nut 66 may be tightened against bracket 64 to prevent movement of the set screw 62 relative to the bracket 64 . Operation [0028] With reference to FIGS. 1, 3 and 4 , the operation of the clamping guide 10 will now be explained. As shown in FIG. 1, a procession of blocks B are conveyed by power conveyor 100 downstream in the direction of arrow A toward patterning conveyor 200 or any other block manipulating station as desired. To initiate stopping the procession of blocks B toward the downstream patterning station, the power conveyor 100 is shut down so that it no longer propels the procession of product B, however, downstream. Upstream line pressure from blocks accumulating in the procession B naturally urges the blocks on the power conveyor 100 downstream toward the patterning station 200 . [0029] To prevent the procession B from flowing downstream and affecting tasks performed on the patterning station 200 , and to align blocks in the procession B, the clamping guides 10 are activated. The clamps 20 , and consequently, the alignment guides 30 are driven inward, toward the product procession B, by the clamp actuators 50 . Clamps 20 clamp against block B 2 (or more blocks if more blocks are between the clamps), to prevent block B 2 from moving past the clamps 20 . Via the linkage 40 , the guides 30 are actuated simultaneously with the clamps 20 . The alignment guides push upstream mis-aligned blocks, for example, B 1 , into alignment so that the procession B generally includes aligned blocks. Preferably, the alignment guides 30 align, but do not clamp against the blocks. Specifically, if only the alignment guides 30 contacted blocks in procession B, the force in contact would not be sufficient to stop the procession B from progressing downstream due to upstream line pressure. Optionally, however, some alignment guides may actually clamp blocks in procession B. [0030] With reference to FIGS. 3 and 4, the interaction of the alignment guides 30 , linkage 40 and clamps 20 is shown in more detail. As clamp actuator 50 is actuated, ram 52 drives drive arm 21 , and subsequently clamp plate 20 , in an extending direction C toward and into contact with block B 2 . As clamp arm 24 moves with clamping plate 22 the guide pin 26 moves within the journal 36 . When the guide pin 26 contacts the journal end 36 a , this causes the alignment guide 30 to move inward in direction C toward block B 1 , which is upstream from block B 2 . [0031] Preferably, the guide pin 26 and guide arm 34 interact so that in a fully extended position as shown in FIG. 3, the clamp plate 22 clamps against the block B 2 whereas the alignment guide 30 and friction-reducing plate 32 align, but do not exert a force that prevents or restricts blocks therebetween from being pushed downstream due to upstream line pressure. More preferably, the effective pressure of the clamping guides against the blocks B 1 therebetween is enough to align but not clamp the blocks. Additionally, the set screws 62 may be used to establish the most retracted position of the alignment guides, as shown in FIG. 4. There, the set screw 62 abuts the alignment guide 30 so that it cannot be retracted farther than illustrated. [0032] After the alignment guides 30 have aligned the procession of product therebetween and/or the operations downstream from the clamping guide 10 are completed, the clamp actuator 50 retracts, thereby retracting the clamp plate 22 and alignment guide 30 toward a retracted position as shown in FIG. 4. As the clamp actuator 50 moves the clamp plate 22 in direction 0 , the guide pin 26 moves relative to the journal 36 until it engages journal end 36 b . At this point, the alignment guide 30 begins to move in direction O with the clamping plate 22 . With reference to FIG. 2, the alignment guide pivots about the mounting pin 35 so that the guides are at a slight angle with respect to the product procession D. With reference again to FIGS. 3 and 4, the stabilizer arm 38 slides relative to the drive arm 21 as the clamps 20 and alignment guides extend in direction C toward the procession of blocks or retract in direction O away from the procession. The interaction of the stabilizer arm and drive arm 21 holds the alignment guide 30 off the conveyor 100 . Additionally, the stabilizer arm 38 restricts or prevents the alignment guide 30 from excessively tilting or angling from the vertical and horizontal planes. [0033] Preferably, the guide pin 26 engages the journal end 36 b so that as the clamps 20 are retracted, the alignment guides 30 lag behind the clamps 20 some distance D. In the fully retracted position, the alignment guides are closer to the product procession a distance D. The set screw 62 may be used to establish this distance D by screwing it into or out from the bracket 64 . Accordingly, the alignment guides 30 shield edges of the clamps 20 from product. With this feature, individual blocks moving on the conveyor are less prone to snag on the edges 29 of the clamps 20 and misalign. [0034] After the procession of blocks has been stopped and the blocks upstream from the clamps align between the alignment guides 30 , the power conveyor 100 is re-power to move the next block or group of blocks to the patterning station. The process explained above is then repeated again to stop and align the next portion of the product procession. [0035] Although the preferred embodiment of the clamping guide includes pairs of opposing clamps and opposing alignment guides that move toward each other to clamp and align a portion of a procession of product, the clamping guide may alternatively include one clamp and one alignment guide on one side of the power conveyor 100 and a fixed plate or frame member (not shown) on the opposite side of the procession. The operation of this embodiment is identical to that of the preferred embodiment except that a portion of the procession of blocks is clamped and aligned against a fixed member rather than a second set of clamps and alignment guides. [0036] The above descriptions are those of the preferred embodiments of the invention. Various alterations and changes can be made without departing from the spirit and broader aspects of the invention as defined in the appended claims, which are to be interpreted in accordance with the principles of patent law including the doctrine of equivalents. Any references to claim elements in the singular, for example, using the articles “a,” “an,” “the,” or “said,” is not to be construed as limiting the element to the singular.
A clamping guide including clamps, a clamp actuator and alignment guides where the alignment guides are coupled to and actuated with the clamps. In the preferred embodiment, a pair of clamps and alignment guides are positioned on opposite sides of a power conveyor so that a procession of product, such as blocks, passes between the clamps and between the alignment guides. Each alignment guide is coupled to a corresponding clamp with a linkage. The linkage is configured so that as the clamps close against a portion of the procession on the conveyor, the alignment guides engage another portion of the procession upstream from the clamps to align product between the guides. In another preferred embodiment, the linkage couples the alignment guides to the clamps so that when the clamps are partially or fully withdrawn from the procession, the alignment guides are closer to the procession than the clamps, thereby preventing product from contacting and twisting on edges of the clamps.
1
RELATED U.S. APPLICATION This application is a continuation of U.S. patent application Ser. No. 13/405,495 filed Feb. 27, 2012, which claims the benefit of U.S. Provisional Application No. 61/466,588 filed Mar. 23, 2011. FIELD OF THE INVENTION The present invention relates to containers for storage of liquids, granular materials and the like, and methods and apparatuses for forming the same. More particularly, the container of the present invention is a single piece blow-molded plastic container formed in a multi-sided configuration with modified corner radii, utilizing a smaller volume of raw material to obtain volumes and strength equivalent to the prior art. DESCRIPTION OF THE RELATED ART Blow-molded plastic bottles are well known for use for holding a wide variety of liquids such as milk, water and juice. The same types of containers may be used for granular materials. Containers of this type are manufactured in a variety of sizes, conventionally formed of a variety of thermoplastic materials. Typical of these containers are those disclosed in U.S. Pat. No. 6,527,133, issued to McCollum et al.; U.S. Pat. No. 4,805,793, issued to Brandt et al.; and U.S. Pat. No. 6,237,792, issued to Skolnicki et al. Containers of this type are relatively thin-walled, and are generally square or rectangular in cross-section, feature a molded handle, and typically have a finished weight of over 60 grams. Such weight of material is essential to maintaining sufficient strength for the container to withstand the industrial filling process, in particular, the loads imposed for securement of a closure, such as a cap, lid or screw top to the spout on the top of the container. FIGS. 1A , 1 B, 1 C and 1 D show top, front, side and bottom views, respectively of blow-molded containers formed according to the prior art. The typical prior art container is depicted in FIGS. 1A-1D incorporates a top 102 , a bottom 104 and spout 120 . Top 102 and bottom 104 are interconnected by sidewalls 106 , and includes a handle 122 . In the prior art, a relatively acute transition occurs at the top corner 130 of the top 102 of the container, where the top 102 joins the lower circumference of the spout 120 . Then, when the top 102 joins the sidewall 106 , a second relative abrupt transition occurs at upper corner 124 , generating a comparatively sharp angle between the top 102 and the sidewall 106 . Transitioning to the bottom section of the prior art container, a first intermediate corner 126 creates a first transition between the sidewall 106 and the bottom 128 of the container. A bottom corner 128 completes the transition between the sidewall 106 and bottom 104 . The combination of the corner transitions at intermediate corner 126 and bottom 128 , coupled with the substantial distance between intermediate corners 126 and 128 demand a substantial distribution of material to the bottom section of the container to provide the necessary strength. The same problem is evident at the top of the container 102 , where the top 102 of the container joins the sidewall 106 at upper corner 124 . These multiple spaced apart transitions often result in excessively thin walls at the transitions, thereby weakening the container. More recently, containers have been created which incorporate ribs and other design features in the upper sidewalls of the container to increase mechanical strength, well at the same time decreasing the wall thickness of the finished container. By reducing the overall thickness of the container, substantial savings in materials cost can be realized. Newer containers utilizing these design methodologies have resulted in reductions in material required for each container, and corresponding reductions in material cost, of between five and seven percent. Such reductions in the typical production environment can result in substantial cost savings over time. The existing containers, however, suffer from important limitations. Particularly, as known in the prior art, the manufacture of thin-walled thermoplastic containers utilizing the blow-molding techniques can create unacceptably thin wall dimensions near the top and bottom of the containers, where the tops and bottoms of the containers join the side walls. Excessive thinning in these areas weakens the overall container and reduces its ability to withstand the forces typically imposed during the filling process. To insure that sufficient wall thickness remains in these vital sections, the current containers require a minimum of approximately fifty-eight to sixty grams in weight. A need exists, therefore, for a container design and method of manufacture, which permits more even distribution of thermoplastic material throughout the wall of the container, while allowing significant reductions in the amount of material required to produce the container. SUMMARY OF THE INVENTION In summary, a thin-walled container in accordance with the present invention is formed having sidewalls, a bottom, a top having a neck, a handle, and a spout. The container has eight sides, and a smoothly tapered radius between the spout and the sidewall. To form the container, specialized round tooling is utilized in the die and its associated mandrel to achieve more even distribution of the thermoplastic material during the molding process. The resulting container displays a more efficient distribution of the materials along the sidewalls, top and bottom of the container, typically at a weight of fifty-two grams or less. It is an object of the present invention, therefore, to provide a thin-walled container having an extremely light weight. Further, it is an object of the present invention to provide a thin-walled container having six or more sides and a specially radiused transition between the spout and sidewall of the container. It is another object of the present invention to position the handle of the container to improve venting of the interior of the container during the pouring process. It is another object of the present invention to provide a system for manufacturing the same volume of container as taught in the prior art, while maintaining the necessary structural integrity of the container to withstand the industrial filling process. It is a further object of the present invention to provide and improved container having the same volume and fitting in the same standard case as taught in the prior art. These, and other objects of the invention, will be apparent from the associated drawings and description. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A us a top view of a prior art container, constructed according to the methods of the prior art. FIG. 1B is a front view of a prior art container, constructed according to the methods of the prior art. FIG. 1C is a side view of a prior art container, constructed according to the methods of the prior art. FIG. 1D is a bottom view of a prior art container, constructed according to the methods of the prior art. FIG. 2A is a front view of a first embodiment of the present invention. FIG. 2B is a side view of a first embodiment of the present invention. FIG. 2C is a bottom view of a first embodiment of the present invention. FIG. 2D is an alternate bottom view of a current embodiment of the present invention. FIG. 2E is an additional bottom view of another variant of a current embodiment of the present invention. FIG. 3A is a front view of the present invention. FIG. 3B is a side view of another embodiment of the present invention. FIG. 3C is a top view of another embodiment of the present invention. FIG. 3D is a bottom view of another embodiment of the present invention. FIG. 4 is a diagram showing a die and mandrel according to an embodiment of the present invention. FIG. 5 is a diagram showing a parison and a mold according to an embodiment of the present invention. FIG. 6 is a top view of embodiments of the present invention held in a standard dairy crate. FIG. 7A is a top view of an embodiment of the present invention; FIG. 7B is a side view of an embodiment of the present invention; FIG. 7C is a side view of an embodiment of the present invention; DESCRIPTION OF THE PREFERRED EMBODIMENT The description which follows will be best appreciated by reference to the accompanying drawings. Although the invention is described in conjunction with the drawings, and a plurality of preferred embodiments is described, it will be appreciated that these descriptions are not intended to limit the invention to those embodiments. The invention includes a variety of alternatives, modifications and equivalents which may be included within the spirit and scope of the invention as defined by the appended claims. The invention will be better understood by a full appreciation of the process of manufacture typically used in the art. A conventional blow-molding machine includes a loading station where pelletized thermoplastic material, such as polyethylene, may be introduced into a hopper or feed bin. The hopper, in turn, feeds the pelletized or granular thermoplastic materials, which is at room temperature, to a heater/drive system. Such a system typically includes a screw drive provided with one or more heating mechanisms or elements which gradually raise the temperature of the thermoplastic material to approximately 365° F. Once the material has attained this temperature, the material liquefies and becomes taffy-like in its consistency. The material is then introduced into the mold through a die and mandrel combination, whereby the thermoplastic material is evenly distributed in the mold. The blob of thermoplastic material which forms as it is extruded through the gauged opening between the die and mandrel is called a parison. Once the parison is formed the mold is closed around the parison possibly imparting the general shape of the interior of the mold onto the parison. This aids in distributing the material of the parison evenly throughout the interior of the mold when the mold is pressurized. The mold is then pressurized via the blow pin thereby forcing the parison to expand throughout the interior of the walls of the mold, and imparting to the material the finished shape of a container. To facilitate the molding process, the mold walls are cooled to approximately 30° to 40° F., to restore the liquefied thermoplastic material to solid state. Once the part has formed, the mold is opened and the part is removed from the mold. Turning now to FIGS. 2A-2E , a first embodiment of a container formed according to the present invention is disclosed. Container 10 consists of a top section 12 , a bottom 14 and a plurality of sidewalls. Eight sidewalls alternate in dimension, four being long sidewalls 16 and four being short sidewalls 18 . The top section 12 is configured with a spout 20 having an opening 21 by which material may be introduced into the interior of the container 10 . The container is molded as a single piece, and includes a handle 22 which is hollow and permits liquid and air to pass inside it. Preferably, the handle is configured adjacent to a short sidewall 18 , so that when the container is held for pouring, the center of mass is concentrated along the axis which intersects both the handle and the opposing short sidewall of the container. In a first embodiment, the height of the container 10 is measured from the bottom of the container to the bottom of the spout is approximately 9.231 inches, for a container having a volume of approximately 234 cubic inches, essentially a one-gallon container. In this embodiment, a radius transition 24 is formed between the upper limit of the sidewalls 16 , 18 and spout 20 . Preferably, the radius R has a dimension of approximately three inches, thereby providing a smooth transition between the sidewalls 16 , 18 and spout 20 of the container 10 in comparison to the prior art. This area of transition may include one or more ribs 28 to provide additional strength to the container. The container 10 is blow-molded, and includes a single piece thin wall construction. The sidewalls, when viewed from above, form a generally octagonal configuration as seen in top or bottom plan views. The container 10 includes a bottom 14 which is interconnected to the sidewalls 16 and 18 and has a plurality of ribs 30 . In one example, the radius transition 24 in between the sidewalls 16 , 18 and the spout 20 has a radius of approximately 3″ and a transition section length of about 2.5″ in a container having an overall height of approximately 10″. A second embodiment of the invention as disclosed in FIGS. 3A and 3B , which does not include the ribs 30 but does include the same upper radius transition 24 . Containers of either configuration may be formed with one or more volume control inserts 32 molded into one or more sides of the container to adjust the total internal volume of the container 10 . Turning now to first embodiment of the invention as shown in FIGS. 2A-E , it will be appreciated that the top section 12 of the container 10 incorporates an upper radius transition of radius R between the bottom of the spout 20 and the top of sidewalls 16 and 18 . The absence of the sharp transitions between the bottom of the spout and the container top, and the top of the sidewall in the container top results in increased strength while allowing for even distribution of the thermoplastic material, eliminating the sharp transitions of the prior art. The inclusion of rib 28 imparts additional strength to this vital section of the container. Likewise, the intermediate corners 34 and bottom corners 36 are positioned closer than the corresponding transition corners in the prior art, resulting in a more even distribution of the thermoplastic material at those critical locations. As shown in FIGS. 2C-2E , a variety of methods may be adopted for placement of strengthening ribs 30 on the bottom of the container to impart a higher degree of rigidity, utilizing a thinner bottom wall section than required by the prior art. A variety of planiforms may be selected as depicted in FIGS. 2C-2E , each of which forms the desired function of imparting the necessary strength to the bottom of the container. FIGS. 3A-3D show a second embodiment of the invention, where the bottom 44 of the container 38 is provided with a plurality of impressions 40 , 42 which may facilitate stacking of containers 38 . FIGS. 3A , B, C and D show a first side view, a second side view, a top view and a bottom view, respectively of an embodiment of the invention showing impressions 40 , 42 cast into the bottom 44 of container 38 . It will be further appreciated that additional strength may be obtained by multiplying the number of sidewalls as shown in FIGS. 2C and 3C . In each of the embodiments therein depicted, it will be appreciated that the container has eight sidewalls. The utilization of multiple sidewalls decreases the angles between the sidewalls, and the gentler radiuses therein incorporated allows for more even distribution of the thermoplastic material during the molding process. Embodiments of this disclosure have sidewalls arranged as opposing pairs where the distance between pairs of sidewalls is arranged so that two pairs of sidewalls are separated by a first distance and a third pair of sidewalls are separated by a second distance. The ratio of the first distance to the second distance is between about 1:1 to about 1:1.10, with the preferred ratio equal to about 1:1.06. A further advantage of incorporation of the upper radius transition 24 is the improved pouring characteristics of the container. In a prior art, the sharp transitions between the top of the container and the spout and the upper part of the handle and the top of the container results in periodic difficulty in pouring from the container as liquid blocks movement of the contents of the container away from the handle, causing the contents of the container to pour in spurts, rather than in a continuous stream as air is admitted past the liquid. By utilization of the extended upper radius transition of the present invention, the contents of the container flow easily. In addition, the handle section is designed to be hollow and allow air to escape during poring due to its proximity to the spout to thereby mitigate splashing as liquid is poured from the container. It is also noted that the curved nature of the upper radius transition between the sidewalls and the spout permits the handle to be attached higher on the container proximate to the spout and have a smaller hole between the handle and the container, thereby improving the pouring characteristics as mentioned above and permitting the container to contain a greater volume of material. Improved characteristics of containers produced according to embodiments of this invention are due at least in part to improvements to the equipment used to produce the containers, in particular the die and mandrel combination and the shape and size of the mold. FIG. 4 shows a cross-sectional view of an extrusion mechanism 50 according to an embodiment of this invention. This extrusion mechanism 50 operates as part of a blow molding machine, where the extrusion mechanism 50 positions a circular mandrel 54 having an air passage 56 in a circular die 60 so that a predetermined die gap 66 exists between the mandrel 54 and the die 60 a predetermined die angle 64 . Thermoplastic material is forced into the extrusion mechanism 50 in the direction indicated by arrow “A”, flows around the mandrel 54 and through the die gap 66 to form a parison. A parison is typically a hollow tube or bulb of semi-molten material which extends past the mandrel into the volume which will be the cavity of the mold. Once the desired parison is created, the mold (not shown) closes around the parison so that air can be introduced into the air passage 56 to inflate the parison to fill the enclosing mold. The size and shape of the die angle 64 and die gap 66 with respect to the mandrel 54 can determine the exact proportions of the parison. In this case the die 60 and mandrel 54 are both circular. The first parameter is the die angle 64 which measures the angle of the die 60 with respect to the mandrel 54 . Die angles 64 can range from 0° to 30° or more particularly about 15°-18°. Using a die angle 64 of less than 30° allows the die gap 66 to be smaller. In the case of one gallon containers, a die gap 66 of between about 0.001″ and about 0.025″ or more particularly about 0.006″ produces a parison with the desired shape and size when the appropriate amount of material is forced through the die/mandrel combination. In addition to the shape due to the die angle 64 and die gap 66 , as shown in FIG. 5 , a parison can change shape when the mold is closed. FIG. 5 shows a cross-sectional view of a parison 70 with a hollow core 72 inside a mold cavity 74 formed by the two parts of a two-part mold 76 , 78 according to an embodiment of this invention. The parison 70 has elongated and formed an elliptical shape following closure of the mold halves 76 , 78 . Embodiments of this invention use the elliptical shape of the parison 70 in combination with improved design of the mold cavity 74 to improve the quality of the finished container. By forming a container with an elongated or diamond shape, shown in FIG. 5 , the walls of the mold 88 can be kept at a substantially small similar distance from the parison 70 . Replacing corners with short sidewall sections 80 , 82 , 84 and 86 and shaping the mold to mirror the shape of the parison improves the structural rigidity of the resulting blow molded container while maintaining overall container strength using less material. In addition, this design helps to avoid dented corners as the resulting container is used, thereby enhancing its appearance. The elongated parison 70 fits the mold cavity 74 more closely than a mold cavity having four symmetric sides. Shaping the interior of the mold to form an elongated shape similar to the parison 70 , where the distance from the parison to the mold wall 88 is substantially equal causes the parison 70 to mold to the interior shape of the mold when the interior of the parison is pressurized. Having the interior of the mold closely mirror the elongate shape of the parison will provide the strongest container for the least amount of material by distributing the material evenly and thereby providing uniform wall thickness. Typical gallon containers manufactured by blow molding can use a minimum of 58 grams of thermoplastic material to form successfully, with 61-64 grams being typical in manufacturing operations. Embodiments of this invention can manufacture gallon containers with desirable strength and appearance using less than about 55 grams of thermoplastic materials, or more preferably less than about 52 grams of thermoplastic material. FIG. 6 shows a top view of embodiments of this invention held in a standard dairy crate. Dairy crates are cases constructed to hold multiple containers so that dairy crates with full containers may be stacked without damage to the containers or contents. Dairy crates are manufactured in standard configurations and it is an advantage of embodiments of this invention that these embodiments fit in a standard dairy crate. As shown in FIG. 6 , a standard 4-gallon dairy crate 51 holds four 1-gallon containers 52 made in accordance with embodiments of this invention. FIG. 7A shows a top view an embodiment of this invention with the 6″×6″ footprint of the container indicated. FIGS. 7B and 7C show side views of an embodiment of this invention showing how the container can fit in a space with height 10.040″. As can be seen from FIGS. 7A , 7 B and 7 C, containers constructed according to disclosed embodiments can fit in a 6″×6″×10.040″ cube. Fill percentage is the percentage of the volume of a minimal enclosing cube that is contained within the container. Disclosed embodiments have a fill percentage greater than about 60%. More particularly, containers constructed according to disclosed embodiments fill about 64.7% of the 6″×6″×10.040″ cube required to hold a container. Disclosed embodiments provide a fill percentage in excess of 60%, which permits more material to be stored in containers in a given volume while maintaining ease of use features such as handle placement. The above-described embodiments have been described in order to allow easy understanding of the present invention and do not limit the present invention. On the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims, which scope is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structure as is permitted under the law.
An improved lightweight container incorporates a thinner wall structure in an essentially octagonal container having a bottom member, a plurality of sidewalls, a spout, an upwardly converging neck member coupling the sidewalls of the spout, a handle molded into the container and a radiused transiting section between the sidewalls and the spout which eliminates weakened corner sections and improves overall strength to weight ratios.
1
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] This invention relates to the separation of digestible carbohydrate components from the indigestible carbohydrate components of oat, barley, or combinations of grain products and also relates to conversion of these components to cereal hydrocolloidal soluble fiber and protein-enhanced compositions that are useful as texturizers and nutrients for improving the health benefits of foods. [0003] Cereal grains contain large quantities of digestible starch along with proteins, lipids, ash, and indigestible components. The indigestible components are called dietary fibers that are the soluble and insoluble components of cell walls. They are resistant to endogenous digestion in the human upper digestive tract [ Am. J. Clin. Nutr., 25: 464-465 (1972)]. Such fibers consist primarily of cellulose, hemicellulose, pectin substances, oligosaccharides, lignin, gums and mucilages and have been an important food component since early times. Diets containing significant amounts of dietary fiber are known to assist in the digestive process and contribute to improved health. Burkitt et al. [ Lancet, 2: 1408-1411 (1972)] teach that dietary fiber has a role in the prevention of certain large-intestine diseases, including cancer of the colon and diverticulitis. Burkitt et al. also indicate that serum cholesterol rises when dietary fiber is removed froth the diet, and that eating a fiber-rich diet lowers serum cholesterol. Trowell [ Am. J. Clin. Nutr., 25: 464-465 (1972)] and Dreher [Handbook of Dietary Fiber, An Applied Approach, Marcel Dekker, Inc., New York, N.Y. (1987)] have reported on similar conclusions regarding the relationship between fiber and health benefits. [0004] It is now known that soluble and Insoluble fibers provide different health benefits. For example, wheat bran is very rich in insoluble crude fiber (mainly cellulose and hemicelluloses) and is excellent for decreasing the transit time of food through the digestive tract [Anderson et al., Am. J. Clin. Nutr., 32: 346-363 (1979)]. Some soluble fibers, especially β-glucan, are reported to reduce total plasma cholesterol [Behall et al., J. Am. Coll. Nutr. 16: 46-51 (1997)]. [0005] Diet has been recognized as a major factor in diabetes mellitus treatment since the discovery of insulin. Over many years, the calorie contributing components in the diet have shifted among the portions of digestible carbohydrates, proteins, and fat. Early recommendations were to limit dietary digestible carbohydrates. These low-carbohydrate diets with high-fat, mainly saturated fats, were associated with dyslipidemias and cardiovascular disease. More recently, the American Diabetes Association (ADA) recommended a diet in which protein contributes 10% to 20% of the total calories. The ADA recommends that saturated fat should contribute less than 10% of total calories, and polyunsaturated fat contributing no more than 10% of total calories, with the remainder of fat calories coming from monounsaturated fat. Fiber intake is recommended to be approximately 20 to 35 g/day. [0006] There is a need in the art for a dietary fiber food ingredient with decreased carbohydrate (particularly starch) digestible components that is functionally useful in foods and acts to delay the absorption curve of digestible carbohydrates after a meal. The ingredient should be capable of being easily incorporated into food products without interfering with taste and texture. The functional properties of the ingredient should have about the same rheological qualities as the original starting material with its higher starch component. It is also important in the art to provide nutrients for several health benefits including heart diseases and diabetes Type 2. [0007] 2. Description of the Prior Art [0008] Dietary fiber typically consists of morphologically intact cellular tissues of various seed brans, hulls, and other agricultural by-products that have a high content of crude fiber [Dintzis et al., Cereal Chem., 56:123-127 (1979)]. When added to foods, these fibers impart a gritty texture to the final product. One solution to this problem has been to grind the fibers to give finer powders, but these powders still lack smooth hydrocolloidal character. Also, the alkaline or alkaline/peroxide treatment of agricultural byproducts as reported by Gould (U.S. Pat. Nos. 4,649,113 and 4,806,475), Gould et al. (U.S. Pat. No. 4,774,098), Ramaswamy (U.S. Pat. No. 5,023,103); and Antrim (U.S. Pat. No. 4,038,481) does not remove the crude fiber components but completely eliminates the soluble fiber components. Morley et al. (U.S. Pat. No. 4,565,702) and Sharma (U.S. Pat. No. 4,619,831) teach enrobing the high crude fiber insoluble dietary fibers with soluble fibers (gums) for providing better texture and mouth feel. [0009] Soluble fibers are water-soluble polysaccharides such as pectin-like fruit and beet by-products (Thibault et al., U.S. Pat. No. 5,275,834). There have been a number of reports of alkaline extraction of agricultural materials, including hulls and brans, for obtaining their soluble hemicellulose components (Wolf, U.S. Pat. No. 2,709,699; Rutenberg et al., U.S. Pat. No. 2,801,955; and Gerrish et al., U.S. Pat. No. 3,879,373). [0010] Gould et al., U.S. Pat. No. 4,497,840, describe foods made from oat bran which contains at least 150% more crude fiber than whole oat flour. Also, Murtaugh et al., U.S. Pat. No. 4,908,223, show grinding oat bran and rice products to make frozen desserts without any separation of crude fiber components. Rudel, U.S. Pat. No. 4,961,937, also used non-separated oat products in baked products. [0011] The oat soluble fiber, also called oat gum or β-glucan, of the oat groat was fractionated as a separate component by an extensive series of separation described by Hohner and Hyldon, U.S. Pat. No. 4,028,468. Another wet-milling of oats to give various fractions including oat proteins was described by Cluskey et al. [ Cereal Chem., 50:475(1973)]. Also β-glucan enriched cellulose-containing fiber with little starch was described by Lehtomaki et al., U.S. Pat. No. 5,183,677. Oat β-glucan was water-extracted from oat groat in U.S. Pat. No. 5,512,287 by Wang et al. Also, barley β-glucan was purified by an alkaline extraction procedure of Bhatty (U.S. Pat. No. 5,518,710). [0012] U.S. Pat. No. 4,028,468 to Hohner et al. (1977) outlines a method to extract β-glucan from oat groat. Groats are hulled, usually crushed grain, especially oats. According to Hohner et al., oat groat is flaked, the oil extracted, dried, ground and air classified to produce a coarse milling fraction. The extraction of β-glucan includes mixing the coarse fraction with water, adjusting the pH twice, chilling the water extract to 4° C., and drying recovered β-glucan in a vacuum dryer. The multiple pH adjustments, the use of oil extraction, air classification and vacuum drying are expensive processing steps which make the invention economically disadvantageous from a commercial production point of view. High purity β-glucan fractions, (over 50 percent pure β-glucan) were not reported using this technique. [0013] U.S. Pat. Nos. 4,804,545 (1989) and 5,013,561 (1991), both to Goering et al., outline a method for extracting β-glucan from waxy barley grain. Waxy barley grain is ground and mixed with water, centrifuged to remove bran and starch, boiled to destroy the activity of β-glucanase, centrifuged to remove the coagulated protein which contains a high percentage of oil, and the extract passed through an ultrafilter to purify the β-glucan. The β-glucan solids are dried on a drum dryer or a spray dryer. Recovering the solids using this technique with a drum dryer or a spray dryer produces alight yellowish-brown-colored product with a purity of β-glucan less than 50 percent by weight of the product. These two inventions produce β-glucan products with undesirable β-glucan purity and low molecular weights. [0014] U.S. Pat. Nos. 5,106,640 (1992) and 5,183,677 (1993) both to Lehtomaki et al., describe a method for producing a β-glucan-enriched alimentary fiber from oats and barley. Barley or oat grains are dehulled, optionally ground and slurried in water at about 8° C. with ethanol addition. The slurry is screened and a product is collected. The product contains 15-40 percent β-glucan and about equal amounts of starch and protein. This invention does not produce a β-glucan product having a purity of more than 50 percent by weight of the product. [0015] U.S. Pat. No. 5,512,287 by Wang et al. teaches a method of recovering β-glucan as a white-colored powder containing about 75 percent of the naturally occurring β-glucan in cereal grains with molecular weights of the β-glucan ranging between 400,000 daltons to 2,000,000 daltons. [0016] Potter et al. (U.S. Pat. No. 6,485,945) found that an all aqueous system using ultrafiltration gave solids with high soluble β-glucan contents. Also, when an aqueous solution was heated in an open vessel such as tray evaporator, a thin, solid film, or “skin”, spontaneously formed on the surface of the liquid that was predominantly β-glucan and separated out from a very dilute β-glucan solution. [0017] Previous processes for concentrating soluble β-glucan from cereals such as oats or barley, have been considered to be impractical for application to commercial manufacturing processes becauie of high cost of processing the high-viscosity, low-concentrations of oat or barley grain solids in aqueous solution. The reliance upon a water-miscible solvent, such as ethanol or isopropanol, to precipitate soluble β-glucan from aqueous solutions by these solvents, entails high in-process losses and difficult reclamation. The low solid contents of the aqueous solutions require huge amounts of solvent for precipitation. If the solids concentration could be elevated, considerable saving could be made. [0018] Inglett (U.S. Pat. No. 4,996,063) teaches that water-soluble dietary fiber compositions are prepared by treatment of milled oat products with α-amylase and removal of insoluble components by centrifugation. In a related development, Inglett (U.S. Pat. No. 5,082,673) teaches that a soluble dietary fiber and maltodextrin-containing product is prepared by hydrolyzing a cereal flour or a blend of cereal flour and starch with an α-amylase. This soluble, fiber composition has been described for use in ready-to-eat cereal (Smith and Meschewski, U.S. Pat. No. 5,275,831) and low fat comminuted meat products (Jenkins and Wild, U.S. Pat. Nos. 5,294,457 and 5,585,131). [0019] Also, U.S. Pat. No. 6,060,519 by Inglett discovered a novel class of hydrocolloidal compositions recovered from the liquid fraction obtained by subjecting oat or barley substrates to a heat-shearing treatment. These compositions contain soluble fiber, principally β-glucan, and are substantially free of insoluble fiber particles. The hydrocolloidal products are smooth in texture and display the properties of a dairy cream, coconut cream, or fat imitation on rehydration. They are recovered in about 70-95% yields. [0020] Cahill et al. (U.S. Pat. No. 6,531,178) found that high levels of β-glucan from oat or barley grains could be extracted from an aqueous solution using various pH adjustments at around 6% oat slurry in order to carryout the extraction procedure at temperatures below the gelatinization of starch. Their soluble β-glucan products could be agglomerated for use in foods, and have approximately 50% available carbohydrate content. [0021] Malkki and Myllymaki (U.S. Pat. No 5,846,590) found that trypsin in a mild treatment of oat products with a proteolytic enzyme leads to an elevation of viscosity of β-glucan of certain varieties. This effect was accentuated by subsequent thermal, solvent and mechanical treatments that resulted in an enrichment of dietary fibers. SUMMARY OF THE INVENTION [0022] I have now invented a novel class of low-carbohydrate digestible hydrocolloidal compositions by separating them from an aqueous slurry of a cereal substrate, preferably oat and/or barley grain, without pH modifications. These all-natural compositions are low in digestible carbohydrates, principally starches, and rich in soluble fiber, principally β-glucan. They are also rich in proteins. The hydrocolloidal products are recovered in high yields, are smooth in texture, and are characterized by properties suitable for texturizing food, especially bakery products. These hydrocolloidal products can also be used as food ingredients for increasing the nutritional level of foods and supplements. [0023] In accordance with this discovery, it is an object of the invention to provide hydrocolloids that are smooth in texture, low in starchy carbohydrates, and rich in β-glucans and proteins with sensory properties that render them suitable for a wide-range of food applications. [0024] It is also an object of the invention to provide a method for isolating the aforementioned hydrocolloids from cereal substrates, especially from oat and barley. [0025] Another object of the invention is to provide a hydrocolloidal composition having a low carbohydrate content and a relatively high β-glucan content without the addition of chemicals to change the pH function. [0026] A further object of the invention is to decrease the digestible carbohydrate content of a food product while increasing its soluble β-glucan content without the use of unnatural additives in the processing operation. [0027] Still another object of the invention is to extend the visco-elastic properties of the subject hydrocolloids by demonstrating their unexpected thickening effects despite their decreased digestible carbohydrate contents. [0028] Yet another object of the invention is to yield hydrocolloids having an unexpectedly bland taste and other favorable sensory properties and to impart these properties to co-processed compositions with other food products. [0029] Other objects and advantages of the invention will become readily apparent from the ensuing description. BRIEF DESCRIPTION OF THE DRAWINGS [0030] FIG. 1 is a flow diagram depicting the steps of the process of the invention. [0031] FIG. 2 is a graph depicting a series of Rapid Visco-Analyzer (RVA) curves for three products of the invention described in Examples 4A, 4B and 4C in comparison with an oat bran starting material and with a material produced by a prior art method (Nutrim OB, U.S. Pat. No. 6,060,519). The curves show the change in viscosity as temperature is changed over a period of time. DETAILED DESCRIPTION OF THE INVENTION [0032] Any cereal grain with a soluble fiber component therein may be used as a starting material in the present invention. Cereal grains, including wheat, rice, rye, corn, sorghum and millet, have a relatively low concentration of β-glucan. Oats and barley are preferred because of their higher levels of naturally-occurring soluble fiber component. Oat grain has about 4% soluble fiber, β-glucan, on a dry weight basis (dwb), while the β-glucan content of barley grain can vary from about 5 to 15%, dwb. [0033] Any processed grain product may likewise be utilized as a starting material in the present invention including cereal flour, cereal flakes, cereal bran, defatted grain, and mixtures of grains including grain flour or grain fractions. Methods for grinding oat groat to separate the bran layers from the endosperm giving whole oat flour and oat bran flour are commonly known in the art. Oat bran flour, for example, may contain up to 12% β-glucan, dwb. [0034] As shown in FIG. 1 , the extraction process of the present invention begins by forming a first aqueous slurry of grain material at a concentration of about 5 to 30% by weight. A critical element of the process of the invention is in providing adequate physical disruptive forces to the cereal-based substrate in order to break down the cellular structures of the substrate. Accordingly, the cereal-based substrate slurry is subjected to shear forces in an initial treatment sufficient to yield a flowable liquid slurry (second slurry) capable of being separated into a liquid fraction and a fiber (bran)-containing solid fraction. It is desirable to conduct the initial shear treatment at temperatures in the range of about 20-60° C., and preferably in the range of about 30-50° C., more preferably at a temperature of approximately 50° C. The requisite time period of treatment will, of course, vary with the starting substrate, the nature of the shear apparatus, and other conditions of treatment; but the period will typically be on the order of about 1-120 minutes, and more typically 30-120 minutes. It is preferred to have an initial viscosity of the first slurry of less than 20 poise (P) at temperatures in the range of 20-60° C. in order to pump the liquid continuously through shear devices necessary for cellular disruptions throughout the treatment and recovery process. Typically, the pH of the slurry is between 6 and 7, and does not require adjustment. [0035] The forces for mechanically shearing the cereal-based substrate in the initial treatment are provided by a variety of shearing devices, such as dispersator, colloid mill, Waring™ blender, extruder, homogenizer, shear pump or the like. Exemplary of these is a Bostonshear three stage pump. [0036] The insoluble fiber solids are separated in a first liquid-solid separation step by any means as known in the art, such as on rapidly vibrating sieves or centrifugal sieves with openings between 80 to 500 mesh sieve (210-25 microns; 0.21-0.025 mm); with an opening size of 100 mesh being preferred. Suitable for use herein is a Kek-Gardner centrifugal sifter. Both the fiber-containing solids fraction and the liquid fraction are recovered from the first separation step. The collected fiber solids are reserved for recombining with the liquid fraction obtained from the second liquid-solid separation step, as described, below. [0037] The liquid fraction from the first liquid-solid separation step is enriched in starch as compared to the sheared slurry. This liquid is then subjected to a second liquid-solid separation, such as centrifugation or decantation, to remove any remaining solids. These solids are predominantly starch. If a centrifuge is used, the most suitable centrifugation forces (RCF) are between about 50 and 15,000×g. The starch-depleted liquid fraction from the second liquid-solid separation step is then recombined with the saved fiber solids obtained from the first liquid-solid separation to yield a third slurry. [0038] The third slurry is then subjected to heat and shear in a cooking step. A preliminary stage of this step may consist of circulating the slurry through a shear pump at elevated temperatures, such as 38-93° C. (100-200° F.). The substantive shear-cook stage is optimally provided by a continuous steam jet cooker, particularly excess steam jet-cooker [see R. E. Klem and D. A. Brogley, Pulp & Paper, Vol. 55, pages 98-103 (May 1981)] over a period of 5 to 30 min. As previously mentioned, the viscosity of the resultant cooked cereal slurry should be maintained at less than 20 Poises in order to have the requisite flowability through the cooker and for subsequent processing. [0039] Although jet cooking conditions may be varied by one skilled in the art according to the particular cereal substrate being processed, preferred cooking conditions for these compositions are in the range of about 120-150° C. with a steam pressure of at least 1.4 bar (20 psig) within the cooker and a pumping rate of about 0.75-2.0 l/min. Typical conditions are 130-140° C. with a steam pressure of at least 5.2 bar (75 psig) and a pumping rate of 1.1 l/min. Line pressure steam entering the cooker to achieve such conditions would be 5.5-6.9 bar (80-100 psig). Thus the excess steam flowing through the cooker, over and above that needed to maintain the desired cook temperature, should be at least about 1 bar :(15 psig), and preferably in the range of 1.7 bar (25-30 psig). Under these conditions, sufficient turbulence is provided in the cooker to substantially disrupt the remaining solids and to release the β-glucan into the slurry. The high steam pressure used during the cooking process is suddenly released as the cooked dispersion exits the jet cooker. This instantaneous pressure release further promotes the physical disruption and/or molecular degradation of the fibrous material. At the time of the pressure release, the temperature of the cooked slurry (fourth slurry) rapidly drops to 100° C. (212° F.) or lower. [0040] After heating and shearing, β-glucan-containing products of the invention are recovered from the cooked slurry (fourth slurry). For example, the cooked slurry may be subjected to a third liquid-solid separation, such as by centrifugation filtration or on vibrating sieves having openings in the range of 210-25 microns. The crude fiber particle solids removed by this separation step are characterized by a β-glucan content of approximately 6-8%, dwb, and for purposes of the invention are considered to be a by-product. The flowable liquid fraction from the third separation step is subjected to further recovery steps to yield the hydrocolloidal product of the invention. For example, the liquid fraction may be dried by conventional methods, including drum drying, spray drying, freeze drying, hot-air, and the like. In a commercial operation, drum drying would be considered a preferred embodiment. Alternatively, the liquid from the third separation may be passed through a centrifuge to remove suspended solids. The remaining liquid fraction is then either dried directly as described above, or is subjected to further processing, such as alcohol precipitation and a final centrifugation prior to drying. Drum-drying the liquid obtained directly from the third separation step will yield a product having at least about 20% β-glucan, dwb. Drum-drying the liquid obtained directly from centrifugation of liquid from the third separation step will yield a product having at least aboUt 30% β-glucan, dwb. A dried product obtained from alcohol precipitation of the centrifugation liquid will have a β-glucan content of at least about 40-50%, dwb. Alcohol precipitation of the liquid from the third separation without centrifugation will yield a product having a β-glucan content of 35-40%, dwb. The products of the invention are readily dispersible in water to give a high viscosity creamy fluid. [0041] The products of the invention are hydrocolloids that have “thermo-shear-thinning” properties. These properties are evident in aqueous dispersions of the hydrocolloids, which are characterized, for example, by viscosities that are substantially higher than those manifest by the products taught by Inglett et al., U.S. Pat. No. 6,060,519. As shown in FIG. 2 , the hydrocolloids of the invention display pasting properties that are considerably distinct as compared to those for the product (Nutrim OB) described in U.S. Pat. No. 6,060,519, supra, and as compared to the oat bran starting material. The Rapid Visco-Analyzer (RVA) curves of FIG. 2 show viscosities for the hydrocolloids of the invention that are significantly higher than for Nutrim OB and the oat bran starting material, particularly in the 200- to 450-second region and also in the 1200- to 1800-second region. The 200- to 450-second region is within the initial RVA heating cycle, that is, during that part of the heating cycle before which the maximum heating temperature is attained and the subsequent cooling (or gelling) cycle begins. In a standard RVA analysis, the hydrocolloid is made up as an 8% w/w aqueous suspension and is then heated at a uniform rate from an initial equilibrated temperature (e.g. 30° C.) to a preselected maximum temperature, usually exceeding 90° C. After holding the paste for a period of time at the maximum temperature, the temperature is gradually decreased at a uniform rate to some predetermined plateau (e.g. 50° C.) This cooling period is referred to as the gelling cycle. The hydrocolloids of the invention having at least about 20% β-glucan, dwb, are characterized by a viscosity greater than 1000 centipoises when initially heated to 40° C., and perhaps greater than, 1500, 2000, or even 2500 centipoises. Generally, the higher the β-glucan content, the higher the viscosity. Hydrocolloids having 50% β-glucan, dwb, are characterized by viscosities of approximately 4000 centipoises at 40° C. when initially heated. The aforementioned viscosity values correspond to approximately 4 minutes in the initial heating cycle in the RVA program shown in FIG. 2 . [0042] The hydrocolloids of the invention are also unique in terms of having a ratio of digestible starch to β-glucan soluble fiber of 2.0 or less, and typically in the range of 0.1-2.0. For instance, Table 1 lists the ratios of digestible starch to β-glucan of the subject hydrocolloids in comparison with the starch to β-glucan ratios of oat bran starting material and the Nutrim-OB product described in U.S. Pat. No. 6,060,519. The digestible carbohydrate content for the values given in the table was measured by standard methods for total starch analysis (AACC Method 76-13). The β-glucan contents were measured by a standard procedure (AACC Method 32-23). [0043] The smooth textured hydrocolloids of the invention are suitable as ingredients in preparing low carbohydrate and low fat foods without imparting undesirable cotton-like or dry mouthfeel, or a sandy, bulky, chalky, or gritty texture characteristic of most dietary fiber materials. The hydrocolloids of the invention can be used as ingredients in a variety of food products, particularly in baked goods and desserts. They are especially suitable in baked goods as replacements of a portion of the fat and/or replacement of a portion of the flour. Such replacements result in an elevation in the food of the soluble fiber, β-glucan, with acceptable textural qualities, including moistness. The hydrocolloids of the invention are also useful as nutritional supplements in nutrition bars, weight loss bars, beverages, smoothies, soups, pancake mixes and the like. The level of incorporation of the hydrocolloid into a food composition may be within the range of 0.1-99%, by weight. It is further envisioned that the products of the invention can be prepared in essentially pure form as recovered from any of the aforementioned processes for administration as a oral supplement, such as in capsular form, or as a powder or granule for sprinkling over a food product at the time of consumption. [0044] The following examples are presented only to further illustrate the invention and are not intended to limit the scope of the invention which is defined by the claims. [0045] All references disclosed herein or relied upon in whole or in part in the description of the invention are incorporated by reference. EXAMPLE 1 [0046] Oat Bran (OBC), 100 lb (45 kg; Quaker Oats Company, Chicago, Ill., Lot No. 26629; MAR132003) was mixed with 1900 lb (862 kg) of water [8.345 lb/gal or 228 gallons] and heated to 105° F. (41° C.) in a mixing tank and circulated with a Bostonshear pump with a three stage head for 1 hour. The solids were removed using a Kek-Gardner centrifugal sifter with a 200 mesh sieve. After collecting 100 gals (379 L) of liquid, another 75 gals (284 L) were added to the mixing tank and the circulation continued passing the slurry through the 200 mesh sieve until 150 gal (568 L) of sieve liquid was obtained. The liquid from the sieve (DD2-SL-1) was centrifuged to separate the solid carbohydrate particles. The centrifuge liquid (DD2-SL-CL1) was mixed with the separated wet sieve solids (DD2-SS-1) from the Kek-Gardner centrifugal sifter separation procedure. The slurry was heated to 180° F. (82° C.) and circulated with a Bostonshear pump for 30 min before the slurry was jet cooked at 270° F. (132° C.) and 5.4 bar (78 psig). The jet cooked slurry was circulated through a Kek-Gardner centrifugal sifter with a 100 mesh sieve to remove the insoluble solids. The liquid from the Kek-Gardner was drum dried to give a cream-colored solid Invention Product (DD2-PP1-JC-SL-DD) having a β-glucan content of 20% dwb, a digestible carbohydrate content of 29% dwb, and a starch: β-glucan ratio of 1.40. EXAMPLE 2 [0047] Oat Bran (OBC), 100 lb (45 kg; Quaker Oats Company, Chicago, Ill., Lot No. 26629; JUNE262003) was mixed with 1900 lb (862 kg) of water [8.345 lb/gal or 228 gallons] and heated to 108° F. (42° C.) in a mixing tank and circulated with a Bostonshear pump with a three stage head for 1 hour. The solids were separated using a Kek-Gardner centrifugal sifter with a 200 mesh sieve over the course of about an hour. The resultant wet sieve solids (DD3-SS-1) were saved for the step, below. The liquid (DD3-SL-1) from the Kek-Gardner centrifugal sifter was centrifuged with a Westfalia clarifier to separate out the solid particles that had passed through the sieve (DD3-SL-1-CS-1), and the solid particles were discarded. The centrifuge liquid (DD3-SL-CL1) was mixed with the wet solids (DD3-SS-1) from the Kek-Gardner centrifugal sifter separation. The slurry was heated to approximately 200° F. (93° C.) while being circulated through a Bostonshear pump for 60 min. The cooked slurry was jet-cooked at a steam pressure of 5.4 bar (78 psig) to maintain a temperature of 270° F. (132° C.). The hot liquid from the jet cooker was circulated through a Kek-Gardner centrifugal sifter with a 100 mesh sieve (to remove the insoluble materials, DD3-PP3-JC-SS) to give a milky liquid (DD3-PP3-JC-SL). A portion of this liquid was drum dried to give Invention Product (DD3-PP3-JC-SL-DD) having a β-glucan content of 25%, a digestible carbohydrate content of 21% dwb, and a starch to β-glucan ratio of 0.84. The remainder of the milky liquid was returned to a mixing tank and was cooled to less than 40° (104° F.) by storing overnight. This sample was designated DD3-PP4-JC-SL2. The spent oat bran solids that were separated from the sieve were drum dried to yield a by-product (DD3-PP3-JC-SS-DD, Natural Cooked Oat Fiber) comprising about 6-8%, dwb, β-glucan. EXAMPLE 3A [0048] The stored milky liquid DD3-PP4-JC-SL2 from Example 2 was blended with ethyl, alcohol in the ratio of two parts DD3-PP4-JC-SL2 to one part ethyl alcohol. The mixture was circulated at low shear for one hour, and centrifuged to remove the precipitated product. A first portion of the precipitate was drum dried and was designated Invention Product DD3-PP4-JC-SL2-ETOH-CS-DS-DD having 37% dwb β-glucan, 9% dwb digestible starch, and a starch:β-glucan ratio of 0.24. EXAMPLE 3B [0049] A second portion of the precipitate obtained in Example 3A was freeze dried and was designated Invention Product DD3-PP4-JC-SL2-ETOH-CS-DS-FD having 40%, dwb, β-glucan, 10% dwb digestible starch, and a starch:β-glucan ratio of 0.25. EXAMPLE 4A [0050] Oat Bran (OBC), 100 lb (45 kg; Quaker Oats Company, Chicago, Ill.) was ground until all particles passed through a −20/840μ screen. The ground OBC was mixed with 1900 lb (862 kg) water (8.345 lb/gal or 228 gallons), heated to 108° F. (42° C.) in a mixing tank, and circulated for maximum shear using a three stage shear pump (Bostonshear pump) for 1 hour. The solids were separated using a Kek-Gardner centrifugal sifter with a 200 mesh screen bag recycled continuously for 2 hours. The separated wet sieve solids (DD6-PP6-SS1) were saved in the retaining tank for a later step. Sieved liquid (DD6-PP6-SL1) was centrifuged with a Westfalia clarifier to separate out the particles that passed through the sieve. The separated solids (DD6-PP6-CS-1) were discarded. Centrifuge liquid (DD6-PP6-CL1) was mixed with the wet solids (DD6-PP6-SS1) from the initial sieve separation procedure. The slurry was heated to approximately 200° F. (93° C.) while being circulated through the Bostonshear three shear stage pump with maximum shear for 1 hr. The hot slurry was jet-cooked at a steam pressure of 78 psi to maintain a temperature of 270° F. (132° C.), and hot liquid from the jet-cook was circulated through a Kek centrifugal sifter with a 100 mesh sieve (to remove the insoluble materials. A portion of the liquid was drum dried to give Invention Product DD6-PP6-JC-SL-DD having 21.3% dwb β-glucan, 21.6% dwb digestible starch, and a starch:β-glucan ratio of 1.01. EXAMPLE 4B [0051] The remaining sieved liquid from Example 4A (DD6-PP6-JC-SL2) was centrifuged through a Westphalia clarifier and the centrifuge liquid (DD6-PP6-JC-SL2-CL) was cooled to 60-100° F. (15-37° C.). A first portion of the cooled liquid was drum dried to give Invention Product DD6-PP6-JC-SL3-CL-DD having 31.7% dwb β-glucan, 26.0% dwb digestible starch, and a starch:β-glucan ratio of 0.77. EXAMPLE 4C [0052] A second portion of the cooled liquid from Example 4B (DD6-PP6-JC-SL2-CL) was blended with 200 proof ethanol (30% volume/70% volume of cooled DD6-PP6-JC-SL2-CL) with continuous moderate stirring for 30 min and then allowed to stand for 2 hours. The resultant slurry was continuously passed thru the Westfalia clarifier to separate out an emulsion that was allowed to settle into a liquid fraction and an insoluble fraction that was freeze-dried to give Invention Product (DD6-PP6-JC-SL2-CL-ETOH-CS1-DS-FD2) having 47.0% dwb β-glucan, 20.6% dwb digestible starch, and a starch:β-glucan ratio of 0.44. EXAMPLE 5 Hydrocolloidal Pasting Properties Using Rapid Visco-Analyzer (RVA) Measurements [0053] Visco-elastic pasting properties of the hydrocolloidal β-glucan compositions described in Examples 4A, 4B and 4C were determined using a Rapid Visco-Analyzer (RVA-4, Foss North America, Eden Prairie, Minn.) based on a procedure applied to starch compositions. The oat β-glucan hydrocolloids were suspended in water at an 8% w/w level in duplicate for each replicate. These suspensions were prepared by weighing the hydrocolloidal materials (2.24 g on a dry basis) into a RVA canister and making up the total weight to 28 grams with deionized water. The hydrocolloidal suspensions were equilibrated at 30° C. for 1 min, heated at a uniform rate so as to attain 40° C. in 4 min for a first comparison point to display the unique pasting properties of the hydrocolloid compositions of the invention. The complete spectrum of pasting was then continued by heating to 95° C., maintaining that temperature for 5.5 min, and then cooling at a uniform rate to return the temperature to 50° C. Constant paddle rotating speed (160 rpm) was used throughout entire analysis except for a speed of 960 rpm for the first 10 seconds to disperse the hydrocolloid compositions. [0000] TABLE 1 Hydrocolloid Digestible Starch and β-Glucan Contents Digestible Starch in β-Glucan in Ratio Composition, Composition, Starch/β- Product % dwb % dwb Glucan Invention Product 29 20 1.4 DD2-PP1-JC-SL-DD (Ex. 1) Invention Product 21 25 0.8 DD3-PP3-JC-SL-DD, (Ex. 2) Invention Product 9 37 0.2 DD3-PP4-JC-SL2-ETOH- CS-DS-DD (Ex. 3A) Invention Product 10 40 0.3 DD3-PP4-JC-SL2-ETOH- CS-DS-FD, (Ex. 3B) Invention Product 22 21 1.0 DD6-PP6-JC-SL-DD, (Ex. 4A) Invention Product 26 32 0.8 DD6-PP6-JC-SL3-CL- DD, (Ex. 4B) Invention Product 21 47 0.4 DD6-PP6-JC-SL2-CL- ETOH-CS1-DS-FD2, (Ex. 4C) Starting Material 41 10 4.1 OBC-VDF-PP1&2 Prior Art Product 56 10 5.6 Nutrim-OB-VOF (from same starting material as above; U.S. Pat. No. 6,060,519)
A novel low-carbohydrate digestible hydrocolloidal composition is separated from a cereal-based substrate by means of a specific sequence of steps for treating an aqueous slurry of the substrate. These all-natural compositions are low in digestible carbohydrates, principally starches, and rich in soluble fiber, principally β-glucan, as well as proteins. The hydrocolloidal products are recovered in high yields, are smooth in texture, have unexpected thickening properties, have a bland flavor, and are useful for texturizing food, especially bakery products. These hydrocolloidal products can also be used as food ingredients for increasing the nutritional level of foods and supplements.
0
BACKGROUND [0001] Portable electronic devices such as cellular telephones and music players are ubiquitous. Users often like to carry their devices in holsters that may be mounted on a belt or may place the devices in holders on a bicycle, car, or desk. SUMMARY [0002] A holster for an electronic device may have a pair of flexible hollow cushions that may hold the device in the holster. The cushions may be flexible enough to allow the device to be held in the holster both with and without a protective cover over the device. The cushions may have a hollow portion that collapses when compressed during insertion of the device. The cushion material may be a molded silicone that may have a nonslip surface finish. In some embodiments, the cushion may protrude through a bottom surface of the holster to provide a nonslip foot when the holster is used as a stand support for the device. [0003] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS [0004] In the drawings, [0005] FIG. 1 is a perspective illustration of an embodiment showing a holster. [0006] FIG. 2 is a perspective illustration of an embodiment showing the holster of FIG. 1 with an electronic device installed. [0007] FIG. 3 is a perspective illustration of an embodiment showing the holster of FIG. 1 from the rear. [0008] FIG. 4A is a lower perspective view of an embodiment showing a cushion. [0009] FIG. 4B is an upper perspective view of an embodiment showing a cushion. [0010] FIG. 4C is a cross-sectional view of an embodiment showing a cushion. [0011] FIG. 5 is a side view of an embodiment showing a holster with a device in a stand position. DETAILED DESCRIPTION [0012] A holster for an electronic device may have one or more collapsible cushions that flex during installation and removal of the device from the holster. The cushions may have a large amount of flex such that the holster may hold multiple sizes of devices or devices with or without additional protective cases. [0013] The cushions may have a nonslip surface that helps hold the device securely while in the device. In many embodiments, the cushions may be molded of thermoplastic elastomer, silicone, or other moldable material that may or may not contain silicone. Some embodiments may have the cushions extend outside of the holster cavity such that the portion of the cushions outside the cavity may act as nonslip feet when the holster is used in a stand position. [0014] Throughout this specification, like reference numbers signify the same elements throughout the description of the figures. [0015] When elements are referred to as being “connected” or “coupled,” the elements can be directly connected or coupled together or one or more intervening elements may also be present. In contrast, when elements are referred to as being “directly connected” or “directly coupled,” there are no intervening elements present. [0016] FIG. 1 is a perspective view of an embodiment 100 showing a holster assembly 102 . FIG. 1 is not to scale. [0017] The holster assembly 102 is composed of a holster body 118 , cushions 104 and 106 , and a belt clip 110 . [0018] The holster body 118 may be a rigid component that has a cavity 108 into which a device may be stored. The device may be held on top by upper lips 112 and 114 , and held on the bottom by a lower trough 116 . [0019] Within the lower trough 116 may be two cushions 104 and 106 . The cushions may conform or deflect to provide a spring-like effect to hold a device in the holster. The cushions may be hollow on the inside and may be made from a silicone or thermoplastic elastomer material. [0020] FIG. 2 is a perspective view of an embodiment 200 showing the holster assembly 102 with a device 202 . FIG. 2 is not to scale. [0021] In embodiment 200 , a device 202 is shown installed into the holster assembly 102 . The cushions 104 and 106 are shown. [0022] The device 202 may be a cellular telephone, music player, camera, or other device. [0023] The device 202 may be installed by first placing the device 202 against the cushions 104 and 106 , then pressing down to deflect the cushions 104 and 106 until the top of the device 202 fits underneath the upper lips 112 and 114 . The device may then be rotated into the holster cavity and released, allowing the cushions 104 and 106 to raise the device 202 against the upper lips 112 and 114 . [0024] When the device 202 is in the holster cavity as shown in embodiment 200 , the spring force of the cushions 104 and 106 may force the device 202 against the upper lips 112 and 114 , holding the device 202 in the holster in a secure fashion. The upper lips 112 and 114 may have a lip that contains the device 202 from falling forward (as viewed in the figure). Further, the device 202 may be oriented in the lower trough 116 such that the device 202 is within the lower trough. In such an orientation, the lower trough may contain the device 202 within the holster, as the lower edge of the device 202 may be lower than the upper edge of the lower trough. [0025] Because the cushions 104 and 106 may have a large amount of deflection while still providing a return spring force, the holster assembly 102 may be able to accommodate several different sized devices. Some embodiments may be able to securely hold a device 202 both with and without a protective case assembled onto the device 202 , or with a variety of protective cases. [0026] The holster assembly 102 is shown in the position where the upper lips 112 and 114 are at the top of the illustration. The holster assembly 102 may hold the device 202 in any orientation, including upside down from the illustration, rotated ninety degrees from the illustration, or any other configuration. In some embodiments, the holster may be oriented such that the belt clip is facing upwards, such as if the belt clip 110 were attached to a sun visor in a user's car, for example. [0027] FIG. 3 is a perspective view of an embodiment 300 showing the holster assembly 102 from the rear. [0028] The holster assembly 102 is illustrated showing the belt clip 110 , upper lips 112 and 114 , and the cushion 104 . The belt clip 110 may be rotatable 360 degrees with respect to the holster body, allowing the user to configure the belt clip to mount on a variety of applications while holding the holster in a variety of orientations. [0029] FIGS. 4A , 4 B, and 4 C illustrate three views of a typical cushion. FIGS. 4A , 4 B, and 4 C are not to scale. [0030] FIG. 4A shows an embodiment 400 of a cushion from a lower perspective view. [0031] FIG. 4B shows an embodiment 402 of a cushion from an upper perspective view. [0032] FIG. 4C shows an embodiment 404 of a cross-sectional view of a cushion. [0033] The cushion 406 may be a hollow component that is manufactured from a flexible material. In many embodiments, the cushion 406 may be molded from a thermoplastic elastomer, silicone, or some other flexible material. [0034] The cushion 406 may have a hollow area 412 . The hollow area 412 may collapse when crushed, but may return to the normal position, thus acting as a spring. The hollow area 412 may allow the cushion 406 to collapse to approximately 10-20% of its overall height. [0035] The cushion 406 may have a post 408 and tab 410 that may be used to attach the cushion 406 to a holster. The post 408 and tab 410 may be inserted into an opening or hole in the holster that corresponds with the shape of the post 408 . The tab 410 may protrude fully or partially from the hole in the holster. [0036] The thickness 422 may be the approximate thickness of the top and walls of the cushion 406 . The thickness 422 may be 0.010 in, 0.020 in, 0.050 in, 0.070 in, 0.100 in, or larger. [0037] The post 408 may have dimensions of a height 414 and width 416 . In some embodiments, the width 416 may be the same as the thickness 422 . The width 416 may be various sizes, including 0.010 in, 0.020 in, 0.050 in, 0.070 in, 0.100 in, or larger, depending on the embodiment. Similarly, the height 414 may be various sizes, including 0.010 in, 0.020 in, 0.050 in, 0.070 in, 0.100 in, or larger, depending on the embodiment. In many embodiments, the height 414 may be the same thickness as the thickness of a holster body into which the cushion 406 may be attached. [0038] The tab 410 may have dimensions of a height 418 and width 420 . The height 418 may be selected to provide a nonslip foot for a holster when the holster is placed in a stand position. The height 418 may be the same as thickness 422 . The height 418 may be various sizes, including 0.010 in, 0.020 in, 0.050 in, 0.070 in, 0.100 in, or larger, depending on the embodiment. [0039] The tab width 420 may be larger than the post width 416 and may serve as a mechanism to keep the cushion 406 attached to the holster. The tab width 420 may be various sizes, including 0.010 in, 0.020 in, 0.050 in, 0.070 in, 0.100 in, or larger, depending on the embodiment. [0040] FIG. 5 is a side view of an embodiment 500 showing the holster assembly 102 in a stand position. FIG. 5 is not to scale. [0041] The holster assembly 102 is shown with a belt clip 110 in an open position and with the device 202 installed into the holster assembly 102 . The cushion 106 protrudes from the holster assembly 102 and may serve as a nonslip foot for the assembly. [0042] The foregoing description of the subject matter has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the subject matter to the precise form disclosed, and other modifications and variations may be possible in light of the above teachings. The embodiment was chosen and described in order to best explain the principles of the invention and its practical application to thereby enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the appended claims be construed to include other alternative embodiments except insofar as limited by the prior art.
A holster for an electronic device may have a pair of flexible hollow cushions that may hold the device in the holster. The cushions may be flexible enough to allow the device to be held in the holster both with and without a protective cover over the device. The cushions may have a hollow portion that collapses when compressed during insertion of the device. The cushion material may be a molded silicone that may have a nonslip surface finish. In some embodiments, the cushion may protrude through a bottom surface of the holster to provide a nonslip foot when the holster is used as a stand support for the device.
0
CROSS REFERENCE TO RELATED APPLICATION [0001] This application is a non-provisional application claiming priority to U.S. provisional application Ser. No. 60/640,015, filed Dec. 30, 2004, the disclosure of which is hereby incorporated by reference. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates generally to cellular coverings for architectural openings and particularly those utilizing a panel of material formed from two sheets of fabric that are interconnected along horizontal lines of attachment with one sheet defining expanded but drooped cells off a confronting face of the other sheet. The cells are uniquely creased and interconnected to encourage the cells to retain an expanded form. A system for rolling the shade on a roller is also disclosed which encourages a retention of the expanded cellular form, once the panel is unrolled. A system is further disclosed for attaching the top edge and the bottom edge of a panel of material to rollers so the panel can be easily inverted if desired. [0004] 2. Description of the Relevant Art [0005] Retractable coverings for architectural openings are in common use and include by way of example venetian blinds, vertical blinds, roll-up shades, cellular shades, and the like. Some cellular shades are transversely collapsible and are raised and lowered similarly to a venetian blind while other collapsible shades are retractable about rollers. An example of the later type disclosed in U.S. Pat. No. 5,603,368 which is of common ownership with the present application. [0006] Improvements in roll-up cellular shades are continually being made and it is to provide an alternative to conventional roll-up cellular shades that the present invention has been developed. SUMMARY OF THE INVENTION [0007] The cellular panel of the present invention includes a back-up or support structure such as a sheet of flexible material to which a second sheet is attached along vertically spaced horizontal lines of attachment to define a plurality of vertically spaced horizontally extending expanded cells. The second sheet is creased at two locations to form each cell into a generally D-shaped cross-sectional configuration having a rounded soft-hanging curvature. The creases in the cells encourage the cells to be expanded when the panel of material is extended across all or a portion of an architectural opening. The panel can be retracted by rolling it around a roller at the top or bottom of the architectural opening and the creases in the second sheet of fabric are formed so as to be reinforced by being repeatedly folded consistent with the direction of the creases each time the panel is wrapped around a roller. [0008] A method of creasing the second sheet of material during the formation of the panel of material is disclosed with the creased sheet of material being formed in a shoe that is divided between heating and cooling components. In the heating component, the fabric is drawn into the desired folded configuration and compressed between the heated confronting shoe component and a cylindrical mandrel to form the creases and then the material is cooled as it is drawn between the mandrel and the cooling component to set the creases. [0009] Several embodiments for retracting the panel of material about rollers are disclosed with each system folding the panel on a roller in a manner to reinforce the creases formed in the second sheet of material so as to encourage the cellular panel to remain expanded each time the covering is extended. [0010] A unique system for quickly inverting the panel of material by flip flopping the top and bottom edges of the panel is also shown which could be used with most roll-up coverings. [0011] Other aspects, features and details of the present invention can be more completely understood by reference to the following detailed description of a preferred embodiment, taken in conjunction with the drawings and from the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS [0012] FIG. 1 is a fragmentary vertical section taken through a panel of material used in a covering in accordance with the present invention with the panel of material shown in an extended position. [0013] FIG. 1A is an isometric of a covering in accordance with the present invention utilizing the panel of material shown in FIG. 1 . [0014] FIG. 2 is a vertical diagrammatic section taken through a shoe in which the panel of material shown in FIG. 1 can be formed. [0015] FIG. 3 is an enlarged fragmentary vertical section taken through a lower portion of the covering of FIG. 1A . [0016] FIG. 4 is an isometric similar to FIG. 1A showing a second embodiment of the covering of the present invention. [0017] FIG. 5 is an isometric looking at the rear of the covering of FIG. 4 . [0018] FIG. 5A is an enlarged section taken along line 5 A- 5 A of FIG. 5 . [0019] FIG. 5B is an enlarged section taken along line 5 B- 5 B of FIG. 5 . [0020] FIG. 6 is a fragmentary elevation of a roller in which the top or bottom edge of a panel of flexible material is secured with a semi-rigid strip of material illustrating a method of attachment/detachment. [0021] FIG. 7 is a section taken along line 7 - 7 of FIG. 6 . [0022] FIG. 8 is a bottom plan view illustrating the roller of FIG. 6 . [0023] FIG. 9 is a fragmentary vertical diagrammatic section through an alternative system for extending and retracting a flexible panel of material in a top down/bottom up environment with the covering partially extended. [0024] FIG. 10 is a fragmentary section similar to FIG. 9 with the covering fully retracted. [0025] FIG. 11 is a fragmentary section similar to FIG. 9 with the covering fully extended. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0026] Referring first to FIGS. 1 and 1 A, a covering 12 incorporating a panel 14 of cellular material in accordance with the present invention is shown to include a head rail 16 , the panel 14 of cellular material with cells 15 anchored at its top edge to the head rail and at its bottom edge to a bottom roller 20 , a pair of looped lift cords 22 , and an endless drive or control cord 24 . [0027] As is probably best seen in FIG. 1 , the panel 14 of cellular material is comprised of a support structure which could be a first sheet 26 of backing or support material and a second sheet 28 of looped and creased material that is secured to the first sheet along vertically spaced horizontal lines of attachment 30 in any suitable manner such as with adhesive, ultrasonic bonding or the like. The sheets of material 26 and 28 can be the same or different and can, by way of example, be a sheer fabric, a translucent material, or even an opaque material. Both sheets of material are flexible with at least the second sheet of material being semi-rigid and creasable. The second sheet has enough rigidity to retain the full expanded shape shown in FIG. 1 . A suitable fibrous material made with a thermo-forming resin is well suited for at least the second sheet of material with thermoset or thermoplastic resins being acceptable binders for the fibers. The support structure would not necessarily have to be a sheet of material 26 but could be for example, a plurality of vertical cords or micro fibers (not shown) to which the second sheet is attached. [0028] Each cell 15 constitutes an elongated tube of generally D shaped cross section and with each elongated cell overlying a next adjacent lower cell and being identical therewith. Each cell includes a first inwardly directed or pointed crease 32 along the lower edge of its upper line of attachment 30 and a relatively straight upper segment 34 extending from the first crease to a second outwardly directed or pointed crease 36 . The first segment 34 of the cell which might be referred to as a top wall, slopes downwardly at a small acute angle (e.g. between 5° and 45°) to the second crease. A second segment 38 of the cell which might be referred to as a front wall hangs downwardly in a soft drooping or looped fashion from the second crease in a soft hanging curve and is substantially vertically directed. A third segment 40 or bottom wall of the cell extends from a curved and drooped lower edge 42 of the front wall substantially horizontally and rearwardly to the next lower line of attachment 30 . The bottom wall is of generally S shaped configuration. The outwardly pointed or directed second crease 36 as well as the first crease 32 serve to assist in supporting the cell in the fully expanded configuration illustrated in FIG. 1 , which of course is facilitated further by the semi-rigid character of the material from which the second sheet 28 is made. By making the second sheet from a thermo-forming resin material in which fibers are imbedded, the sheet is resilient in that even after having been deformed as when the material is wrapped around a roller, it will return dependably to the form or configuration shown in FIG. 1 . This is particularly true, due to the nature in which the material is wrapped around the bottom roller 20 , as will be described in more detail hereafter. [0029] The panel 14 can be formed in numerous ways, but it has been found desirable to make the panel by first securing the second sheet of material 28 to the first sheet of material 26 along the lines of attachment 30 so the second sheet of material is looped off a front face of the first sheet of material i.e., there is more of the second sheet of material between lines of attachment than of the first sheet of material. The double-layered panel can then be pulled around a mandrel 44 ( FIG. 2 ) beneath a pair of generally semi-cylindrical compressive shoes 46 and 48 which are yieldingly forced against the opposed faces of the mandrel with coil springs 50 . One shoe 46 is heated in a conventional manner such as with a hot fluid passed through internal passages 52 in the shoe while the other shoe 48 is cooled as with a cooling fluid passed through passages 52 in the shoe. [0030] When the panel of material 14 is pulled into the space between the mandrel 44 and the compressive shoes 46 and 48 as shown in FIG. 2 , the first sheet of material 26 passes smoothly around the mandrel in a counterclockwise direction while the second sheet of material 28 is laid smoothly against the first sheet of material from a first line of attachment 30 downwardly but as the panel is advanced around the mandrel, the second sheet of material is continuously forced into a smaller and smaller loop until it defines the two creases 32 and 36 and an overlapped fold 54 of generally S-shaped configuration. The overlapped fold is confined between the mandrel and the compressive shoes with the heated shoe forming the creases in the material along the overlapped fold and the cooling shoe setting the creases before the panel of material exits the mandrel. The fold 54 defines overlapping layers of the second sheet of material which includes a line of attachment 30 in the top wall 34 and a top portion of the front wall 38 of a cell 15 . The creases surge the second sheet of material to expand or billow away from the first sheet of material to establish the desired D-shape of the cell as shown in FIG. 1 . The first crease 32 is secured to the first sheet of material 26 while the second crease 36 is allowed to billow or flex away from the first crease along the first segment or top wall 34 of the cell again as fully appreciated by reference to FIG. 1 . [0031] Referring to FIGS. 1A and 3 , it will be appreciated the panel of material 14 is secured along an upper edge 56 in a fixed relationship and in any suitable manner to the head rail 16 . Preferably the upper edge is concealed within the head rail for aesthetic purposes. The bottom edge 58 of the panel 14 is anchored to the bottom roller 20 of the covering, which is generally cylindrical in configuration, having a longitudinal channel 60 formed in an outer surface thereof defining a relatively small slot 62 in the outer surface between a pair of opposed lips 64 . The lower edge of the panel is hemmed and a rigid or semi-rigid anchor strip 66 is positioned within the hem. The anchor strip with the hem may be slid axially along the length of the roller 20 from one end to the other to secure the lower hemmed edge of the panel to the bottom roller in a conventional manner. The bottom edge could also be secured to the roller in an alternative manner as will be described hereafter. [0032] The bottom roller 20 is rolled in a counterclockwise direction as viewed in FIG. 3 when retracting the covering from the extended position of FIG. 1A to a fully retracted position wherein the bottom roller is disposed adjacent to the head rail 16 . The bottom roller is rolled with the looped lift cords 22 which are anchored at a front end 68 ( FIG. 1A ) to a concealed location at the front of the head rail and at a back end 70 to a take-up roller 72 in the head rail. The take-up roller is rotated with the endless control cord 24 by moving the control cord in a rotating direction to thereby correspondingly rotate the take-up roller allowing the lift cords 22 to be wrapped therearound. In this manner, the size of the loop of the lift cords is adjustable from a maximum size when the shade is fully extended as shown in FIG. 1A , to a minimum size when the covering is fully retracted. The rotation of the bottom roller occurs through friction between the lift cords and the panel of material 14 with the lift cords engaging the panel of material around the underside of the bottom roller 20 . As the lift cords are raised along the back of the panel, the shortening of the loop of lift cords causes the bottom roller to be raised while it is being rotated in a counterclockwise direction thereby wrapping the panel of material thereabout. This type of lift system is common in bamboo shades wherein horizontal slats of bamboo are interconnected with elongated vertical cords and the bottom rail is raised with endless lift cords as described above. [0033] As is best illustrated in FIG. 3 , as the bottom roller 20 is rotated in a counterclockwise direction, the panel of material 14 is wrapped therearound with the second crease 36 in the panel being encouraged from the configuration of the panel to overlap and form a fold 74 configured identically to the fold 54 in the material as it exits the compressive shoes 46 and 48 as shown in FIG. 2 . The second sheet of material 28 in the panel is compressed by the lift cords 22 as the panel is initially wrapped onto the bottom roller. The free-hanging soft loop in the front wall 38 of each cell 15 in the second sheet of material adjacent to the bottom of each cell is also forced to fold at 76 in an opposite direction to the second crease 36 and toward an overlying relationship with the preceding or underlying line of attachment 30 . Accordingly, as seen in FIG. 3 , there are two folds 74 and 76 established as the panel of material wraps around the bottom roller with the folds being directed toward each other and in overlying relationship with a line of attachment 30 . [0034] As will be appreciated, inasmuch as the first and second creases 32 and 36 are compressed into their original configuration shown in FIG. 2 as they are wrapped around the bottom roller in the fold 74 , the creases are reinforced each time the panel of material is wrapped around the roller. In this manner, the creases in the second sheet of material are reinforced continually upon operation of the covering encouraging the second sheet to fully deploy to the expanded position shown in FIG. 1 with repeated use and over long periods of time. [0035] As will be appreciated, the upper edge 56 of the panel of material 14 , which is secured to the head rail 16 , could be secured to an upper roller (not shown) which is not rotatable but rather statically positioned within the head rail but wherein the upper edge is secured to that roller identically to the manner in which it is secured to the bottom roller 20 , i.e. with a hem and a rigid or semi-rigid anchor strip inserted within the outwardly opening channel 60 of the roller. This system for anchoring the upper edge of the fabric is useful in accordance with features of the present invention which will be described in more detail hereafter. [0036] FIGS. 4-5B show an alternative embodiment of the present invention wherein the panel of material 14 is identical to that previously described and wherein the upper edge 56 of the panel of material is secured as with adhesive or the like to the head rail 16 and the bottom edge 58 is secured to the bottom roller 20 in a manner identically to that previously described. In this embodiment of the invention, however, the lift cords have been replaced with lift straps 78 at opposite ends of the panel 14 with the front end 80 of each lift strap being secured preferably in a confined location to the head rail and a rear end 82 of the lift strap being anchored to a spool 84 fixed for unitary rotation with a take-up rod 86 . The take-up rod is supported by a pair of brackets 88 fixed to the head rail and is rotated with an endless control cord 24 with the upper end of the endless control cord 24 being confined within a housing 90 and frictionally engaged with the take-up rod for unitary rotation therewith. In other words, as the control cord is rotated, the take-up rod is simultaneously rotated along with the spools anchoring the rear ends of the lift straps 78 . [0037] A pair of guide straps 92 have their upper ends 94 secured to the take-up rod 86 and their lower ends 96 secured to a guide rod 98 . The guide rod as shown in FIG. 5A has a slot 100 at each end thereof which slidably receives an associated lift strap 78 and a second slot 102 spaced inwardly thereof for anchoring the lower end of an associated guide strap 92 . As seen in FIG. 5B , the lower ends 104 of the guide straps are hemmed and a rigid rod 106 is inserted therethrough and seated in a recess 108 communicating with the associated slot 102 . [0038] As the take-up rod is rotated with the control cord 24 , the guide straps 92 are wrapped around the take-up rod 86 on a smaller diameter than the lift straps 78 so that the guide straps will lift the guide rod 98 at about the same speed as the bottom roller 20 is being raised by the lift straps inasmuch as the lift straps pass around a greater and increasing diameter of the bottom roller as the panel of material accumulates thereon. The guide rod therefore retains the position of the lift straps as the covering is moved between retracted and extended positions. [0039] With reference to FIGS. 6-8 , a system is shown for easily connecting and/or disconnecting a hemmed edge 110 of a panel of material 112 to/or from an elongated element such as a roller 114 of the type described previously. The panel could be any flexible panel including a panel 14 of the type previously described herein. The roller as seen in FIG. 7 is of cylindrical configuration having a channel 116 formed therein that opens through a slot 118 in the outer surface of the roller between a pair of confronting lips 120 . The confronting lips are uniformly spaced from each other commencing at each end of the cylinder. However, at a centered location along the length of the cylinder, the lips are retracted as shown in FIG. 8 to define a relatively wide gap 122 . The wide gap at the longitudinal center of the cylinder or roller 114 is wide enough to allow an anchor strip 124 of semi-rigid material to be removed therefrom while the anchor strip is inserted into the hem 110 along the edge of the panel. When attaching the panel of material 112 to the roller 114 , rather than inserting the hem along with the anchor strip into an open end of the channel and sliding the strip along with the hemmed material therealong as is conventional, the ends of the anchor strip 124 with the hem of the panel therearound can be inserted into the gap 122 and forced in opposite directions until the entire anchor strip has been received with the hemmed edge of the material within the channel 116 . The hemmed edge of the material can be removed in a reverse manner by grasping the anchor strip with the hemmed material at the location of the wide gap and pulling the semi-rigid strip of anchor material out of the channel as illustrated in FIG. 6 . [0040] This system for connecting and disconnecting a panel of material 112 to/or from a roller 114 is useful with any flexible panel of material as the material can be removed from the roller without removing the roller from the hardware of the covering in which it is mounted since the anchor strip does not have to be slid longitudinally out of an open end of the roller but can be removed laterally. This also enables one to easily invert a panel of material should the panel lose its resilience and desired cellular configuration in the case with a cellular panel. The resilience of the panel, of course, permits the cells in the panel to fully expand as desired and as illustrated for example in FIG. 1 . In other words, should the material start drooping more than desired, it can be inverted by easily removing the opposite top and bottom edges of the panel from their anchor rollers and after inverting the panel of material reattaching the edges to the opposite anchor rollers as described above without disassembling the hardware for the covering. [0041] As can be appreciated by reference to FIG. 4 , the location where the lift straps 78 or in the case of the embodiment of FIG. 1A the lift cords 22 , engage the panel of material 14 , the panel can become deformed at 126 . To avoid such a deformation in the panel, a system of the type shown in FIGS. 9-11 can be utilized. In this embodiment of the invention, the bottom edge 58 of the panel of material is again secured to the bottom roller 20 as described previously so that the panel of material can be wrapped around the bottom roller as the roller is raised and rotated with the lift cords 22 or straps 78 . For purposes of the present disclosure, lift cords are utilized but lift straps could be used in lieu of the lift cords. In the embodiment of FIGS. 9-11 and as best appreciated by reference to FIG. 9 , there is an upper lift cord 22 U and a lower lift cord 22 L with the bottom edge 128 of the upper lift cord being secured to the upper edge of an elongated sling or flexible strip of material 130 with a batten 132 that runs along the full length of the strip of material. Similarly, the upper end 134 of the lower lift cord 22 L is secured to a batten 136 along the bottom edge of the sling of flexible material 130 . The upper lift cord 22 U extends around a pulley 138 in the head rail 140 with the lower lift cord 22 L extending around a pulley 142 disposed beneath and at a rearwardly displaced position in the head rail relative to the pulley 138 . Both the upper and lower lift cords can be manually pulled or released and conventional cleats (not shown) are provided for anchoring the lift cords at any desired location along their length. The panel of covering material 14 has an upper edge 144 adhesively or otherwise secured to the lower cord 22 L immediately beneath the batten 136 as seen in FIG. 9 with an anchor bar 146 and the lower or opposite edge of the panel is anchored to the bottom roller 20 , for example, in a manner as previously described herein. [0042] When operating the covering so that the panel of material 14 lowers from the head rail 140 as it is being extended across an architectural opening, the upper lift cord 22 U is raised to its fullest extent and cleated or anchored in a fixed position as shown in FIG. 1 D and the lower lift cord 22 L is allowed to extend so that the panel of material is unrolled from the bottom roller 20 which rotates in a clockwise direction allowing the panel of material to be unwrapped therefrom. Of course, the panel can be fully extended in this manner so as to extend from the lower edge of the sling of flexible material 130 down to its bottom edge which is anchored to the bottom roller. Further, leaving the upper lift cord anchored and shortening the lower lift cord will cause the panel to roll up about the bottom roller to raise the shade to the retracted position of FIG. 1D adjacent to the head rail. As will be appreciated, by raising the panel of material in this manner, the roller will ultimately become horizontally aligned with the sling 130 and as fully appreciated by reference to FIG. 10 , the sling will pass beneath the roller and thereby support the roller in the fully retracted position along its full length thereby not deforming the panel 14 as might incur in the embodiments of FIGS. 1A and 4 . [0043] The covering of FIG. 9-11 could also be operated by extending both the upper 22 U and lower 22 L cords with the panel 14 wrapped around the bottom roller 20 and supported by the sling 130 until the bottom roller is positioned adjacent to the lower edge of the architectural opening in which the covering is mounted as shown in FIG. 11 . By then lowering the lower cord at a rate simultaneous to that of raising the upper lift cord, the panel will unroll from the bottom roller while the bottom roller remains adjacent to the bottom edge of the architectural opening. Accordingly, the panel of material will extend from the bottom of the opening toward the top of the opening. Of course, the reverse would be applicable to lower the top edge of the panel back to a rolled position about the bottom roller at its lowered location. This would be accomplished by raising the bottom lift cord at the same rate that the upper lift cord is extended. [0044] It will be appreciated that the sling of flexible material 130 can support the bottom roller 20 at any position of the bottom roller by appropriately manipulating the upper 22 U and lower 22 L lift cords and the sling of material, of course, uniformly supports the roller and panel 14 along its entire length to avoid deformation of the roll of panel material. It should also be appreciated that while the embodiment of the invention shown in FIGS. 9-11 could be used with a panel of material 14 of the type shown in FIGS. 1 and 1 A, it can also be used with any flexible panel of material capable of being rolled around a roller. [0045] Although the present invention has been described with a certain degree of particularity, it is understood the disclosure has been made by way of example, and changes in detail or structure may be made without departing from the spirit of the invention as defined in the appended claims.
A covering for an architectural opening includes a panel of material consisting of a first flexible sheet of material on which a second flexible sheet of material is secured along vertically spaced horizontal lines of attachment so that the second sheet of material billows or flexes away from the first sheet of material to define a plurality of vertically superimposed cells. The creases placed in the cells are designed so that as the panel of material is wrapped around a roller, the creases are reinforced to extend the life of the creases and thus the desired billowing effect of the cellular panel of material. Various systems are disclosed for extending and retracting a panel of material as well as for anchoring the top and bottom edges of the panel to a roller in a manner so that they can be easily attached/detached without disassembling the hardware for the covering.
0
RELATED APPLICATIONS This application is a national stage application, filed under 35 U.S.C. §371, of International Application No. PCT/US2013/031396, filed on Mar. 14, 2013, which claims priority to, and benefit of U.S. Provisional Application No. 61/614,449, filed on Mar. 22, 2012, each of which is herein incorporated by reference in its entirety. INCORPORATION BY REFERENCE OF SEQUENCE LISTING The contents of the text file named “21486-612001WO_ST25.txt”, which was created on Apr. 24, 2013 and is 864 bytes in size, are hereby incorporated by reference in their entireties. GOVERNMENT SUPPORT This invention was made with Government support under NIHR21AR057156 awarded by the National Institutes of Health. The Government has certain rights in the invention. FIELD OF THE INVENTION The field of the invention relates to cancer therapy. BACKGROUND OF THE INVENTION Cartilage tumors account for 22% of all skeletal system tumors and are characterized by the formation of exostoses and/or endostoses and subsequently cause significant morbidity and mortality. Clinical treatment of cartilage tumors, such as metachondromatosis, largely relies on surgical intervention, and no effective medical therapy is currently available. SUMMARY OF THE INVENTION Hedgehog (Hh) pathway inhibitors, such as small molecules, e.g., PF-04449913, are used to prevent, slow, or block the formation of exostosis or enchondromas. Such compounds are also useful to prevent and/or reduce cartilage tumorigenesis such as metachondromatosis, a type of tumor caused by an autosomal dominant skeletal disorder that affects the growth of bones, leading to multiple enchondromas and osteochondromas. The latter disorder affects mainly tubular bones, though it can involve the vertebrae. The compositions and methods described herein lead to a reduction in tumor burden or tumor mass. Exemplary Hh inhibitors include Smoothened inhibitors (SMOi). The inhibitor or combination of inhibitors is administered systemically or locally to a diseased site. Preferably, the inhibitor is a small molecule. However, proteins, peptides, antibody or antibody fragment based inhibitors are also useful. In preferred embodiments, the methods do not encompass use of MEK (MAP kinase kinase) and ERK (extracellular signal-regulated kinase) inhibitors, e.g., long term use of such inhibitors. The methods are useful to treat human patients, as well as animals such as companion animals (e.g., dogs, cats), as well as livestock and working animals (e.g., horses, cattle, goats, sheep, chickens). In addition to methods of treating cartilage diseases and cartilage tumors, the methods are useful to reduce or prevent development of a benign or non-malignant cartilage disorder such as metachondromatosis (a benign cartilage tumor syndrome with malignant potential) into malignant disease such as malignant chondrosarcoma. Also within the invention is a composition, e.g., a pharmaceutical composition, comprising a cartilage tumor-inhibiting amount of a hedgehog pathway inhibitor such as a Smoothened inhibitor or Smoothened receptor inhibitor. A pharmaceutical composition includes an active therapeutic agent, e.g., small molecule inhibitor, and a pharmaceutically acceptable or physiologically acceptable excipient or inactive ingredient(s). Compounds described herein, e.g., those used for therapy are purified and/or isolated. As used herein, an “isolated” or “purified” compound (e.g., small molecule drug), nucleic acid molecule, polynucleotide, polypeptide, or protein, is substantially free of other cellular material, or culture medium when produced by recombinant techniques, or chemical precursors or other chemicals when chemically synthesized. Purified compounds are at least 60% by weight (dry weight) the compound of interest. Preferably, the preparation is at least 75%, more preferably at least 90%, and most preferably at least 99%, or 100%, by weight the compound of interest. Purity is measured by any appropriate standard method, for example, by column chromatography, polyacrylamide gel electrophoresis, or HPLC analysis. Publications, U.S. patents and applications, Genbank/NCBI accession numbers, and all other references cited herein, are hereby incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 a is a diagram showing breeding schemes for generating Ctsk-KO, LysM-KO, and their respective Control mice. FIGS. 2 b - c are photographs showing gross images (b) and Faxitron radiographs (c) of 12 week-old Ctsk-KO mice showing dwarfism, scoliosis (black arrowheads), increased bone mineral density, and multiple exostoses of knees, ankles, and metatarsals (arrowheads), accompanied by joint destruction. FIG. 1 d is a series of photomicrographs showing sagittal sections of metatarsal joints stained with H&E (i-iii), Safranin O (iv-vi) and Alcian blue (vii-ix) showing cartilaginous exostoses and enchondromas (arrows) in Ctsk-KO mice. Images in iii, vi and ix are magnified (10×) views of boxed areas in ii, iv and viii, respectively. These data show that Ptpn11 deletion in Cathepsin K-expressing cells causes metachondromatosis. FIGS. 2 a - d are photomicrographs showing that skeletal tumors in Ctsk-KO mice originate from Shp2-deficient chondroid cells in the perichondrial Groove of Ranvier. a, X-gal staining of knee joint sections from 1-week-old R26lacZ; Ctsk-Cre and R26lacZ; LysM-Cre reporter mice shows that the Ctsk (but not the LysM) promoter is active not only in osteoclasts, but also in a subset of cells residing in Perichondrial Groove of Ranvier. b, H&E and Safranin O staining of knee joint sections from day P10 Ctsk-Control (i,iv) and Ctsk-KO (ii, iii, v, vi) mice showing expansion of chondroid cells within the Perichondrial Groove of Ranvier region in Ctsk-KO mice (arrows). Images in iii & vi are magnified (10×) views of boxed areas in ii & v respectively; c, H&E-and Safranin O-stained section showing expanding YFP+ population within the Perichondrial Groove of Ranvier (boxed region in top panels, magnified below) that also stains with Safranin O, indicative of cartilage. d, frozen section of an exostosis from the metatarsal joint of Ctsk-KO/YFP mice showing co-localization of YFP reporter with cartilaginous tumor cells (boxed-in area). Note that the lesion contains proliferating and hypertrophic chondrocytes, as revealed by Col2α1 and Col10α1 immunostaining, respectively. FIG. 3 a is a graph showing the results of a flow cytometric analysis showing YFP+ cells from the epiphyseal cartilage of Ctsk-Control/YFP mice; note increased number of these cells in 2-week-old Ctsk-KO/YFP mice. CC: Chondroid cells. FIG. 3 b is a graph showing the results of a flow cytometric analysis of YFP+ perichondrial cells showing staining for CD31, CD44, CD90, and CD166. FIG. 3 c is a photomicrograph showing immunofluorescence staining showing Stro1 and Jagged1 expression in YFP+ perichondrial cells. These data show that Ptpn11 deletion in Ctsk-expressing cells causes expansion of novel chondroprogenitor cell population within the Perichondrial Groove of Ranvier region. FIG. 4 a , Left panel, is a bar graph of qPCR results showing increased Col2α1, Col10α1, Ihh, and Pthrp expression in laser-captured cartilaginous cells from exostoses, compared with normal articular cartilage cells (n=4, *p<0.05, Student t test). FIG. 4 a , Right panel, is a series of photomicrographs showing immunostaining of paraffin sections from Perichondrial Groove of Ranvier region of Ctsk-KO and Control mice. Note the decreased number of p-Erk+ cells, but increased Ihh expression in Ctsk-KO, compared with Control, mice. FIG. 4 b , Left Panel, is a photograph of an immunoblot showing Shp2 levels in ATDC5 chondroprogenitor cell lines stably expressing shRNAs against murine Ptpn11 (ATDC5-KD1, ATDC5-KD2, respectively) or a scrambled control hairpin. FIG. 4 b , Right panels, is an immunoblot and bar graph showing that Shp2 deficiency decreases Erk activation in response to Fgf18 (top), while q-PCR (bottom) shows increased Ihh and Pthrp expression in Shp2 deficient ATDC5 cells (n=3, *p<0.05, Student t test). FIG. 4 c is a bar graph showing that FGFR (PD173074, 10 nM) or MEK (UO126, 1 μM) inhibitor treatment of parental ATDC5 cells enhances Ihh and Pthrp expression, as shown by q-PCR (n=3, *p<0.05, Student t test). FIG. 4 d is a series of Faxitron radiographs showing that blockade of the Hedgehog pathway by administration of the Smoothened inhibitor PF-04449913 (100 μg/g body weight) by daily gavage to Ctsk-KO mice (n=5) ameliorates tumor formation compared with vehicle control (0.5% methylcellulose)-treated mice. Images of representative posterior paws (i-iv) and knese (v-vii) taken pre-treatment (i, iii, v, vii) and post-treatment with vehicle (ii, vi) or Smoothened inhibitor (SMOi) (iv, viii) for 4 weeks. Note continued development of exostoses and endochromas in Vehicle-treated mice, and their amelioration in SMOi-treated group (arrows). Also, see FIGS. 7 a,b and 8 a,b . These data show that Shp2 deficiency compromises Erk activation but promotes Ihh and Pthrp expression. FIG. 5 a is a series of immunoblots showing Shp2 levels in bone marrow-derived macrophages (left), osteoclasts (middle), and in YFP+ perichondrial cells (CCPs) (right) from Ctsk-Control/YFP and KO/YFP mice, as indicated; Erk2 levels serve as a loading control. FIG. 5 b is a series of Faxitron radiographs that demonstrate increased bone mineral density in LysM-KO mice compared with Controls, but no exostoses or joint deformation. FIG. 5 c is a series of photomicrographs showing H&E-(i-iii), Safranin O-(iv-vi) and Alcian blue (vii-ix) staining of sagittal sections of knee joints from 12-week-old Ctsk-Control (i, iv, vii) and Ctsk-KO (ii, iii, v, vi, viii, ix) mice. Image iii, vi & ix are magnified views (10×) of the boxed areas in ii, v, and viii, respectively. Note exostoses (arrows) in Ctsk-KO mice. Compared with Controls, Ctsk-KO mice have markedly enlarged distal femurs and proximal tibiae and elongated metaphyses with a broad and coast shape-like growth plate cartilage (ii, v, viii). Newly forming cartilage masses are seen readily at the epiphyses (iii, vi, ix). FIG. 5 d is a series of photomicrographs of Safranin O stain showing enchondromas (arrows) in tubular bones of Ctsk-KO mice. FIG. 6 a is a diagram showing a scheme for using bone marrow transplantation to examine the role of osteoclasts (or other bone marrow-derived cells) in skeletal pathogenesis in Ctsk-KO mice. FIG. 6 b is a graph showing the results of a flow cytometric analysis of peripheral blood showing high engraftment of donor BM cells from Ctsk-KO/YFP+ and Ctsk-Control/YFP+ (C57BL/6; CD45.2) mice in lethally irradiated recipients (B6.SJL; CD45.1). Tail vein bleeding was performed 12 weeks post-BMT. FIG. 6 c is a series of Faxitron radiographs show that recipients of Ctsk-KO, but not Ctsk-Control, bone marrow have increased bone mineral density, but do not develop exostoses even after >12 months of observation. FIGS. 7 a - b are a series of Faxitron radiographs showing that blockade of the Hedgehog pathway by administration of the Smoothened inhibitor (SMOi) PF-04449913 (100 μg/g body weight) or vehicle control (0.5% methylcellulose) by daily gavage to Ctsk-KO mice ameliorates tumor formation compared with vehicle alone treated mice. All animals used for these experiments are shown. Note the reduction of number and size of exostoses (arrows) in SMOi-, but not vehicle-treated Ctsk-KO mice (also see FIG. 8 a,b ). SMOi was administered by oral gavage to Ctsk-KO mice beginning at post-natal week 5 for four weeks, and mice were euthanized at week 9. FIG. 8 a is a series of charts showing number and size of exostoses in Ctsk-KO mice post-treatment (n=5) with vehicle or Smoothened inhibitor (SMOi). Note decrease in average number of exostoses/per paw, knee, and tibiae (n=10). # indicates that only small exostoses were observed. p value was determined by Student t test. FIG. 8 b is a bar graph of qPCR results showing that oral administration of the Smoothened inhibitor SMOi to wild type mice for 1 week blunts the expression of Col2α1, Col10α1, Mmp13 and Gli1 in epiphyseal cartilage (n=3, *p<0.05, student t test). FIGS. 9A-F are a series of photographs, a bar graph and schematic showing that inhibition of hedgehog signaling by oral administration of an inhibitory agent leads to prevention and inhibition of the development of exostosis and enchondromas. FIG. 10 is a diagram of Hedgehog (Hh) signaling pathway and exemplary inhibitors, e.g., Smoothened (Smo) inhibitor (GDC-0449, IPI-926, etc.), inhibition of the transformation of inactive Smo into active Smo (SANT 74, SANT 75), inhibition of the transport of cytoplasmic inactive Smo to cilia (SANT 1-4), inhibition of binding of Gli to DNA (GANT 58, GANT 61), Shh antagonist (Robotnikinin) and anti-Patched (Ptch) antibody. DETAILED DESCRIPTION Src-homology 2 domain-containing phosphatase 2 (SHP2) belongs to the protein-tyrosine phosphatase family of proteins. It is a member of the non-receptor class 2 subfamily and contains 2 SH2 domains and 1 tyrosine-protein phosphatase domain. Based on tissue specific gene knockout approaches, whole-genome sequencing, and linkage analysis with high-density SNP array assays, mutations in Ptpn11 gene, encoding the src homology 2 domain-containing protein tyrosine phosphspahtases Shp2, were found to be associated with metachondromatosis (MC), a benign cartilage tumor syndrome with malignant potential. Further biological and biochemical studies uncovered that 1) It is the Ptpn11 loss-of-function mutations in a novel perichondrial cartilaginous cell population that causes metachondromatosis; 2) cartilage tumor lesions in Shp2 mutant mice express elevated levels of Indian hedgehog and parathyroid hormone related protein (PTHrP); and 3) blockade of hedgehog signaling in Shp2 mutant animals by administration of hedgehog pathway inhibitors, such as the Smoothened inhibitor PF-0444993 can stop or slow down the disease process. The data indicates that inhibition or attenuation of hedgehog pathway pharmacologically is useful to treat and prevent cartilage tumorigenesis, such as metachondromatosis ( FIGS. 9A-F ). By using transgenic animals that lack Shp2 in a unique perichondrial cartilaginous cell population, elevated expression of IHH and PTHrP and ectopic hedgehog signaling in epiphyseal cartilage cells were found to play an important role in the formation of exostosis and enchondromas. PF04449913 is a hedgehog signaling pathway inhibitor of the SMOi class. This inhibitor is orally administered and has antineoplastic activity. The inhibitor was found to block or attenuate hedgehog signaling. Systematic PF04449913 administration reduces the cartilage tumor condition developed in Shp2 mutant mice. PF04449913 is a Smoothened (Smo) inhibitor that is available from Pfizer, Inc. This small molecule and other hedgehog pathway inhibitors such as Smo inhibitors, are known in the art, e.g., Onishi et al., 2011, Cancer Science 102:1756-1760, hereby incorporated by reference. IPI-926 and GDC-0449 are the 2 leading compounds in the class. Exemplary members of the Hedgehog inhibitor class of compounds include Cyclopamine (C 27 H 41 NO 2 ), Jervine (C 27 H 39 NO 3 ), Infinity IPI-926/saridegib, Genentech GDC-0449/vismodegib, and Novartis LDE-225/erismodegib, and Millennium Pharmaceuticals's TAK-441. For example, other Smo inhibitors include BMS-833923 (a.k.a., XL-139; Bristol-Meyers Squibb) and LDE225 (Novartis). Additional Hh pathway inhibitors are known in the art, see, e.g., FIG. 10 , e.g., Cyclopamine, which suppresses the Hh signaling pathway through direct interaction with Smo; a Cyclopamine with improved solubility (IPI-926); non-cyclopamine-based Smo inhibitors (GDC-0499, LDE225, BMS-833923, XL-139, PF-0449913), inhibitors of the transformation of inactive Smo into active Smo (SANT 74-75), and inhibitors of the transport of cytoplasmic inactive Smo to cilia (SANT 1-4). Small molecule inhibitors such as those described above are generally 1000 daltons or smaller in molecular mass, e.g., 700, 500, 250, 200, 100 daltons. Exemplary doses range from about 0.1 mg/Kg to about 1000 mg/Kg. For example, some inhibitors are administered at a dose of 10-500, e.g., 100-300 mg per day. Effective doses may vary, as recognized by those skilled in the art, depending on the types of tumors treated, route of administration, excipient usage, and co-administration with other agents. Routes of administration include systemically (e.g., orally, intravenously, or intramuscularly) or locally (e.g., by directly contacting the tumor by injection or implantation of a drug-eluting device). For treatment of metachondromatosis, oral administration is a preferred route of administration of therapeutic agent. This discovery allows one to use hedgehog pathway inhibitors to stop or slow down the unguided chondrogenic cell proliferation and differentiation and treat metachondromatosis and other cartilage tumors. The administration of hedgehog pathway inhibitors locally or systematically to prevents, slows down, or blocks the formation of exostosis and enchondromas and treat cartilage tumorigenesis, such as metachondromatosis. Treating patients with cartilage tumors provides clinicians with an alternative and noninvasive approach to treat patients with cartilage tumors, such as metachondromatosis. The methods exclude treatment of non-cartilage tumors, hematopoetic system tumors (leukemia, lymphoma), basal cell carcinoma, brain (such as medulloblastoma), lung, pancreatic, colorectal, ovarian, gastric, glioblastoma, prostate, sarcoma, multiple myeloma, breast, leukemia, small cell lung cancer, gastric, multiple myeloma, osteosarcoma, and/or stomach/gastroesophageal cancers. In some instances, the methods exclude treatment of malignant chondrosarcoma. However, the methods are used for early treatment of cartilage tumors, e.g., benign metachondromatosis and other benign/non-malignant or pre-malignant cartilage disorders, prior to development into a malignant phenotype. Thus, early intervention at benign or pre-malignant stage of a cartilage disease or disorder reduces or prevents progression to a malignant state, thereby representing an important advantage of this therapeutic approach. Thus, the Hh inhibitor, e.g., SMOi, are administered prior to diagnosis of malignant chrondrosarcoma. Methods of diagnosing a benign/non-malignant phenotype from malignant chondrosarcoma are known in the art, e.g., by histological analysis of biopsied tissue. Ptpn11 Deficiency in a Novel Cartilage Stem/Progenitor Cell Causes Metachondromatosis by Activating the Hedgehog Pathway SHP2, encoded by PTPN11, is required for survival, proliferation and differentiation of various cell types. Germ line activating mutations in PTPN11 cause Noonan Syndrome, while somatic PTPN11 mutations cause childhood myeloproliferative disease and contribute to some solid tumors (Chan et al., 2008, Cancer Metastasis Rev 27, 179-192; Chan et al., 2007, Blood 109, 862-867). Heterozygous inactivating mutations in PTPN11 were found in metachondromatosis, a rare inherited disorder featuring multiple exostoses, endochondromas, joint destruction and bony deformities (Bowen et al., 2011 PLoS Genet 7, e1002050; Sobreira et al., 2010, PLoS Genet 6, e1000991). The detailed pathogenesis of this disorder has remained unclear. Here, we used a conditional knockout allele (Ptpn11fl) and Cre recombinase (Cre) transgenic mice to delete Ptpn11 specifically in monocytes, macrophages and osteoclasts (lysozyme M-Cre; LysMCre) or in cathepsin K (Ctsk)-expressing cells, previously thought to be osteoclasts. LysMCre; Ptpn11 fl/fl mice had mild osteopetrosis. Surprisingly, however, CtskCre; Ptpn11 fl/fl mice developed features strikingly similar to metachondromatosis. Lineage tracing revealed a novel population of Ctsk-Cre-expressing cells in the “Perichondrial Groove of Ranvier” that expressed markers consistent with mesenchymal progenitors. Chondroid neoplasms arose from these cells and showed decreased Erk activation, increased Indian Hedgehog (Ihh) and Parathyroid hormone-related protein (Pthrp) expression and excessive proliferation. Shp2-deficient chondroprogenitors had decreased FGF-evoked Erk activation and enhanced Ihh and Pthrp expression, whereas FGFR or MEK inhibitor treatment of chondroid cells increased Ihh and Pthrp expression. Most importantly, Smoothened inhibitor treatment ameliorated metachondromatosis features in CtskCre; Ptpn11 fl/fl mice. Thus, in contrast to its pro-oncogenic role in hematopoietic and epithelial cells, Ptpn11 is a tumor suppressor in cartilage, acting via an FGFR/MEK/ERK-dependent pathway in a novel progenitor cell population to prevent excessive Ihh production. Cartilage Tumors Cartilage tumors, which include exostoses, enchondromas and chondrosarcomas, account for ˜20% of skeletal neoplasms and cause significant morbidity/mortality (Bovee, et al., 2010, Nat Rev Cancer 10, 481-488). Methods of diagnosing such tumors is well known in the art (Adler, C L, 1979, Pathol Res Pract. 166(1):45-58). Benign and malignant cartilaginous tumors arise sporadically at all ages, but there are also cartilage tumor syndromes, including hereditary multiple exostoses (HME) (Pannier et al., 2009, Best Pract Res Clin Rheumatol 22, 45-54; Pansuriya et al., 2010, Int J Clin Exp Pathol 3, 557-569)., the multiple enchondromatosis disorders (Ollier disease and Maffucci syndrome), and metachondromatosis (MC) (Kennedy, L. A., 2003, Radiology 148, 117-118). The molecular mechanisms underlying the development and progression of most cartilage tumors remain incompletely understood. MC is an autosomal dominant tumor syndrome featuring multiple exostoses and enchondromas. Recently, disease-associated whole-genome sequencing and linkage analysis using high-density SNP arrays uncovered heterogyzous early frameshift or nonsense mutations in PTPN11 in >50% of MC cases. PTPN11 encodes the non-receptor protein-tyrosine phosphatase SHP2, which is required for RAS/ERK pathway activation in most receptor tyrosine kinase (RTK), cytokine receptor, and integrin signaling pathways1,2. Germ line activating mutations in PTPN11 cause Noonan syndrome (NS), whereas PTPN11 mutations that substantially impair SHP2 catalytic activity cause LEOPARD syndrome (LS), both of which show incompletely penetrant skeletal abnormalities. Somatic activating mutations in PTPN11 are the most common cause of the childhood myeloproliferative disease juvenile myelomyelogenous leukemia (JMML) and contribute to several solid tumors. Although PTPN11 is a well established human oncogene, prior to the invention it was unclear how heterozygous loss-of-function PTPN11 alleles cause the cartilage neoplasms in MC. The following materials and methods were used to generate the data described herein. Mice. Ptpn11 floxed (Ptpn11fl) (Yang et al. 2006, Dev Cell 10, 317-327), cathepsin K-Cre (CtskCre) (Nakamura et al., 2007, Cell 130, 811-823, Roza26lacZ (R26lacZ) (Soriano et al., 1999, Nat Genet 21, 70-71), and Rosa26EYFP (YFP) (Srinivas et al., 2001, BMC Dev Biol 1, 41). Cre reporter mice have been described previously. All mice were analyzed on the C57BL/6 background. PCR genotyping was performed using known methods. Antibodies and Reagents. The following antibodies were purchased: monoclonal anti-phospho(p)-tyrosine (4G10) was from Millipore; polyclonal antibodies against phospho(p)-Erk1/2, Erk2, p-Akt(Ser473), Akt, Shp2, p-Stat1(Tyr701) and Stat1 were from Cell Signaling Inc.; antibodies against Ihh, Col2α1, and Col10α1 were from Santa Cruz Biotechnology and ABcam, respectively; polyclonal antibodies against YFP were from Invitrogen; and fluorescence-labeled antibodies against CD31, CD44, CD45, CD90, and CD166 were purchased from eBioscience. FGF18 was purchased from Peprotech Inc. UO126 and PD173074 was from Calbiochem and Selleckbio respectively. PF-04449913 was obtained from Pfizer, Inc. Cell isolation and cultures. To isolate YFP+ cartilage cells (CCPs), epiphyseal cartilage was dissected from 2-week-old Ctsk-Control/YFP and Ctsk-KO/YFP mice, digested with hyaluronidase (2.5 mg/ml, Sigma) and Trypsin-EDTA (0.25%, Invitrogen) to remove soft tissues, and then with collagenase D (2.5 mg/ml, Roche) to release all cartilage cells. After washing in PBS, cartilage cells were either analyzed by flow cytometry or YFP+ cells were purified by FACS and placed in short-term cultures of murine mesenchymal culture medium (StemCell Technologies Inc.) containing 10% FBS. Parental ATDC5 cells were purchased from the ATCC and cultured in complete DMEM/F12 medium (1:1) (Invitrogen) as described46. ATDC5 cells stably expressing short hairpin RNAs against murine Shp2 (oligoA:5′GATCCCCGATTCAGAACACTGGGGACTTCAAGAGAGTCCCCAGTGT TCTGAATCTT TTTGGAAA (SEQ ID NO:1)); Oligo B: 5-GATCCCCGATTCAGAACACTGGGGACTTCAAGAGAGTCCC CAGTGTTCTGAATCTTTTTGGAAA (SEQ ID NO:2)) or its scrambled control were established by using pSuper(retro)/puro retroviral vector (Oligoengine, Inc) and pEcopac. Quantitative RT-PCR. RNA was extracted from cultured cells or cartilage lesions captured by laser dissection by using the RNeasy kit (Qiagen). cDNA was synthesized using iScript™cDNA Synthesis Kit (Bio-Rad) and q-PCR was performed by using the RT2SYBR®Green qPCR kit. All values were normalized to Gapdh levels, and qPCR data are expressed as fold-increases compared with controls. Flow Cytometry and FACS. Epiphyseal cartilage cells were stained with fluorescence-labeled antibodies as described47 and analyzed on a BD™ LSR II flow cytometer. YFP+ cells were purified by FACS using a BD Influx™ cell sorter (BD Bioscience, San Diego, Calif.). All flow cytometric data were analyzed with FlowJo software (TreeStar). Histology. Ctsk-Control and KO mice were euthanized at the indicated ages, and femurs, tibiae, and paws were removed and fixed in 4% paraformaldehyde (PFA) overnight at 4° C. Postnatal skeletal tissues were decalcified in 0.5M EDTA before embedding. Tissue sections (5 μm) were stained with Hematoxylin & Eosin (H&E), Alcian blue, or Safranin O. Immunohistochemical staining was performed using fluorescence- or peroxidase-coupled anti-rabbit, mouse, or -goat secondary antibodies, as per the manufacturer's instructions, with Diaminobenzidine (DAB) serving as the substrate. X-gal staining was performed using known methods. Microcomputed Tomography (μ-CT) and x-Ray Analysis. X-ray images of the entire skeleton, knees, metatarsals and phalanges were obtained immediately after euthanasia by using a Faxitron X-ray system (Wheeling, Ill.). After fixation in 4% PFA, μ-CT images of skeletal tissues were scanned with the desktop microcomputer graphic imaging system (μ-CT40, Scanco Medical AG, CH). The number and size of exostoses were measured visually based on x-ray images. Immunoblotting. Cells were lysed in NP-40 buffer (0.5% NP40, 150 mM NaCl, 1 mM EDTA, 50 mM Tris [pH 7.4]), supplemented with a protease inhibitor cocktail (1 mM PMSF, 1 mM NaF, 1 mM sodium orthovanadate, 10 mg/ml aprotinin, 0.5 mg/ml antipain, and 0.5 mg/ml pepstatin), as described17. For immunoblotting, cell lysates (10-50 μg) were resolved by SDS-PAGE, transferred to PVDF membranes, and incubated with primary antibodies for 2 hr or overnight at 4° C. (according to the manufacturer's instructions), followed by HRP-conjugated secondary antibodies. Detection was by enhanced chemiluminescence (Amersham). Statistical Analysis. Differences between groups were evaluated by Student t test or x2 test, as indicated. A p value of <0.05 was considered significant. All analyses were performed by using Excel (Microsoft, Redmond, Wash.) and Prism 3.0 (GraphPad, San Diego, Calif.). Cellular Context-Specific Tumor Suppression by Ptpn11 Global deletion of mouse Ptpn11 results in early embryonic lethality, whereas postnatal deletion has context-dependent effects on tissue development and function. To assess the role of Shp2 in osteoclasts (OC), we crossed Ptpn11fl mice17 to transgenic mice expressing Cre under the control of the endogenous lysozyme M (LysM)-18 or cathepsin K19 (Ctsk)-promoter. These crosses generated Ptpn11fl/+; LysMCre and Ptpn11fl/fl; LysMCre (hereafter, LysM-Control and LysM-KO) and Ptpn11fl/+; CtskCre and Ptpn11fl/fl; CtskCre (hereafter, Ctsk-Control and Ctsk-KO) ( FIG. 1 a ) mice, respectively. Neither Ptpn11fl/+; LysMCre, nor Ptpn11fl/+; CtskCre, mice had a discernible phenotype, so we focused all subsequent analyses on LysM-KO and Ctsk-KO mice. The LysM promoter is active in monocytes, macrophages and osteoclast precursors, whereas the Ctsk promoter reportedly is active only in mature OC. As expected, Shp2 levels were reduced by >80% in bone marrow-derived macrophages (BMM) and OC in LysM-KO and Ctsk-KO mice ( FIG. 5 a ). LysM-KO and Ctsk-KO mice were born at the expected Mendelian ratios and appeared normal for their first 3 weeks post-birth. Subsequently, LysM-KO mice developed mild, age-related osteopetrosis ( FIG. 5 b ). By contrast, Ctsk-KO mice exhibited a dramatic skeletal phenotype, comprising decreased body length, increased bone mineral density, scoliosis, exostoses at the metaphyses of tubular bones (including femurs, tibiae, metatarsals, and phalanges) and rapidly decreasing mobility ( FIG. 1 b - d ). Sections of hindlimb paw and knee joints from 12-week-old Ctsk-KO mice revealed multiple exostoses and enchondromas at the metaphyses of their metatarsals and phalanges ( FIG. 1 d ), tibiae and femurs ( FIG. 5 c,d ), and other bones (data not shown), features strongly resembling human MC. Given that heterozygous PTPN11 frameshift mutations cause MC5,6, our findings indicate that PTPN11 acts as a tumor suppressor gene in cartilage and strongly suggest that loss (or silencing) of the remaining PTPN11 allele is required for tumor formation in MC. To search for the cells responsible for disease in Ctsk-KO mice, we first injected bone marrow (BM) from 6-week-old Ctsk-KO and Ctsk-Control mice (C57/BL6; CD45.2) into lethally irradiated 3-week-old recipients (n=7) (B6.SJL; CD45.1). Flow cytometric analysis revealed high chimerism in the peripheral blood of all recipients ( FIG. 6 a,b ), but no cartilage tumors developed in recipients of Ctsk-KO BM in over 12 months of observation, although they did show increased bone mineral density ( FIG. 6 c ). Increased bone mineral density, but not cartilage neoplasia, is a consequence of defective OC development/function in Ctsk-KO mice, a conclusion consistent with the mild osteopetrosis seen in LysM-KO mice. Next, we turned to lineage-tracing experiments using Rosa26lacZ (R26lacZ) or Rosa26YFP (YFP) Cre reporter mice. Remarkably, Ctsk-Cre, but not LysM-Cre, was expressed in a subset of perichondrial cells within the so-called “Groove of Ranvier” ( FIG. 2 a ). Sections from knee joints collected at post-natal day 10 revealed significant expansion of a cluster of Alcian blue/Safranin O-positive cells in this region in Ctsk-KO, but not Ctsk-Control, mice ( FIG. 2 b , boxed region and FIG. 5 a ). By 2 weeks post-birth, the YFP+ cells had expanded and differentiated into ectopic cartilaginous tissue in compound Ctsk-KO/YFP reporter mice ( FIG. 2 c . boxed region). Exostoses from 12 week-old compound Ctsk-KO/YFP reporter mice consisted of YFP+ chondroid cells at various stages of development, as revealed by cell morphology and Col2α1 and Col10α1 immunostaining ( FIG. 2 d ). Hence, cartilaginous tumors in Ctsk-KO mice (and, by analogy, most likely in MC) result from lack of Shp2 in Ctsk+ cells from the Perichondrial Groove of Ranvier. The Perichondrial Groove of Ranvier is believed to contain chondroprogenitors responsible for circumferential cartilage growth, but these cells have not been well-characterized. We harvested epiphyseal cartilage cells from the distal femurs and proximal tibiae of Ctsk-Control/YFP and Ctsk-KO/YFP mice at P10-12, and analyzed them by flow cytometry. Compared with controls, the frequency of YFP+ cartilage cells from Ctsk-KO/YFP mice increased from by ˜5-fold ( FIG. 3 a ). Within the YFP+ cell population, the percentage of cells staining positive for CD44, CD90, and CD166, but not CD31, also increased ( FIG. 3 b ). Furthermore, expression of Stro1 and Jagged1, two markers associated with chondroprogenitors within the Groove of Ranvier that retain a BrdU label was increased in the Perichondrial Groove of Ranvier of Ctsk-KO mice ( FIG. 3 c ). Taken together, these data suggest that Shp2 regulates the proliferation of a novel cartilage cell population characterized by Ctsk expression, which we hereafter term “Ctsk+ Chondroid Progenitors” (CCPs). Multiple signaling pathways tightly control cartilage development and homeostasis. Hedgehog and PTHRP signaling are particularly important, and aberrant regulation of these pathways causes developmental defects and skeletal tumors. We examined chondrogenic gene expression in cartilage tumors from Ctsk-KO mice by quantitative reverse-transcription PCR (q-PCR). Consistent with our immunostaining data ( FIG. 2 d ), Col2α1 and Col10α1 transcripts were increased; in addition, Ihh and Pthrp levels were elevated substantially ( FIG. 4 a ). These findings prompted us to examine whether and how Shp2 regulates Ihh and Pthrp. During development, cells within the perichondrium make Fgf, which can signal to adjacent cells via Fgfr3 to suppress Ihh expression. Given that Shp2 is required for Fgfr signaling in other cell types2,32, we hypothesized that Shp2 is required for Fgfr3 to suppress Ihh expression. To test this possibility, we assessed the activation state of Fgfr3 signaling components and Ihh expression in CCPs by immunostaining. Erk activation, as assayed by the phosphorylation of Tyr204Thr202, was compromised in the absence of Shp2, whereas Akt and Stat1/3 activation (based on the phosphorylation of Ser473 and Tyr807, respectively) were unaffected ( FIG. 4 a . Furthermore, consistent with our q-PCR data, Ihh expression was elevated in Shp2-deficient CCPs ( FIG. 4 a ). CCPs are rare, rendering detailed biochemical analyses of these cells unfeasible. We therefore tested the effects of Shp2 depletion in ATDC5 chondroid cells by stably expressing either of two shRNAs directed against murine Ptpn11. As in Ctsk-KO mice ( FIG. 4 a ), Fgf18-evoked Erk activation was decreased, while Ihh and Pthrp levels were increased, in Shp2 deficient-ATDC5 cells, compared with cells expressing an shRNA control ( FIG. 4 b ). Conversely, FGFR (PD173074) or MEK (UO126) inhibitor treatment of randomly growing, parental ATDC5 cells led to enhanced Ihh and Pthrp expression ( FIG. 4 c ). Ihh signaling leads to Pthrp production. Hence, our data, along with previous studies, suggested that increased Ihh levels might play a crucial role in MC pathogenesis. If so, then blocking or attenuating Ihh signaling might slow and/or prevent MC development. To test this hypothesis, Control (wild type) and Ctsk-KO mice (5/group) were treated with the Smoothened inhibitor PF-04449913 (100 μg/g body weight) or vehicle control (0.5% methylcellulose) by daily gavage, beginning at 5 weeks of age and continuing for the succeeding 4 weeks. The skeletal phenotype was examined by X-ray, μ-CT, and histological analysis at the end of experiment. Remarkably, Smoothened inhibitor treatment significantly reduced the number ( FIG. 4 d , 7 a - b , 8 a - b ) and size of exostoses ( FIG. 4 d , 7 a - b ) and improved the function of multiple joints. The data indicate that MC results from loss of SHP2 specifically in CCPs, a heretofore poorly characterized cell population within the Perichondrial Groove of Ranvier, which is believed to function as a stem cell niche for joints and as a reservoir for the germinal layer cells of the growth plate. Cells within the Groove of Ranvier express high levels of FGFR3, and removal of these cells prevents longitudinal bone growth. Groove of Ranvier cells can migrate along and reside in articular cartilage, implicating them in the maintenance of articular cartilage homeostasis and possibly in the pathogenesis of degenerative joint diseases, such as osteoarthritis. YFP+ cells were also observed in the articular cartilage of normal mice in our lineage tracing experiments. SHP2, acting downstream of FGFR3 and upstream of the canonical RAS/ERK pathway, regulates CCP proliferation and chondrogenic differentiation. Consequently, PTPN11 deficiency in these cells causes excessive proliferation, chondrogenic differentiation, and cartilage tumorigenesis. MC is associated with heterozygous inactivating mutations in PTPN11, yet Ptpn11fl/+; CtskCre mice are normal, whereas Ctsk-KO mice display a MC-like syndrome. Although it is formally possible that PTPN11 gene dosage effects differ in mouse and man (and thus 50% reduction in SHP2 levels causes MC in humans but not in mouse), we think it is far more likely that loss of the remaining PTPN11 allele (e.g., by LOH or silencing) is required to cause cartilage tumors in MC. If so, then unlike its oncogenic role in JMML, other hematologic malignancies and solid tumors, PTPN11 acts as a classic tumor suppressor gene in cartilage. It has been reported that liver-specific Ptpn11 deletion results in hepatocellular carcinoma. However, we have not observed any liver tumors in our Ptpn11 conditional knockout mice crossed to the same Cre line, nor is PTPN11 clearly implicated in the pathogenesis of human hepatocellular carcinoma. Moreover, our biochemical and pharmacological analysis, together with previous studies, provide an explanation for the apparently paradoxical pro- and anti-oncogenic effects of PTPN11. In both cases, SHP2 is a critical regulator of ERK activation. The activating PTPN11 mutations associated with cancer promote proliferation and survival at least in part via increased ERK activation. Similarly, over-expression or increased activation of normal SHP2 binding proteins such as GAB2, or the presence of pathologic SHP2 binding proteins such as H. pylori CagA, can hyperactivate ERK and contribute to various malignancies. Conversely, SHP2 deficiency is oncogenic in CCPs because in these cells, ERK normally represses the expression of the growth stimulator IHH (which in turn, promotes PTHRP production). Given the mechanism of MC pathogenesis described herein, the results argue for caution in the long term use of MEK and ERK inhibitors. OTHER EMBODIMENTS While the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. The patent and scientific literature referred to herein establishes the knowledge that is available to those with skill in the art. All United States patents and published or unpublished United States patent applications cited herein are incorporated by reference. All published foreign patents and patent applications cited herein are hereby incorporated by reference. Genbank and NCBI submissions indicated by accession number cited herein are hereby incorporated by reference. All other published references, documents, manuscripts and scientific literature cited herein are hereby incorporated by reference. While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
A method for preventing, slowing, or blocking the formation of an exostosis or an enchondromas comprising administering to an animal in need thereof a hedgehog pathway inhibitor such as a Smoothened inhibitor.
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CROSS-REFERENCE TO RELATED APPLICATIONS The present application is related to and claims the benefit of the earliest available effective filing date(s) from the following listed application(s) (the “Related Applications”) (e.g., claims earliest available priority dates for other than provisional patent applications or claims benefits under 35 USC §119(e) for provisional patent applications, for any and all parent, grandparent, great-grandparent, etc. applications of the Related Application(s)). RELATED APPLICATIONS For purposes of the USPTO extra-statutory requirements, the present application constitutes a continuation-in-part of U.S. patent application Ser. No. 11/185,925, entitled PLASMON PHOTOCATALYSIS, naming Roderick A. Hyde as inventor, filed 20 Jul., 2005, which issued on Nov. 13, 2007, U.S. Pat. No. 7,295,723 and is entitled to the benefit of the filing date. For purposes of the USPTO extra-statutory requirements, the present application constitutes a continuation-in-part of U.S. patent application Ser. No. 11/496,763, titled PLASMON PHOTOCATALYSIS, naming Roderick A. Hyde as inventor, filed on 31 Jul., 2006, which issued on Apr. 15, 2008, U.S. Pat. No. 7,359,585 and is entitled to the benefit of the filing date. For purposes of the USPTO extra-statutory requirements, the present application constitutes a continuation-in-part of U.S. patent application Ser. No. 11/496,759, entitled PLASMON PHOTOCATALYSIS, naming Roderick A. Hyde as inventor, filed 31 Jul., 2006 now U.S. Pat. No. 7,406,217, or is an application of which a currently co-pending application is entitled to the benefit of the filing date. For purposes of the USPTO extra-statutory requirements, the present application constitutes a continuation-in-part of U.S. patent application Ser. No. 11/496,766, entitled PLASMON PHOTOCATALYSIS, naming Roderick A. Hyde as inventor, filed 31 Jul., 2006 now U.S. Pat. No. 7,426,322, or is an application of which a currently co-pending application is entitled to the benefit of the filing date. The United States Patent Office (USPTO) has published a notice to the effect that the USPTO's computer programs require that patent applicants reference both a serial number and indicate whether an application is a continuation or continuation-in-part. Stephen G. Kunin, Benefit of Prior - Filed Application , USPTO Official Gazette Mar. 18, 2003. The present Applicant Entity (hereinafter “Applicant”) has provided above a specific reference to the application(s) from which priority is being claimed as recited by statute. Applicant understands that the statute is unambiguous in its specific reference language and does not require either a serial number or any characterization, such as “continuation” or “continuation-in-part,” for claiming priority to U.S. patent applications. Notwithstanding the foregoing, Applicant understands that the USPTO's computer programs have certain data entry requirements, and hence Applicant is designating the present application as a continuation-in-part of its parent applications as set forth above, but expressly points out that such designations are not to be construed in any way as any type of commentary and/or admission as to whether or not the present application contains any new matter in addition to the matter of its parent application(s). All subject matter of the Related Applications and of any and all parent, grandparent, great-grandparent, etc. applications of the Related Applications is incorporated herein by reference to the extent such subject matter is not inconsistent herewith. TECHNICAL FIELD The present application relates, in general, to plasmons and photocatalysis. SUMMARY A waveguide or other approach may deliver plasmon energy to induce, change the rate of, or otherwise affect a chemical reaction, such as a photocatalytic reaction. In one embodiment, a waveguide includes a conductive layer that converts electromagnetic energy into plasmon energy. A portion of the waveguide and/or the conductive layer may have variations configured to produce and/or support plasmons. In one embodiment, the waveguide is incorporated in a system that may include an energy source and/or elements configured to direct and/or focus the energy. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 a shows a waveguide with a conductive layer, a plasmon propagating on the outer surface of the conductive layer, and a photocatalyst in the field of the plasmon. FIG. 1 b shows a waveguide with an outer conductive layer, a plasmon propagating on the outer surface of the conductive layer, and a defect on the conductive layer that converts plasmons into electromagnetic energy. FIG. 1 c shows a photocatalyst with energy incident on it, having a band gap between energy levels. FIG. 1 d shows a bent fiber waveguide with a particle near the bend and a photocatalyst near the particle. FIG. 2 a shows a vessel with material and a waveguide, where a laser emits electromagnetic energy that is reflected from a mirror into the waveguide. FIG. 2 b shows the vessel with material after photocatalysis. FIG. 2 c shows a laser with a fiber that extends over a long distance to a vessel with a material in it. FIG. 3 a shows a source of electromagnetic energy, a mirror, and a vessel that holds an array of waveguides, where the electromagnetic energy reflects off the mirror into the waveguides. FIG. 3 b shows a top view of the array of waveguides. FIG. 4 shows a waveguide that is partially covered with a conductive layer. FIG. 5 shows a waveguide that has a conductive layer, a dielectric layer, and a photocatalyst layer, where the waveguide is near an interaction material. FIG. 6 shows a waveguide having a conductive layer with an aperture, where the aperture is bordered by a grating. FIG. 7 shows a waveguide with a periodic array of conductive material. DETAILED DESCRIPTION Methods for interacting electromagnetic energy with matter are known; for example, in U.S. Pat. No. 4,481,091 entitled CHEMICAL PROCESSING USING ELECTROMAGNETIC FIELD ENHANCEMENT to Brus, et al., which is incorporated herein by reference. Specifically, electromagnetic energy may be delivered to a spatial position in order to induce a photocatalytic reaction, as described in U.S. Pat. No. 5,439,652 entitled USE OF CONTROLLED PERIODIC ILLUMINATION FOR AN IMPROVED METHOD OF PHOTOCATALYSIS AND AN IMPROVED REACTOR DESIGN to Sczechowski, et al., which is incorporated herein by reference. Further, electromagnetic energy may be delivered to a given area using surface plasmons. Surface plasmons have been used as sensors, as described in J. Homola, S. S. Yee, and G. Gauglitz, “Surface plasmon resonance sensors: review”, Sensors and Actuators B, Volume 54, 1999, 3-15, which is incorporated herein by reference. One type of surface plasmon resonance sensor uses optical waveguides. In this technique, electromagnetic energy propagates down a metal-coated waveguide, a portion of the electromagnetic energy couples to an evanescent wave in the metal coating, and the evanescent wave couples to plasmons on the outer surface of the metal. Surface plasmons may exist on a boundary between two materials when the real parts of their dielectric constants ∈ and ∈′ have different signs, for example between a metal and a dielectric. In a first embodiment, shown in FIG. 1 a , a waveguide 102 includes an outer conductive layer 104 . Electromagnetic energy 106 is coupled into the waveguide 102 and propagates in the waveguide 102 . This electromagnetic energy couples to an evanescent wave in the conductive layer 104 , which couples to a plasmon 113 on an outer surface 108 of the conductive layer 104 . The conductive layer 104 forms a boundary with an interaction material 110 . The conductive layer 104 may be a high conductivity metal such as silver, gold, or copper, or it may be another type of metal or conductive material. The waveguide may be an optical fiber, a 2d dielectric slab waveguide, or another kind of waveguide. Metal-coated fibers are known to those skilled in the art and various methods exist for coating a fiber with metal, including vacuum evaporation and sputtering. In one embodiment, a chemical reaction is induced by the plasmons 113 . In one embodiment, the chemical reaction is a photocatalytic reaction. In this embodiment, the interaction material 110 may include a photocatalyst 112 . Plasmon energy may be delivered to the photocatalyst 112 by placing the photocatalyst 112 substantially in the field of the plasmon 113 . Plasmon energy may also be delivered to the photocatalyst by causing the plasmon 113 to radiate electromagnetic energy 115 , for example by forming a defect 114 on the surface of the conductive layer, as shown in FIG. 1 b . Although the defect 114 in FIG. 1 b is shown as extending from the conductive layer 104 , in other embodiments the defect may be a deficit of material, may include material or defect integral to the conductive layer 104 , material that is not in intimate contact with the conductive layer 104 , or any other material or structure known to produce electromagnetic energy responsive to plasmon energy. Although the outer layer 104 is described as a conductive layer in the exemplary embodiments of FIGS. 1 a and 1 b , it is not necessary for the layer 104 to be conductive for plasmons 113 to be induced at the interface between layer 104 and the interaction material 110 . Plasmons may occur in other configurations. For example, if the real parts of the dielectric constants (∈ and ∈′) of layer 104 and the interaction material 110 have opposite signs at the interface, plasmons can be produced and one skilled in the art may find a number of configurations and material configurations that establish these conditions. The outer layer may, in one embodiment, comprise vanadium dioxide, which is known to undergo an insulator-to-metal or semiconductor-to-metal phase transition at a certain temperature, as described in R. Lopez, L. A. Boatner, T. E. Haynes, L. C. Feldman, and R. F. Haglund, Jr., “Synthesis and characterization of size-controlled vanadium dioxide nanocrystals in a fused silica matrix”, Journal of Applied Physics, Volume 92, Number 7, Oct. 1, 2002, which is incorporated herein by reference. By incorporating vanadium dioxide into the structure, the ability to produce plasmons could be switched on or off depending on the temperature of the material. In the above description of the generation of plasmons in the waveguide, the plasmons are generated by a guided optical wave, typically through total internal reflection or other guiding or partially guiding approaches in a fiber. Other methods of coupling an electromagnetic wave to a plasmon are possible, some of which are described in W. L. Barnes, A. Dereux, and T. W. Ebbesen, “Surface plasmon subwavelength optics”, Nature, Volume 424, Aug. 14, 2003, 824-830, which is incorporated herein by reference. These methods include and are not limited to prism coupling, scattering from a topological defect on the surface on which the plasmon is to be generated, and periodic corrugation in the surface on which the plasmon is to be generated. These methods may be used to generate plasmons at any point along the waveguide. FIG. 1 a shows plasmons occurring as surface plasmons at the interface between the layer 104 and the interaction material 110 , but plasmons may occur in other spatial locations. Plasmons may also occur at the interface between the layer 104 and the inner material 103 of the waveguide, or they may occur within a material. Plasmons are described in C. Kittel, “Introduction to Solid State Physics”, Wiley, 1995, which is incorporated herein by reference. Generally, photocatalysis is the change in the rate of a chemical reaction in the presence of electromagnetic energy. Many different types of photocatalytic reactions exist. In some types of photocatalysis, the electromagnetic energy directly interacts with the reagents (e.g., by raising a molecule to an excited state, thereby increasing its reactivity). In other cases, the interaction is indirect, with the electromagnetic energy activating an intermediate material which then induces the desired reaction (e.g., by creating an electromagnetic pair in a semiconductor, leading to an activated reaction surface). In photocatalysis, the electromagnetic energy may directly supply the reaction's driving energy, or it may indirectly enable a self-energized reaction (e.g., rhodopsin activated phototransduction in the eye). More detailed description of photocatalysis can be found in Masao Kaneko and Ichiro Okura, “Photocatalysis: Science and Technology”, Springer-Verlag, 2002; and photocatalytic properties and processes involving plasmons can be found, for example, in P. V. Kamat, “Photoinduced transformation in semiconductor-metal nanocomposite assemblies”, Pure & Applied Chemistry, Volume 74, Number 9, 2002, pages 1693-1706; each of which is incorporated herein by reference. A simplified example of a mechanism by which photocatalysis may occur is illustrated in FIG. 1 c , where electromagnetic energy 152 is incident on a photocatalyst 112 . In the embodiment shown in FIG. 1 c , the electromagnetic energy 152 may include energy in the form of a plasmon 113 or in the form of radiated electromagnetic energy 115 as shown in FIGS. 1 a and 1 b , or it may include a combination of both. In the case where the electromagnetic energy 152 includes energy in the form of a plasmon 113 , the electromagnetic energy may include a portion of the plasmon field that extends into the material 110 and/or a portion of the plasmon field that extends into the layer 104 , or it may include a different portion of the plasmon field. The electromagnetic energy 152 causes an electron 153 to move from the valence band 154 to the conduction band 156 of the photocatalyst 112 , creating an electron-hole pair, e− 158 and h+ 160 . The photocatalyst 112 may be chosen according to the frequency of electromagnetic energy 152 that is incident on it. For example, the photocatalyst 112 may be chosen to be one having an energy gap between the valence band 154 and the conduction band 156 corresponding to the energy of the incident electromagnetic energy 152 . Or, for a given photocatalyst 112 , the energy of the incident electromagnetic energy may be chosen to match the energy gap between the valence band 154 and the conduction band 156 . As previously described, plasmon energy may be delivered to the photocatalyst 112 by placing the photocatalyst 112 substantially in the field of the plasmon 113 , or it may also be delivered to the photocatalyst 112 by causing the plasmon 113 to radiate electromagnetic energy 115 . A wide range of general applications of photocatalysis are described later in this application. FIG. 1 d shows an embodiment where the waveguide 102 is an optical fiber that does not have a conductive layer 104 . In this embodiment, the waveguide 102 includes an electromagnetic field 180 outside the waveguide, where there exists a metal nanoparticle 182 . The electromagnetic field 180 couples to plasmons 184 on the nanoparticle 182 , and the plasmons 184 on the nanoparticle 182 may deliver energy to a photocatalyst 112 . Creation of plasmons on a particle in an electromagnetic field is described in P. G. Kik, A. L. Martin, S. A. Maier, and H. A. Atwater, “Metal nanoparticle arrays for near field optical lithography”, Proceedings of SPIE, 4810, 2002 which is incorporated herein by reference. Such a configuration may be useful, for example, in photocatalytic lithography. In the embodiment shown in FIG. 1 d , the waveguide 102 is an optical fiber and the electromagnetic field 180 outside the fiber is created by a bend 186 in the fiber, such a bend being known to cause electromagnetic energy to leave the fiber. The waveguide 102 may, in other embodiments, be a different kind of waveguide, and electromagnetic energy 180 may be incident on the nanoparticle 182 from the waveguide 102 via ways other than a bend in a fiber. In one embodiment, shown in FIG. 2 a , a laser 202 that emits electromagnetic energy in a first wavelength band provides electromagnetic energy 204 . Various methods exist for coupling electromagnetic energy into a waveguide, and those skilled in the art will be familiar with the various methods for guiding and coupling electromagnetic energy. In the embodiment shown in FIG. 2 a , the emitted electromagnetic energy 204 is reflected from a mirror 206 into the waveguide 208 that, in turn, guides the electromagnetic energy 204 into or near to a vessel 210 configured to hold an interaction material 212 . The interaction material 212 may be any state of matter including but not limited to a solid, liquid, gas, or plasma. The interaction material before photocatalysis 212 is shown in FIG. 2 a and the interaction material after photocatalysis 213 is shown in FIG. 2 b . Although FIGS. 2 a and 2 b are drawn with a vessel 210 , the vessel is not critical and the waveguide may be configured to deliver energy to, for example, ground water or another environment in which the material that receives energy from the waveguide does not require a vessel. Although a mirror 206 is shown here as an example of an optical element that may be used to direct energy into the waveguide, in some cases different or additional optical elements may be used, such as lenses, polarizers, filters, or other elements, which may be used alone or in combination. Further, the preceding list refers to elements typically associated with optical wavelengths of energy, and for other wavelength bands different elements may be required for directing and focusing the energy. Moreover, in various embodiments, the source of electromagnetic energy may be formed integrally with other elements, may be coupled evanescently to a waveguide, may be a pigtailed assembly, or may be any other configuration for producing the appropriate coupled electromagnetic energy. Moreover, although a single laser 202 is presented in FIG. 2 a , more than one source of electromagnetic energy may be coupled to the waveguide 208 . For example two or more lasers may be coupled to the waveguide 208 . Such lasers may be of a common wavelength or may, in some configurations, have different wavelengths, depending upon various design considerations. FIG. 2 a shows the source of electromagnetic energy being a laser 202 that is outside the waveguide 208 . In other embodiments the source of electromagnetic energy may be inside the waveguide 208 , or there may be a source or sources outside the waveguide 208 and/or a source or sources inside the waveguide 208 . Sources of electromagnetic radiation that may be included in a waveguide are known to those skilled in the art, and may include a microcavity semiconductor laser such as that described in U.S. Pat. No. 5,825,799, to Seng-Tiong Ho, Daniel Yen Chu, Jian-Ping Zhang, and Shengli Wu, which is incorporated herein by reference. FIG. 2 c shows a case similar to that in FIG. 2 a , but where electromagnetic energy 204 is configured to travel some distance to the interaction material 212 . In one case, the electromagnetic energy is guided by a preliminary waveguide 214 , where the preliminary waveguide 214 may be an optical fiber configured to guide electromagnetic energy over distances of thousands of miles or more. The waveguide may be continuous, where the preliminary waveguide 214 is substantially the same as the waveguide 208 , or, as shown in FIG. 2 c , the waveguide may be discontinuous, and may possibly include elements such as the mirror 206 shown in FIG. 2 c . In other embodiments, the preliminary waveguide 214 may be configured to guide the electromagnetic energy over shorter distances, for example, distances on the order of meters. In other embodiments, there may be no preliminary waveguide 214 , and the electromagnetic energy may travel in free space to the waveguide 208 . In one embodiment, the electromagnetic energy is in the visible or UV portion of the electromagnetic spectrum. In this case, the waveguide may be an optical fiber, an integrated waveguide, a polymeric waveguide, or any other waveguide suited for such energy. The optical fiber may comprise a graded index of refraction or a step index of refraction, or the optical fiber could be another of the many types of optical fibers known to those skilled in the art. In the case of electromagnetic energy in the UV portion of the electromagnetic spectrum, the waveguide may comprise quartz. In another embodiment, the waveguide may comprise a photonic band-gap material and/or a photonic band-gap like structure. One example of such a guide may be found in S. A. Maier, P. E. Barclay, T. J. Johnson, M. D. Friedman, and O. Painter, “Low-loss fiber accessible plasmon waveguide for planar energy guiding and sensing,” Applied Physics Letters, Volume 84, Number 20, May 17, 2004, 3990-3992, which is incorporated herein by reference, where a waveguide is formed from a silicon membrane having a two-dimensional pattern of gold dots patterned on one side of the substrate. The patterned gold dots constrain propagating electromagnetic energy to the silicon by forming a photonic band gap, and also allow plasmons to propagate along the array of gold dots. The size and spacing of the gold dots affect the guiding properties of the waveguide. While the exemplary embodiment above implements a waveguide and plasmon generator with a photonic bandgap material in a particular arrangement, a variety of other configurations employing photonic bandgap materials may be implemented. In some approaches the photonic bandgap structure and plasmon generating structure may be integral, while in other approaches, the photonic bandgap material may be arranged primary for guiding and a second structure can be combined to produce plasmons responsive to the guided energy. In another embodiment, shown in FIG. 3 a , a source 302 produces electromagnetic energy 304 . Optical elements 306 , 308 (in this case, a converging lens 306 and a mirror 308 ) direct the energy to an array of waveguides 310 . Although the array 310 in FIG. 3 is shown having seven waveguides, it may have any number of waveguides. A vessel 312 is configured to hold the array of waveguides 310 and a material 314 that reacts with electromagnetic energy. Although FIG. 3 a is drawn with a vessel 312 , the vessel is not critical and the array of waveguides may be configured to deliver energy to, for example, ground water or another environment in which the material that receives energy from the fibers does not require a vessel. The waveguides in the array may be configured so that the distribution of energy near the waveguides depends on the separations 316 between the waveguides (illustrated in FIG. 3 b ). Such an energy dependence was demonstrated in J. P. Kottmann and O. J. F. Martin, “Plasmon resonant coupling in metallic nanowires”, Optics Express, Volume 8, Number 12, Jun. 4, 2001; V. A. Podolskiy, A. K. Sarychev, and V. M. Shalaev, “Plasmon modes and negative refraction in metal nanowire composites”, Optics Express, Volume 11, Number 7, Apr. 7, 2003; S. A. Maier, M. L. Brongersma, P. G. Kik, and H. A. Atwater, “Observation of near-field coupling in metal nanoparticle chains using far-field polarization spectroscopy”, Physical Review B, Volume 65, page 193408; and V. A. Podolskiy, A. K. Sarychev, E. E. Narimanov, and E. M. Shalaev, “Resonant light interaction with plasmonic nanowire systems”, Journal of Optics A, Volume 7, S32-S37, Jan. 20, 2005; each of which is incorporated herein by reference. For example, plasmon modes of waveguides were shown to interact under certain conditions. Placing waveguides in relatively close proximity can create relatively high field strengths between the waveguides, so the reacting material 314 may be placed in the region where a high field strength is expected to induce or speed up a reaction. Further, the plasmon modes (spatial distribution and excitation frequency) may be a function of the number, type, and separation of the plasmon waveguides, so the location, distribution, and/or type of the reacting material 314 may be chosen according to the modes excited in the array. The array may be a random array, possibly characterized by an average separation 316 between waveguides, or it may be a substantially ordered array, possibly having separations 316 between waveguides characterized by a mathematical formula. Although the references above describe plasmons on a wire or arrays of conducting dots, plasmons on different kinds of waveguides, such as a metal-coated fiber, may also interact. Further, although FIGS. 3 a and 3 b show the waveguides not touching, crossing, joining, or intersecting, in some embodiments it may be desirable for the waveguides to be non-parallel, and the waveguides may in some cases touch, cross, join, or intersect, depending on the particular design. In some embodiments, the waveguide may be completely coated with a conductor, as shown in FIG. 1 . However, it may be desirable in other embodiments to only partially cover the waveguide with a conductor, as shown in FIG. 4 . In the embodiment shown in FIG. 4 , electromagnetic energy 404 is directed into the waveguide 406 . A portion of the waveguide 406 is covered with a conductor 402 , and surface plasmons may be created on the surface of the conductor 402 . Although FIG. 4 shows a waveguide having a single portion of the waveguide coated with a conductor, in other embodiments more than one portion of the waveguide may be coated with a conductor. FIGS. 1 a and 1 b show examples of configurations in which a photocatalyst 112 is near the outer surface 108 of the conductive layer 104 . It may also be possible for the photocatalyst 112 to be joined to the waveguide 102 . FIG. 5 shows a waveguide 102 having a conductive layer 104 , a dielectric layer 501 in intimate contact with the conductive layer 104 , and a photocatalyst layer 502 in intimate contact with the dielectric layer 501 . FIG. 5 shows the dielectric layer 501 and the photocatalyst layer 502 as being continuous, but this need not be the case and in some cases the conductive layer 104 , the dielectric layer 501 , and/or the photocatalyst layer 502 may only partially cover the waveguide, possibly in a periodic or semi-periodic array. The thicknesses and materials of the layers 104 , 501 , and 502 may be chosen to produce plasmons in the layer 501 that interact with the photocatalyst layer 502 . The layer 501 is described as a dielectric layer, however in a different configuration the layers 104 and 501 may be a different combination of materials for which plasmons exist at the interface, as previously described. In an arrangement shown in FIG. 6 , the configuration may be used to deliver energy to a location, such as a location containing a photocatalyst 112 , using a waveguide. In this approach a set of gratings 602 , 604 are positioned beside a sub-wavelength aperture 606 in a conductive layer 607 . As described for example in A. Degiron and T. W. Ebbeson, “The role of localized surface plasmon modes in the enhanced transmission of periodic subwavelength apertures”, Journal of Optics A: Pure Applied Optics, Volume 7, Jan. 20, 2005, pages S90-S96, incorporated herein by reference, such gratings can produce plasmons 113 that then couple through an aperture 606 and thereby increase throughput of electromagnetic energy 608 through the aperture 606 . By integrating this configuration with a waveguide 610 , energy can couple from the waveguide to locations outside of the waveguide. FIG. 6 is shown with only one aperture in the conductive layer 607 , however it may be desirable to have more than one aperture 606 in the conductive layer 607 . In one approach, each of a plurality of apertures is surrounded by respective gratings 602 , 604 . Further, the gratings 602 , 604 are shown having four periods, but the number of periods may depend on the particular application. As described in Degiron, the wavelength(s) corresponding to the maximum transmission of energy through the aperture 606 may depend on the period 612 of the gratings 602 , 604 , the dielectric constant of the gratings 602 , 604 , and the dielectric constant of the surrounding materials 110 , 614 . The gratings 602 , 604 , although shown only on the interface between the conductive layer 607 and the material 614 , may be on the interface between the conductive layer 607 and the material 110 , or they may be on both interfaces. The gratings 602 , 604 may have periodic variations that are substantially parallel to each other, or the gratings 602 , 604 may extend radially from the aperture 606 . The aperture 606 is described as being sub-wavelength, but transmission of energy 608 may occur in configurations having apertures that are equal to or larger than the wavelength of transmitted energy 608 . Although a photocatalyst 112 is shown as receiving the energy from the aperture 606 , it may be desirable for another type of material to react with the energy. In an arrangement shown in FIG. 7 , a waveguide 704 such as an optical fiber or a 2d dielectric slab may include a patterned array of conductive material 706 . Electromagnetic energy 702 is coupled into the waveguide 704 and propagates in the waveguide 704 . In FIG. 7 , the conductive material is configured with spacings 708 wherein the spacings are separated by a distance 710 . A patterned array of conducting material having an array of holes that are smaller than the wavelength of energy incident on them may have enhanced transmission of this energy through the holes, as described in W. L. Barnes, W. A. Murray, J. Dintinger, E. Devaux, and T. W. Ebbesen, “Surface Plasmon Polaritons and Their Role in the Enhanced Transmission of Light through Periodic Arrays of Subwavelength Holes in a Metal Film”, Physical Review Letters, Volume 92, Number 10, Mar. 9, 2004, page 107401; S. C. Hohng, Y. C. Yoon, D. S. Kim, V. Malyarchuk, R. Müller, Ch. Lienau, J. W. Park, K. H. Yoo, J. Kim, H. Y Ryu, and Q. H. Park, “Light emission from the shadows: Surface plasmon nano-optics at near and far fields”, Applied Physics Letters, Volume 81, Number 17, Oct. 21, 2002, pages 3239-3241; each which is incorporated herein by reference. A waveguide having such an array may therefore have enhanced transmission at certain wavelengths through the array 706 . The wavelengths corresponding to enhanced transmission, as described in Hohng, may depend on the materials 712 , 110 bordering the array. In FIG. 7 the array 706 is shown extending along the entire length of the waveguide 704 , but in other configurations the array may extend over only a portion of the waveguide 704 . The spacings 708 are described as being sub-wavelength, but transmission of energy 716 may occur in configurations having apertures that are larger than the wavelength of transmitted energy 716 . Although FIG. 7 shows a patterned array of conductive material 706 , in another embodiment the dimension of the inner material 712 may be configured to vary, possibly in a periodic or semi-periodic way. The variations may produce a surface having substantially square-wave variations similar to that shown in FIG. 7 , or the variations may produce a different kind of pattern such as a substantially sine-wave variation or another kind of variation. In such an embodiment, the conductive material 706 may also have a thickness that varies, possibly periodically or semi-periodically, or the conductive material 706 may have a substantially uniform thickness. Plasmons may be produced on a boundary between two materials when the real parts of their dielectric constants ∈ and ∈′ have different signs, such as in areas where the conductive layer 104 and the material 110 are in contact. For example, in the periodic or semiperiodic arrangement shown in FIG. 7 , plasmon energy can interact with the interaction material 110 in a corresponding periodic or semiperiodic pattern. Moreover, in configurations such as those shown in FIGS. 4 and 6 it may be possible to produce plasmons or electromagnetic energy in a defined spatial extent. These configurations may allow plasmon energy to be distributed through a reaction area in a selected pattern, and may produce localized reactions, may produce reactions that have asymmetric spatial patterns, or may catalyze a reaction in a distributed fashion. Moreover, in configurations where plasmons are produced in defined areas along the waveguide, the energy may propagate further and/or with less dissipation in the guide than in configurations where the energy is converted to plasmons along the entire length of the waveguide. Such targeted spatial distributions of plasmons and/or electromagnetic energy may be useful, for example, in photocatalytic lithography, as described in J. P. Bearinger, A. L. Hiddessen, K. J. J. Wu, A. T. Christian, L. C. Dugan, G. Stone, J. Camarero, A. K. Hinz and J. A. Hubbell, “Biomolecular Patterning via Photocatalytic Lithography”, in Nanotech, 2005 Vol. 1, “Technical Proceedings of the 2005 NSTI Nanotechnology Conference and Trade Show, Volume 1”, Chapter 7: DNA, Protein, Cells and Tissue Arrays; and in Jae P. Lee and Myung M. Sung, “A new patterning method using photocatalytic lithography and selective atomic layer deposition”, Journal of the American Chemical Society, Volume 126, Number 1, Jan. 14, 2004, pages 28-29, each of which is incorporated herein by reference. Targeted spatial distributions of plasmons and/or electromagnetic energy may also be useful in applications where the interaction material 110 is distributed in an array, where the interaction material 110 may comprise different kinds or different amounts of material in different parts of the array, or where it is desired to control the amount of energy delivered to the material 110 according to spatial position. In general, photocatalysis has many applications and the embodiments shown in FIGS. 1-7 have a wide variety of applications. Some applications of photocatalysis are described in Akira Fujishima, “Discovery and applications of photocatalysis—Creating a comfortable future by making use of light energy”, Japan Nanonet Bulletin, Issue 44, May 12, 2005, which is incorporated herein by reference. These include the extraction of hydrogen from water for use as a clean energy source, oxidation of materials (potentially for disinfection and deodorization or for cleanup of toxic sites), and creating surfaces with “superhydrophilicity” and self-cleaning properties. A wide range of applications is detailed in Fujishima, and one skilled in the art may apply the embodiments shown in FIGS. 1-7 to applications of photocatalysis, including those applications described above and detailed in Fujishima. For example, the photocatalyst layer 502 in FIG. 5 may include titanium dioxide and the material 110 may, in one embodiment, be water, where the photocatalytic process is designed to remove impurities in the water. Some of the embodiments in FIGS. 1-7 include materials that are patterned, potentially on the nanoscale. For example, FIG. 7 shows a metal grating having a periodicity that may be fabricated using techniques such as lithography and/or deposition of material. Such techniques are known to those skilled in the art and may produce features having sizes on the order of nanometers or possibly less. These techniques may be used to fabricate features in a regular array, a desired pattern, or a single defect. In the case of a single defect, the size of the defect may be on the order of a nanometer, as described in Kik. In this disclosure, references to “optical” elements, components, processes or other aspects, as well as references to “light” may also relate in this disclosure to so-called “near-visible” light such as that in the near infrared, infra-red, far infrared and the near and far ultra-violet spectrums. Moreover, many principles herein may be extended to many spectra of electromagnetic radiation where the processing, components, or other factors do not preclude operation at such frequencies, including frequencies that may be outside ranges typically considered to be optical frequencies. The foregoing detailed description has set forth various embodiments of the devices and/or processes via the use of block diagrams, diagrammatic representations, and examples. Insofar as such block diagrams, diagrammatic representations, and examples contain one or more functions and/or operations, it will be understood as notorious by those within the art that each function and/or operation within such block diagrams, diagrammatic representations, or examples can be implemented, individually and/or collectively, by a wide range of hardware, materials, components, or virtually any combination thereof. Those skilled in the art will recognize that it is common within the art to describe devices and/or processes in the fashion set forth herein, and thereafter use standard engineering practices to integrate such described devices and/or processes into elements, processes or systems. That is, at least a portion of the devices and/or processes described herein can be integrated into optical, RF, X-ray, or other electromagnetic elements, processes or systems via a reasonable amount of experimentation. Those having skill in the art will recognize that a typical optical system generally includes one or more of a system housing or support, and may include electrical components, alignment features, one or more interaction devices, such as a touch pad or screen, control systems including feedback loops and control motors (e.g., feedback for sensing lens position and/or velocity; control motors for moving/distorting lenses to give desired focuses). Such systems may include image processing systems, image capture systems, photolithographic systems, scanning systems, or other systems employing optical, RF, X-ray or other focusing or refracting elements or processes. While particular embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that, based upon the teachings herein, changes and modifications may be made without departing from this invention and its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as are within the true spirit and scope of this invention. Furthermore, it is to be understood that the invention is solely defined by the appended claims. It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense, that is as “including, but not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to inventions containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and/or “an” should typically be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, typically means at least two recitations, or two or more recitations).
Plasmons on a waveguide may deliver energy to photocatalyze a reaction. The waveguide or other energy carrier may be configured to carry electromagnetic energy and generate plasmon energy at one or more locations proximate to the waveguide, where the plasmon energy may react chemically with a medium or interaction material.
1
FIELD OF THE INVENTION The present invention is concerned with a class of polymer precursors with narrow molecular weight distribution and the production therefrom of physiologically soluble polymer therapeutics, functionalised polymers, pharmaceutical compositions and materials, all with similar molecular weight characteristics and a narrow molecular weight distribution. BACKGROUND OF THE INVENTION Polymer Therapeutics (Duncan R: Polymer therapeutics for tumour specific delivery Chem & Ind 1997, 7, 262-264) are developed for biomedical applications requiring physiologically soluble polymers and include biologically active polymers, polymer-drug conjugates, polymer-protein conjugates, and other covalent constructs of polymer with bioactive molecules. An exemplary class of a polymer-drug conjugate is derived from copolymers of hydroxypropyl methacrylamide (HPMA) which have been extensively studied for the conjugation of cytotoxic drugs for cancer chemotherapy (Duncan R: Drug-polymer conjugates: potential for improved chemotherapy. Anti - Cancer Drugs, 1992, 3, 175-210. Putnam D, Kopecek J: Polymer conjugates with anticancer activity. Adv.Polym.Sci., 1995, 122, 55-123. Duncan R, Dimitrijevic S, Evagorou E: The role of polymer conjugates in the diagnosis and treatment of cancer. STP Pharma, 1996, 6, 237-263). An HPMA copolymer conjugated to doxorubicin known as PK-1, is currently in Phase II evaluation in the UK. PK-1 displayed reduced toxicity compared to free doxorubicin in the Phase I studies (Vasey P, Twelves C, Kaye S, Wilson P, Morrison R, Duncan R, Thomson A, Hilditch T, Murray T, Burtles S, Cassidy J: Phase I clinical and pharmacokinetic study of PKI (HPMA copolymer doxorubicin): first member of a new class of chemotherapeutic agents: drug-polymer conjugates. Clin. Cancer Res., 1999, 5, 83-94). The maximum tolerated dose of PK-1 was 320 mg/m 2 which is 4-5 times higher than the usual clinical dose of free doxorubicin. The polymers used to develop Polymer Therapeutics may also be separately developed for other biomedical applications where the polymer conjugate is developed (e.g. as a block copolymer) to form aggregates such as polymeric micelles and complexes (Kataoka K, Kwon G, Yokoyama M, Okano T. Sakurai Y: Block copolymer micelles as vehicles for drug delivery. J. Cont.Rel., 1993, 24, 119-132. Inoue T, Chen G, Nakamae K, Hoffman A: An AB block copolymer of oligo(methyl methacrylate) and poly(acrylic acid) for micellar delivery of hydrophobic drugs. J Cont. Rel., 1998, 51, 221-229. Kwon G, Okano T: Polymeric micelles as new drug carriers. Adv. Drug Del. Rev., 1996, 21, 107-116.). The polymers used to develop Polymer Therapeutics may also be separately developed for other biomedical applications that require the polymer be used as a material rather than as a physiologically soluble molecule. Thus, drug release matrices (including microspheres and nanoparticles), hydrogels (including injectable gels and viscious solutions) and hybrid systems (e.g. liposomes with conjugated poly(ethylene glycol) (PEG) on the outer surface) and devices (including rods, pellets, capsules, films, gels) can be fabricated for tissue or site specific drug delivery. Polymers are also clinically widely used as excipients in drug formulation. Within these three broad application areas: (1) physiologically soluble molecules, (2) materials and (3) excipients, biomedical polymers provide a broad technology platform for optimising the efficacy of a therapeutic bioactive agent. Therapeutic bioactive agents which can be covalently conjugated to a polymer include a drug, peptide and protein. Such conjugation to a soluble, biocompatible polymer can result in improved efficacy of the therapeutic agent. Compared to the free, unconjugated bioactive agent, therapeutic polymeric conjugates can exhibit this improvement in efficacy for the following main reasons: (1) altered biodistribution, (2) prolonged circulation, (3) release of the bioactive in the proteolytic and acidic environment of the secondary lysosome after cellular uptake of the conjugate by pinocytosis and (4) more favourable physicochemical properties imparted to the drug due to the characteristics of large molecules (e.g. increased drug solubility in biological fluids) (Note references in Brocchini S and Duncan R: Polymer drug conjugates: drug release from pendent linkers. The Encyclopedia of Controlled Drug Delivery, Wiley, N.Y., 1999, 786-816.). Additionally, the covalent conjugation of bioactive agents to a polymer can lead to improved efficacy that is derived from the multiple interactions of one or more of the conjugated bioactive agents with one or more biological targets. Such polyvalent interactions between multiple proteins and ligands are prevalent in biological systems (e.g. adhesion of influenza virus) and can involve interactions that occur at cell surfaces (e.g. receptors and receptor clusters) (Mammen M, Choi S, Whitesides GM: Polyvalent interactions in biological systems: Implications for design and use of multivalent ligands and inhibitors. Angew. Chem. Int. Ed. 1998, 37, 2754-2794. Whitesides G, Tananbaum JB. Griffin J, Mammen M: Molecules presenting a multitude of active moieties. PCT Int. Appl. WO 9846270). Multiple simultaneous interactions of a polymer bioactive conjugate will have unique collective properties that differ from properties displayed by the separate, individual, unconjugated bioactive components of the conjugate interacting monovalently. Additionally, an appropriately functionalised polymer can interact with mucosal membranes (e.g. in the gastrointestinal, respiratory or vaginal tracts) by polyvalent interactions. Such a property is valuable for prolonged and/or preferential localisation of a functionalised polymeric excipient used for site specific delivery or altering optimally the biodistribution of a bioactive agent. Additionally polymer bioactive agent conjugates and/or aggregates can be designed to be stimuli responsive (Hoffman A, Stayton PS: Interactive molecular conjugates. U.S. Pat. No. 5,998,588), for example, to be for membranelytic after being taken up by a cell by endocytosis. These polymeric constructs must incorporate the membrane penetration features seen in natural macromolecules (toxins and transport proteins) and viruses. Cytosolic access has been shown to be rate limiting during polymer-mediated transfection (Kichler A, Mechtler A, Mechtler K, Behr JP, Wagner E: Influence of membrane-active peptides on lipospermine/DNA complex mediated gene transfer, Bioconjugate Chem., 1997, 8(2), 213-221.). Many of the cationic polymers (e.g. (poly-L-lysine) (PLL) and poly(ethyleneimine) (PEI), chitosan and cationic PAMAM dendrimers) that have been used for in vitro transfection studies are either cytotoxic (IC 50 values <50 μg/ml) or hepatotropic after i.v. injection. Such molecules are totally unsuitable for in vivo/clinical development. Alternative endosomolytic molecules have been proposed but are either too toxic (i.e. poly(ethylenimine) or potentially immunogenic (e.g. fusogenic peptides, reviewed (Plank C, Zauner W, Wagner E: Application of membrane-active peptides for drug and gene delivery across cellular membranes, Advanced Drug Delivery Reviews, 1998, 34, 21-35. Wagner E, Effects of membrane-active agents in gene delivery, J. Cont. Release, 1998, 53, 155-158.). Polymers, some with zwitterionic features, (Richardson S, Kolbe H, Duncan R: Potential of low molecular mass chitosan as a DNA delivery system: Biocompatibility, body distribution and ability to complex and protect DNA Int. J. Pharm., 1999 178, 231-243. Richardson S, Ferruti P, Duncan R: Poly(amidoamine)s as potential endosomolytic polymers: Evaluation of body distribution in normal and tumour baring animals, J. Drug Targeting, 1999) have been shown to have considerable potential for membranelytic activity as a function of pH which could be capable of rupturingthe endosome to gain access to the ctyosolic environment of cells. For the treatment of cancer there are marked improvements in therapeutic efficacy and site specific passive capture through the enhanced permeability and retention (EPR) effect (Matsumura Y, Maeda H: A new concept for macromolecular therapeutics in cancer chemotherapy; mechanism of tumoritropic accumulation of proteins and the antitumour agent SMANCS. Cancer Res., 1986, 6, 6387-6392.). The EPR effect results from enhanced permeability of macromolecules or small particles within the tumour neovasculature due to leakiness of its discontinuous endothelium. In addition to the tumour angiogenesis (hypervasculature) and irregular and incompleteness of vascular networks, the attendant lack of lymphatic drainage promotes accumulation of macromolecules that extravasate. This effect is observed in many solid tumours for macromolecular agents and lipids. The enhanced vascular permeability will support the demand of nutrients and oxygen for the unregulated growth of the tumour. Unless specifically addressed for tumour cell uptake by receptor-medicated endocytosis, polymers entering the intratumoural environment are taken up relatively slowly by fluid-phase pinocytosis. Whereas cellular uptake of low molecular weight molecules usually occurs by rapid transmembrane passage, the uptake of pysiologically soluble polymers occurs almost exclusively by endocytosis (Mellman I: Endocytosis and molecular sorting. Ann. Rev. Cell Develop. Biol., 1996, 12, 575-625. Duncan R, Pratten M: Pinocytosis: Mechanism and Regulation. In: Dean R, Jessup W, eds. Mononuclear Phagocytes: Physiology and Pathology. Amsterdam: Elsevier Biomedical Press, 1985; 27-51.). Polymer bioactive conjugates can additionally include a conjugated bioactive agent that would induce receptor-mediated endocytosis (Putnam D, Kopecek J: Polymer conjugates with anticancer activity. Adv.Polym.Sci., 1995, 122, 55-123. Duncan R: Drug-polymer conjugates: potential for improved chemotherapy. Anti - Cancer Drugs, 1992, 3, 175-210.). For example, HPMA copolymer-doxorubicin containing additionally galactosamine localises selectively in the liver due to uptake by the hepatocyte asialoglycoprotein receptor (Duncan R, Seymour L, Scarlett L, Lloyd J, Rejmanova P, Kopecek J: N-(2-Hydroxypropyl)methacrylamide copolymers with pendant galactosamine residues. Fate after intravenous administration to rats. Biochim. Biophys. Acta., 1986, 880, 62-71. Seymour L, Ulbrich K, Wedge S, Hume I, Strohalm J, Duncan R: N-(2hydroxypropyl)methacrylamide copolymers targeted to the hepatocyte galactose-receptor: pharmacokinetics in DBA-2 mice. Br. J. Cancer, 1991, 63, 859-866.). Enhanced vascular permeability is well known to be present within tissue which has undergone an inflammatory response due to infection or autoimmunedisease. Conjugates of polymers and appropriate bioactive agents could also exploit the vascular premeability gradient between healthy and inflammed tissue in these conditions leading to the passive and preferential accumulation of the conjugate at the inflammed site similar to that observed which has been shown at tumour sites in cancer. Polymer bioactive conjugates designed to be therapeuctically efficacious by multivalent interactions are being developed as agonists, partial agonists, inverse agonists and antagonists for a multitude of clinical applications including the treatment of diseases such as cancer and infection (Griffin JH, Judice JK: Novel multi-binding therapeutic agents that modulate enzymatic processes, WO 99/64037. Yang G, Meier-Davis S, Griffin JH:Multivalent agonists, partial agonists, inverse agonists and antagonists of the 5-HT3 receptors, WO 99/64046. Christensen BG, Natarajan M, Griffin JH: Multibinding bradykinin antagonists, WO 99/64039. Fatheree P. Pace JL, Judice JK, Griffin JH: Preparation of multibinding Type II topoisomerase inhibitors as antibacterial agents, WO 99/64051. Linsell MS, Meier-Davis S, Griffin JH: Multibinding inhibitors of topoisomerase, WO 99/64054. Griffin JH, Moran EJ, Oare D: Novel therapeutic agents for macromolecular structures. PCT Int. Appl. WO 9964036. Griffin JH, Judice JK: Linked polyene macrolide antibiotic compounds and uses, WO 99/64040. Choi S, Mammen M, Whitesides GM, Griffin JH: Polyvalent presenter combinatorial libraries and their uses, WO 98/47002.). The four main parts of a polymer-bioactive agent conjugate are (1) polymer, (2) bioactive agent conjugating linker which can be either a pendent chain conjugating linker or a mainchain terminating conjugating linker, (3) solution solubilising pendent chain and (4) the conjugated bioactive agent. While each component has a defined biological function, the sum is greater than the parts because these four components together as a conjugate produce a distinct profile of pharmacological, pharmacokinetic and physicochemical properties typical of physiologically soluble polymer-bioactive agent conjugates. The polymer is not a mere carrier for the bioactive agent. The polymer component of the conjugate can be synthetic or naturally derived. Synthetically derived polymers have the advantage that structure property correlations can be more effectively modulated and correlated in unique ways (Brocchini S, James K, Tangpasuthadol V, Kohn J: Structure-property correlations in a combinatorial library of degradable biomaterials. J. Biomed. Mater. Res., 1998, 42(1), 66-75. Brocchini S, James K, Tangpasuthadol V, Kohn J: A Combinatorial Approach For Polymer Design. J. Am. Chem. Soc., 1997, 119(19), 4553-4554.). The solution properties of the polymer are directly responsible for defining the circulation half-life, rate of cellular uptake, minimising deleterious side effects of potent cytotoxic drugs and imparting favourable physicochemical properties (e.g. increasing the solubility of lipophilic drugs). The solution properties of a polymer bioactive agent conjugate will be influenced by the structure of the polymer, the conjugating linker and the property modifying pendent chain. Also the amount or loading of the bioactive agent will affect the solution properties of a polymer bioactive conjugate. The solution properties of the conjugate will affect the ultimate biological profile of the conjugate. Solution properties will contribute to the biocompatibility and rate of clearance of polymer bioactive agent conjugates. Biocompatibility includes the lack of conjugate binding to blood proteins and the lack of a immunogenic response. The conjugate will display a plasma clearance which is primarily governed by the rate of kidney glomerular filtration and the rate of liver uptake. Macromolecules of molecular weight of 40,000-70,000 Da, depending on solution structure, readily pass through the kidney glomerulus and can be excreted. However, as the solution size of a molecule increases with molecular weight (or by forming supramolecular aggregates), extended blood clearance times result. Structural features including polymer flexibility, charge, and hydrophobicity affect the renal excretion threshold for macromolecules within this size range (Duncan R, Cable H, Rypacek F, Drobnik J, Lloyd J: Characterization of the adsorptive pinocytic capture of a polyaspartamide modified by the incorporation of tyramine residues. Biochim. Biophys. Acta, 1985, 840, 291-293.). Neutral, hydrophilic polymers including HPMA copolymers, polyvinylpyrrolidone (PVP) and poly(ethylene glycol) (PEG) have flexible, loosely coiled solution structures whereas proteins tend to be charged and exhibit more compact solution structures. For example, the molecular weight threshold limiting glomerular filtration of HPMA copolymer-tyrosinamide in the rat was approximately 45,000 Da (Seymour L, Duncan R, Strohalm J, Kopecek J: Effect of molecular weight (Mw) of N-(2-hydroxypropyl)methacrylamide copolymers on body distributions and rate of excretion after subcutaneous, intraperitoneal and intravenous administration to rats. J. Biomed. Mater. Res., 1987, 21, 1341-1358.) and the threshold for proteins is approximately 60K Da. Copolymers HPMA have been extensively studied for the conjugation of cytotoxic drugs for cancer chemotherapy (Duncan R, Dimitrijevic S, Evagorou E: The role of polymer conjugates in the diagnosis and treatment of cancer. STP Pharma, 1996, 6, 237-263. Putnam D, Kopecek J: Polymer conjugates with anticancer activity. Adv.Polym.Sci., 1995, 122, 55-123. Duncan R: Drugolymer conjugates: potential for improved chemotherapy. Anti - Cancer Drugs, 1992, 3, 175-210.). The homopolymer of HPMA is soluble in biological fluids, readily excreted at molecular weights of less than 40,000 Da [4], is non-toxic up to 30 glkg, does not bind blood proteins [5], and is not immunogenic (Rihova B, Ulbrich K, Kopecek J, Mancal P: Immunogenicity of N-(2-hydroxypropyl)methacrylamide copolymers-potential hapten or drug carriers. Folia Microbioa., 1983, 28, 217-297. Rihova B, Kopecek J, Ulbrich K, Chytry V: Immunogenicity of N-(2-hydroxypropyl)methacrylamide copolymers. Makromol. Chem. Suppl., 1985, 9, 13-24. Rihova B, Riha I: Immunological problems of polymer-bound drugs. CRC Crit. Rev. Therap. Drug Carrier Sys., 1985, 1, 311-374. Rihova B, Ulbrich K, Strohalm J, Vetvicka V, Bilej M, Duncan R, Kopecek J: Biocompatibility of N-(2-hydroxypropyl)methacrylamide copolymers containing adriamycin. Immunogenicity, effect of haematopoietic stem cells in bone marrow in viva and effect on mouse splenocytes and human peripheral blood lymphocytes in vitro. Biomaterials, 1989, 10, 335-342.) Like poly(ethylene glycol) (PEG) which is generally recognised as safe (GRAS) and is used for the conjugation of proteins, HPMA is biocompatible and is thus a good candidate polymer for conjugation with bioactive agents. Since HPMA copolymers are hydrophilic, solublisation of hydrophobic drugs is possible. Since each HPMA copolymer conjugate is a different copolymer, other hydrophilic polymers similar to HPMA may be good candidate polymers for the conjugation of bioactive agents. Additionally, the molecular weight characteristics of a polymer-bioactive agent conjugate will influence the ultimate biological profile of the conjugate. Biodistribution and pharmacological activity are known to be molecular weight-dependent. For example, blood circulation half-life (Cartlidge S, Duncan R. Lloyd J, Kopeckova-Rejmanova P, Kopecek J: Soluble crosslinked N-(2-hydroxypropyl)methacrylamide copolymers as potential drug carriers. 2. Effect of molecular weight on blood clearance and body distribution in the rat intravenous administration. Distribution of unfractionated copolymer after intraperitoneal subcutaneous and oral administration. J Con. Rel., 1986, 4, 253-264.), renal clearance, deposition in organs (Sprincl L, Exner J, Sterba 0, Kopecek J: New types of synthetic infusion solutions III. Elimination and retention of poly[N-(2-hydroxypropyl)methacrylamide] in a test organism. J. Biomed. Mater. Res., 1976, 10, 953-963.), rates of endocytic uptake (Duncan R. Pratten M, Cable H, Ringsdorf H, Lloyd J: Effect of molecular size of 125l-labelled poly(vinylpyrrolidone) on its pinocytosis by rat visceral yolk sacs and peritoneal macrophages. Biochem. J., 1981, 196, 49-55. Cartlidge S, Duncan R, Lloyd J, Rejmanova P, Kopecek J: Soluble crosslinked N2-hydroxypropyl)methacrylamide copolymers as potential drug carriers. 1. Pinocytosis by rat visceral yolk sacs and rat intestinal cultured in vitro. Effect of molecular weight on uptake and intracellular degradation. J. Cont. Rel., 1986, 3, 55-66.) and biological activity can depend on polymer molecular weight characteristics (Kaplan A: Antitumor activity of synthetic polyanion. In: Donaruma L, Ottenbrite R. Vogl O, eds. Anionic Polymeric Drugs. New York: Wiley, 1980; 227-254. Ottenbrite R, Regelson W, Kaplan A, Carchman R, Morahan P, Munson A: Biological activity of poly(carboxylic acid) polymers. In: Donaruma L, Vogi O, eds. Polymeric Drugs. New York: Academic Press, 1978; 263-304. Butler G: Synthesis, characterization, and biological activity of pyran copolymers. In: Donaruma L, Ottenbrite R, Vogl O, eds. Anionic Polymeric Drugs. New York: Wiley, 1980; 49-142. Muck K, Rolly H, Burg K: Makromol. Chem., 1977, 178, 2773. Muck K, Christ O, Keller H: Makromol. Chem., 1977, 178, 2785. Seymour L: Synthetic polymers with intrinsic anticancer activity. J. Bioact. Compat. Polymers, 1991, 6, 178-216.). In clinical applications requiring the cellular uptake of a polymeric bioactive agent conjugate with subsequent release of the bioactive agent intracellularly, the linker must be designed to be degraded to release the bioactive agent at an optimal rate within the cell. It is preferable that a the bioactive agent conjugating linker does not degrade in plasma and serum (Vasey P, Duncan R, Twelves C, Kaye S, Strolin-Benedetti M, Cassidy J: Clinical and pharmacokinetic phase 1 study of PK1(HPMA) copolymer doxorubicin. Annals of Oncology, 1996, 7, 97.). Upon endocytic uptake into the cell, the conjugate will localise in the lysosomes. These cellular organalles contain a vast array of hydrolytic enzymes including proteases, esterases, glycosidases, phosphates and nucleases. For the treatment of cancer, potent cytotoxic drugs have been conjugated to polymers using conjugation linkers that degrade in the lysosome while remaining intact in the bloodstream. Since many drugs are not pharmacologically active while conjugated to a polymer, this results in drastically reduced toxicity compared to the free drug in circulation. The conjugating linker structure must be optimised for optimal biological activity. Incorporation of a polymer-drug linker that will only release drug at the target site can reduce peak plasma concentrations thus reducing drug-medicated toxicity. If the drug release rate is optimised, exposure at the target can be tailored to suit the mechanism of action of the bioactive agent being used (e.g. use of cell-cycle dependent antitumour agents) and to prevent the induction of resistance. To be effective, it is important that polymer bioactive agent conjugates are designed to improve localisation of the bioactive agent in the target tissue, diminish deleterious exposure in potential sites of toxicity in other tissue and to optimise the release rate of the bioactive agent in those applications where its release is required for a biological effect. The rate of drug release from the polymer chain can also vary according to the polymer molecular weight and the amount of drug conjugated to the polymer. As greater amounts of hydrophobic drug are conjugated onto a hydrophilic polymer, the possibility to form polymeric micelles increases (Ulbrich K, Konak C, Tuzar Z, Kopecek J: Solution properties of drug carriers based on poly[N-(2hydroxypropyl)methacrylamide] containing biodegradable bonds. Makromol. Chem., 1987, 188, 1261-1272.). Micellar conjugate structures may hinder access of the lysosomal enzymes to degrade the linker and release the conjugated drug. Additionally, hydrophilic polymers conjugated to hydrophobic drugs can exhibit a lower critical solution temperature (LCST) where phase separation occurs and the conjugate becomes insoluble. Simple turbidometric assays (Chytry V, Netopilik M, Bohdanecky M, Ulbrich K: Phase transition parameters of potential thermosensitive drug release systems based on polymers of N-alkylmethacrylamides. J. Biomater. Sci. Polymer Ed., 1997, 8(11), 817-824.) have been used as a preliminary screen to determine the propensity for phase separation at various HPMA copolymer-doxorubicin conjugates of different molecular weight and drug loading (Uchegbu F, Ringsdorf H, Duncan R: The Lower Critical Solution Temperature of Doxorubicin Polymer Conjugates. Proceed. Intern. Symp. Control. Rel. Bioact. Mater., 1996.). As a bioactive agent is released from a polymer due to linker degradation it would be expected that changes in polymer conformation will occur that might also lead to diffences in drug release rate with time (Pitt C, Wertheim J, Wang C, Shah S: Polymer-drug conjugates: Manipulation of drug delivery kinetics. Macromol. Symp., 1997, 123, 225-234. Shah S, Werthim J, Wang C, Pitt C: Polymer-drug conjugates: manipulating drug delivery kinetics using model LCST systems. J. Cont. Rel., 1997, 45, 95-101.)and therefore pharmacological properties. The extent of drug loading and its influence on polymer solution properties is an important, and yet poorly understood phenomenon which must be correlated to structure-property relationships of the polymer-bioactive agent conjugate to lead to optimisation of the the in viva biological properties of therapeutic polymer bioactive agent conjugates. Currently HPMA copolymer-drug conjugates are prepared by a polymer analogous reaction of a low molecular weight drug (e.g. doxorubicin) with a copolymeric precursor which incorporates both the bioactive agent conjugating linker and the solution solubilising pendent chain (Rihova B, Ulbrich K, Strohalm J, Vetvicka V, Bilej M, Duncan R, Kopecek J: Biocompatibility of N-(2-hydroxypropyl)methacrylamide copolymers containing adriamycin. Immunogenicity, effect of haematopoietic stem cells in bone marrow in viva and effect on mouse splenocytes and human peripheral blood lymphocytes in vitro. Biomaterials, 1989, 10, 335-342. Kopecek J, Bazilova H: Poly[N-(hydroxypropyl)methecrylamide]-I. Radical polymerisation and copolymerisation. Eur. Polymer J., 1973, 9, 7-14. Strohalm J, Kopecek J: Poly[N-(2-hydroxypropyl)methacrylamide] IV. Heterogeneous polymerisation. Angew. Makromol. Chem., 1978, 70, 109-118. Rejmanova P, Labsky J, Kopecek J: Aminolyses of monomeric and polymeric 4-nitrophenyl esters of N-methacryloylamino acids. Makromol. Chem., 1977, 178, 2159-2168. Kopecek J: Reactive copolymers of N-(2-Hydroxypropyl)methacrylamide with N-methacryloylated derivatives of L-leucine and L-phenylalanine. Makromol. Chem., 1977, 178, 2169-2183. Kopecek J: The potential of water-soluble polymeric carriers in targeted and site-specific drug delivery. J. Cont. Rel., 1990, 11, 279-290.). The vast majority of polymer bioactive agent conjugates prepared by the polymer analogous reaction are prepared by the reaction of the bioactive agent with a copolymeric precursor (Note references in Brocchini S and Duncan R: Polymer drug conjugates: drug release from pendent linkers. The Encyclopedia of Controlled Drug Delivery, Wiley, N.Y., 1999, 786-816.). The disadvantage of using a copolymer precursor is that for each change in the structure or relative amounts of (1) the bioactive agent conjugating linker or (2) the solution solubilising pendent chain, a new copolymeric precursor must be prepared. Since pendent chain structure is important for the biological profile of a polymer bioactive agent a copolymeric precursor is required to study each conjugate possessing modified conjugating linkers. Solution structure is a function of all the structural features of a bioactive agent polymer conjugate. To elucidate the solution-structure correlations of either the polymer mainchain, conjugating linker or solution solubilising pendent chain requires a different copolymer precursor for each variation of each component. It is not possible to even use the same copolymeric precursor to vary the amount or loading of the conjugated bioactive agent. If loading of the bioactive agent is to be varied and is to be less than the relative stoichiometry of the conjugating pendent chain, then the remaining conjugating pendent chains will not be conjugated to a drug, and the remaining conjugating pendent chains will be terminate with some other inert molecule. The polymer analogous reaction requires that the copolymeric precursor possess functionality on the conjugation pendent chain termini that is reactive (e.g. a p-nitrophenol active ester of a carboxylic acid) so that upon addition of a bioactive agent, the agent will form a covalent bond with the conjugation pendent chain to become linked to the polymer. Thus if a loading of the bioactive agent is to be less than the relative stoichiometry of the conjugating pendent chain, the reactive functionality must be quenched with a reagent other than the bioactive agent or preferably in this situation, a new polymeric precursor be prepared. These procedures tend to produce polymer conjugates with a wide distribution of structures. It thus becomes impossible to accurately determine structure-property correlations. Clearly, if a loading of the bioactive agent greater than the relative stoichiometry of the conjugation pendent chain is desired, then another copolymeric precursor must be prepared. Since many polymer bioactive agent conjugates are co-poly-(methacrylamides), the polymer analogous reaction is conducted on a co-poly(methacrylamide) precursor. It is not possible to make the vast majority of such precursors with a narrow molecular weight distribution with a polydisperisty index of less than 2 except in special cases where a copolymer precursor happens to precipitate from the polymerisation solution at a molecular weight below the renal threshold. It is also not possible to make several different copoly(methacrylamides) all possessing the same molecular weight characteristics, e.g. all possessing the same degree of polymerisation and the same molecular weight distribution. The copoly-(methacrylamide) precursors tend to be prepared by free radical polymerisation which typically produce random copolymers typically with a polydisperisity (PD)>1.5-2.0. Furthermore since the relative stoichiometry of the conjugated bioactive agent, and thus the conjugating linker, is less than the solution solubilising pendent chain, the polymer analogous reaction is frequently on a copolymer precuresor with a low relative stoichiometry of reactive sites for the conjugation of the bioactive agent. This inefficient conjugation strategy is often burdened with competitive hydrolysis reactions and other consuming side reaction that result in conjugating linkers not covalently linked to the bioactive agent (Mendichi R, Rizzo V, Gigli M, Schieroni A G: Molecular characterisation of polymeric antitumour drug carriers by size exclusion chromatograpgy and universal calibration. J. Liq. Chrom. and Rel. Technol., 1996, 19(10), 1591-1605. Configliacchi E, Razzano G, Rizzo V, Vigevani A: HPLC methods for the determination of bound and free doxorubicin and of bound and free galactosamine in methacrylamide polymer-drug conjugates. J. Pharm. Biomed. Analysis, 1996, 15, 123-129.). This not only causes significant structure heterogenaity between batches, but also causes significant waste of the bioactive agent because it has not been conjuated and its recovery is too expensive. In the case of conjugate developed for endocytic uptake into a cell, the lysosomal degradation of bioactive agent conjugating pendent chains with pendent chains not linked to the bioactive pendent chain. This competition complicates the pharmacology and pharmacokinetics of the polymer bioactive agent conjugate. Polymer-bioactive agent conjugates and biomedical polymers currently used for medical applications are, from the perspective of regulatory agencies (e.g. Medicines Control Agency, FDA) not structurally defined. Many conjugates display broad molecular weight distribution and random incorporation of the conjugated bioactive agent. Frequently, the structure of the conjugating linker is varied due to racimisation or incomplete conjugation of the bioactive agent to each of the conjugating linkers. Future development of physiologically soluble polymers used in the development of polymer-bioactive agent conjugates (i.e. polymer therapeutics) requires that more defined conjugate structures be prepared for study. In this way it will become possible to more accurately elucidate structure-property correlations that influence the biological profile of these macromolecular therapeutics. This is not possible by conducting the polymer analogous reaction on many different copolymeric precursors. There is a need to prepare polymer-bioactive conjugates which have a more narrow molecular weight distribution than are currently available. There is also a need to ensure that each bioactive conjugating linker is structurally the same and is covalently bound to the polymer and the bioactive agent. Additionally there is a need for a more efficient strategy in preclinical development where conjugates with similar molecular weight characteristics are prepared for study and where solution properties can also be varied without changing the molecular weight characteristics of the polymer mainchain. Since HPMA copolymer conjugates are poly(methacrylamides) then any techniques developed that will meet the requirements to prepare such conjugates can also be used to prepare other poly(methacrylates) for other healthcare and consumer applications where the resultant polymer can be used either as a soluble molecule, processible material that can be fabricated into a device or as an excipient. Since only a small limited number of acrylamide homo- and co-polymers with narrow molecular weight distribution can be prepared, then for speciality applications there is need for processes that provide a means to prepare such polymers. These limitations for conducting the polymer analogous reaction on a copolymer precursor can be alleviated by conducting the polymer analogous reaction with a homopolymeric precursor that has a narrow molecular weight distribution and where each repeat unit is reactive site. Conjugation of a bioactive agent or a derivative is carried out in a first reaction to covalently link the bioactive agent to the polymer. The conjugation is efficient because each repeat unit on the homopolymer precursor is a reactive site available for reaction. Upon conjugation of the bioactive agent, the intermediate precursor is a copolymer comprised of most repeat units being terminated still with a reactive chemical functional group. These are are then allowed to react with a reagent which will become the solution solubilising pendent chain in the final conjugate. By using one such narrow molecular weight distribution homopolymeric precursor it becomes possible to prepare many copolymer conjugates all possess the same narrow molecular weight distribution. Each conjugate will also possess the same molecular weight characteristics of the degree of polymerisation and polydispersity index that the homopolymeric percursor possesses. This invention is concerned with the synthesis by controlled radical polymerisation processes (Sawamoto M, Masami K: Living radical polymerizations based on transition metal complexes. Trends Polym. Sci. 1996, 4, 371-377. Matyjaszewski K:, Mechanistic and synthetic aspects of atom transfer radical polymerization. Pure Appl. Chem. 1997, A34, 1785-1801. Chiefari J, Chong Y, Ercole F, Krstina J, Jeffery J, Le T, Mayadunne R, meijs G, Moad C, Moad G, Rizzardo E, Thang S: Living free-radical, polymerization by reversible addition-fragmentation chain transfer: the RAFT process. Macromolecules, 1998, 31, 5559-5562. Benoit D, Chaplinski V, Braslau R. Hawker C: Development of a universal alkoxyamine for “living” free radical polymerizations. J. Am. Chem. Soc., 1999, 121, 3904-3920.) of narrow molecular weight distribution homopolymer precursors with a polydispersity index of less than 1.2. These controlled radical polymerisation processes have so far not been shown to give directly acrylamide homo- and co-polymers with narrow molecular weight distribution. This invention is also concerned with the use of these homopolymeric precursors to prepare physiologically soluble polymer bioactive agent conjugates, polymer therapeutics, functionalised polymers, pharmaceutical compositions and materials. SUMMARY OF THE INVENTION One embodiment of the present invention provides a polymer comprising the unit (I) wherein R is selected from the group consisting of hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl, carboxylic acid, carboxy-C 1-6 alkyl, or any one of C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl substituted with a heteroatom within, or attached to, the carbon backbone; R 1 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl groups; X is an acylating group and wherein the polymer has a polydispersity of less than 1.4, preferably less than 1.2 and a molecular weight (Mw) of less than 100,000. The acylating group X is preferably a carboxylate activating group and is generally selected from the group consisting of N-succinimidyl, pentachlorophenyl, pentafluorophenyl, para-nitrophenyl, dinitrophenyl, N-phthalimido, N-norbornyl, cyanomethyl, pyridyl, trichlorotriazine, 5-chloroquinilino, and imidazole. Preferably X is an N-succinimidyl or imidazole moiety. Preferably R is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 aralkyl and C 1 -C 6 alkaryl, C 1 -C 6 alkylamido and C 1 -C 6 alkylamido. Most preferably R is selected from hydrogen or methyl. Preferably R 1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl or isomers thereof. Most preferably R 1 is selected from hydrogen or methyl. The polymer of the present invention may be a homopolymer incorporating unit (I), or may be a copolymer or block copolymer incorporating other polymeric, oligomeric or monomeric units. For example, further polymeric units incorporated in the polymer may comprise acrylic polymers, alkylene polymers, urethane polymers, amide polymers, polypeptides, polysaccharides and ester polymers. Preferably, where the polymer is a heteropolymer, additional polymeric components comprise polyethylene glycol, polyaconitic acid or polyesters. The molecular weight of the polymer should ideally be less than 100,000, preferably 50,000 where the polymer is to be used as a physiologically soluble polymer (in order that the renal threshold is not exceeded). Preferably the molecular weight of the polymer is in the range of 50,000-4000, more preferably 25,000-40,000. Another embodiment of the present invention is a polymer comprising the unit (II) wherein R 2 is selected from hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl, carboxylic acid and carboxy-C 1-6 alkyl; R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl and isomers thereof, Z is a pendent group selected from the group consisting of NR 4 R 5 , SR 6 and OR 7 , wherein R 4 is an acyl group, preferably an aminoacyl group or oligopeptidyl group; R 5 is selected from hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl; R 6 and R 7 are selected from the group consisting of hydrogen, C 1 C 12 alkyl, C 1 -C 12 alkenyl, C 1 -C 12 aralkyl, C 1 -C 12 alkaryl, C 1 -C 12 alkoxy and C 1 -C 12 hydroxyalkyl, and may contain one or more cleavable bonds and may be covalently linked to a bioactive agent. Generally the polymer has a polydispersity of less than 1.4, preferably less than 1.2 and a molecular weight (Mw) of less than 100,000, preferably 50,000. Preferably R 2 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 aralkyl and C 1 -C 6 alkaryl, C 1 -C 6 alkylamido and C 1 -C 6 alkylamido. Preferably R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl or isomers thereof. Most preferably R 2 is hydrogen and R 3 is hydrogen or methyl. Z may comprise a peptidic group. Preferably Z comprises one or more aminoacyl groups, preferably 2-6 aminoacyl groups, most preferably 4 aminoacyl groups. In a particularly preferred embodiment group Z comprises a glycine-leucine-phenylalanine-glycine linkage. The aminoacyl linkage is most preferably a peptide linkage capable of being cleaved by preselected cellular enzymes, for instance, those found in liposome of cancerous cells. In another preferred embodiment group Z comprises a cis-aconityl group. This group is designed to remain stable in plasma at neutral pH (˜7.4), but degrade intracellularly by hydrolysis in the more acidic environment of the endosome or liposome (˜pH 5.5-6.5). The pendent chain Z may additionally be covalently bound to a ligand or bioactive agent. The ligand may be any ligand which is capable of polyvalent interactions. Preferred bioactive agents are anti-cancer agents such as doxorubicin, daunomycin and paclaxitol. A further preferred polymer of the present invention has the structure (III) wherein R 8 and R 9 are selected from the same groups as R 2 and R 3 respectively, Q is a solubilising groups selected from the group consisting of C 1 C 12 alkyl, C 1 -C 12 alkenyl, C 1 -C 12 aralkyl, C 1 -C 12 alkaryl, C 1 -C 12 alkoxy, C 1 -C 12 hydroxyalkyl, C 1 -C 12 alkylamido, C 1 -C 12 alkylamido, C 1 -C 12 alkanoyl, and wherein p is an integer of less than 500. Preferably Q comprises an amine group, preferably a C 1 -C 12 hydroxyalkylamino group, most preferably a 2-hydroxypropylamino moiety. This group is designed to be a solubilising group for the polymer in aqueous solutions. Generally the polymer of the present invention is a water soluble polyacrylamide homo- or copolymer, preferably a polymethacrylamide or polyethacrylamide homo- or copolymer. In a further embodiment, the present invention provides a process for the production of a polymer, comprising the polymerisation of a compound (IV) wherein R is selected from the group consisting of hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl, carboxylic acid, carboxy-C 1-6 alkyl, or any one of C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl substituted with a heteroatom within, or attached to, the carbon backbone; R 1 is selected from the group consisting of hydrogen and C 1 -C 6 alkyl groups preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl and isomers thereof; X is an acylating group, preferably a carboxylate activating group; wherein the process is a controlled radical polymerization, to produce a narrow weight distribution polymer comprising the unit (I) wherein n is an integer of 1 to 500. Preferably R is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 aralkyl and C 1 -C 6 alkaryl, C 1 -C 6 alkanoyl, C 1 -C 6 alkylamido and C 1 -C 6 alkylamido. Preferably R 1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl or isomers thereof. Where the polymerization is carried out by atom transfer radical polymerization, a suitable radical initiator is utilised. Such initiators commonly comprise alkylhalides, preferably alkylbromides. In particular, the initiator is 2-bromo-2-methyl-(2-hydroxyethyl)propanoate. The polymerisation is also carried out in the presence of a polymerisation mediator comprising a Cu(I) complex. Such complexes are usually Cu(I)Br complexes, complexed by a chelating ligand. Typical mediators are Cu(I)Br (Bipy) 2 , Cu(I)Br(Bipy), Cu(I)Br(Pentamethyl diethylene), Cu(I)Br[methyl 6 tris(2-aminoethyl)amine] and Cu(I)Br(N,N,N′,N″,N″-pentamethyidiethylenetriamine). The reaction should take place in the presence of a suitable solvent. Such solvents are generally aprotic solvents, for example tetrahydrofuran, acetonitrile, dimethylformamide, acetone, dimethylsulphoxide, ethyl acetate, methylformamide and sulpholane and mixtures thereof. Alternatively, water may be used. Particularly preferred solvents are dimethylsulphoxide and dimethylformamide and mixtures thereof. Alternatively the polymerization may take place via Nitroxide Mediated Polymerization. Again, a suitable Nitroxide Mediated Polymerization initiator is required. Such an initiator generally has the structure wherein A is selected from the group consisting of C 1- C 12 alkyl, C 1 -C 12 alkenyl, C 1 -C 12 aralkyl, C 1 -C 12 alkaryl, C 1 -C 12 hydroxyalkyl, B and C are individually selected from the group consisting of C 1 C 12 alkyl, C 1 -C 12 alkenyl, C 1 -C 12 aralkyl, C 1 -C 12 alkaryl, C 1 -C 12 hydroxyalkyl, and may together with N form a C 1 -C 12 heterocyclic group and which may contain a heteroatom selected from nitrogen, sulfur, oxygen and phosphorus. Preferably A is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, methylbenzene, ethyl benzene, propylbenzene or isomers thereof. B and C should generally be sterically crowding the groups capable of stabilising a nitroxide radical. Such groups are generally selected from the group consisting of isopropyl, isobutyl, secbutyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, adamantyl, methylbenzene, ethyl benzene, propylbenzene or isomers thereof. Common initiators have these structures outlined below wherein R 9 to R 11 are selected from the group consisting of C 1 -C 12 alkyl, C 1 -C 12 alkenyl, C 1 -C 12 aralkyl, C 1 -C 12 alkaryl, C 1 -C 12 alkoxy, C 1 -C 12 hydroxyalkyl, C 1 -C 12 alkylamido, C 1 -C 12 alkylamido, C 1 -C 12 alkanoyl. Again, suitable solvents for use with Nitroxide Mediated Polymerisations are aprotic solvents as described above. Alternatively, water may be used. A further embodiment of the present invention provides a process for the production of a polymer, comprising the reaction of a polymer having the formula (VI) wherein R 12 is a group selected from the group consisting of hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl and C 1 -C 18 alkaryl groups; R 13 is selected from the group consisting of C 1 -C 6 alkyl groups; E is a carboxylate activating group and r is an integer of 5 to 500; with a reagent HR x , wherein R x is selected from the group consisting of NR 14 R 15 , SR 16 and OR 17 , wherein R 14 is an acyl group, preferably an aminoacyl group or oligopeptidyl group; R 15 is selected from hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl; R 16 and R 17 are selected from the group consisting of hydrogen, C 1 C 12 alkyl, C 1 -C 12 alkenyl, C 1 -C 12 aralkyl, C 1 -C 12 alkaryl, C 1 -C 12 alkoxy and C 1 -C 12 hydroxyalkyl, and may contain one or more cleavable bonds, to form a derivatised polymer having the structure (VII) wherein 1≦s≦r. R 12 is preferably selected from the group consisting of hydrogen, methyl, ethyl and propyl, R 13 is selected from the group consisting of hydrogen, methyl, ethyl and propyl and preferably R 12 is hydrogen and R 13 are methyl. E is selected from the group consisting of N-succinimidyl, pentachlorophenyl, pentafluorophenyl, para-nitrophenyl, dinitrophenyl, N-phthalimido, N-norbornyl, cyanomethyl, pyridyl, trichlorotriazine, 5-chloroquinilino, and imidazole, preferably N-succinimidyl or imidazole, most preferably N-succinimidyl. Preferably HR x is H 2 NR 14 . HR x is generally a nucleophilic reagent capable of displacing E—O, to form a covalent bond with the acyl group attached to CR 3 . Preferably HR x comprises a primary or secondary amine group. Most preferably HR x comprises a cleavable bond such as a aminoacyl linkage or a cis-aconityl linkage as described hereinbefore. Generally HR x is covalently attached to a bioactive agent prior to reaction with (VI) subsequent to the production of a polymer having the structure (VII), an additional step of quenching the polymer may take place. This involves reacting the previously unreacted groups E with a quenching group. This group has the formula HR x ′, preferably comprises an amine moiety and is generally selected to be a solubilising or solubility modifying group for the polymer. Such a quenching compound is, for example a hydrophilic reagent, for example, hydroxypropylamine. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polymer having a polydispersity of less than 1.2. The polymer is preferably an activated polyacrylate ester that is prepared by Controlled Radical Polymerization. These polymers are designed to be derivitisable and may be used to form polymer-drug conjugates having improved biological profile. A particularly preferred polymer of the present invention comprises the structure (X) The activating moiety is an N-succinimidyl group. This particular group has been found to be particularly stable in solution and resists spontaneous hydrolysis. This polymer may be produced by Atom Transfer Polymerization using a Cu(I)Br(pentamethyidiethylene) mediator. The polymerization involved the reaction of a monomer (IX) with a suitable aprotic solvent. In one preferred embodiment the solvent is tetrahydrofuran. In another preferred embodiment the solvent is dimethylsulphoxide and optionally dimethylformamide in admixture thereof. The reaction is preferably carried out under a nitrogen atmosphere and at a temperature of 0-150° C. A preferred temperature range is 30-80° C., most preferably 50-70° C. The polymer comprising the unit (X) may subsequently be derivatised. The carboxyl activating group may be substituted by a suitable nucleophilic reagent. In order to form polymer drug conjugates it is preferable to derivatise unit (X) with a pendant moiety. Such a moiety could comprise a aminoacyl linkage or a hydrolytically labile linkage as defined hereinbefore. Such a linkage can degrade when entering the lysosome of a diseased cell, thus releasing a drug or drug precursor directly to the target site. Preferably a pendent moiety comprises a Gly-Leu-Phe-Gly linkage or a cis aconityl linkage. Such a pendent linkage may be covalently attached to a drug prior to polymer derivitisation or may be capable of being derivatised subsequent of attachment of the pendent moiety to the polymer backbone, In a preferred embodiment the polymer comprising the unit (X) is reacted with less than 1 equivalent of a pendent group, thus only substituting a pre-specified number of N-succinimidyl moieties. This allows a second, quenching step, which substitutes the remaining N-succinimidyl groups with a solubilising group. Such a group aids in the solubilisation of the polymer in aqueous solutions such as biological fluids. A preferred quenching agent should comprise an amine, for example 2-hydroxypropylamine. An overview of a preferred reaction process is provided in scheme 1 below. In this particular example, the drug doxorubicin is attached to the polymer via a GLFG linkage. n is an integer in the range of 1 to 500 and m is the number equivalent of pendent moieties reacted with the activated polymer. CRP processes are known to result in the presence of dormant initiating moieties at the chain ends of linear polymers. In particular the use of nitroxide mediated radical polymerization may be used to prepare narrow molecular weight distributed block copolymers. This allows more defined introduction of drug conjugating pendent chains in the polymer. Outlined in Scheme 2 is an example of this approach to prepare a block copolymer precursor using the CRP process known as nitroxide mediated polymerization (NMP). wherein x and y are the number equivalent of the pendent moiety and quenching group respectively. Thus, polymeric precursors (XI) and (XIII) are designed to be used as polymeric precursors for polymer analogous reactions that are driven to completion to prepare conjugates with narrow molecular weight distributions and with differing m and n repeat structure. Drug conjugation would be localized only in the n repeat structure. Again it is possible to vary the solubilising pendent chain and the drug conjugating pendent chain starting from the polymeric precursor (XI). Defining the location of the drug conjugating pendent chains is necessary to develop more defined polymer-drug conjugates. The extent and location of drug loading and its influence on polymer solution properties is an important, and yet poorly understood phenomenon and will have a fundamental effect on the in vivo properties of therapeutic polymer-conjugates. Thus, this approach will find utility also in the development and optimization of polymer-drug conjugates. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 shows that the broad molecular weight distribution associated with conventional free radical polymerization can be greatly improved using ATP. FIG. 2 . Superimposed IR spectra of narrow MWD homopolymer precursor 3 before and after reaction with 1-amino-2-propanol. FIG. 3 . The GPC for narrow MWD polymethacrylamide 5 (Labelled “A”) derived from the reaction of precursor 3 and 1-amino-2-propanol (2.0 equivalents). The GPC labelled “B” was obtained for 5 that was prepared by conventional free radical polymerization in acetone using AIBN as initiator. FIG. 4 . Cytotoxicity assay using B16F10 cell line of narrow MWD polymethacrylamide 5 prepare from narrow MWD homopolymeric precursor 3 and polymethacrylamide 5 prepared by conventional free radical polymerisation of monomer 6. FIG. 5 . Superimposed IR spectra in the absorbance mode for the sequence of reactions to produce narrow MWD copolymer conjugate 7. FIG. 6 . Superimposed IR spectra in the absorbance mode for the sequence of reactions to produce the intermediate narrow MWD copolymer conjugate 8. FIG. 7 . Superimposed IR spectra displaying the changes in the active ester peak during this sequence of reactions to prepare conjugate 12. FIG. 8 . Preparation of narrow MWD conjugate 12 at 25% loading of 10. FIG. 9 . Preparation of narrow MWD conjugate 13 at 25% loading of 10. FIG. 10 . Preparation of narrow MWD conjugate 14 at 25% loading of 10. FIG. 11 . Preparation of narrow MWD conjugate 15 at 100% loading of 10. FIG. 12 . The GPC for narrow MWD poly(methacryloxy succinimide) 3 (Labelled “A”) that was used as the starting polymer in the chain extension reaction described in example 6. EXAMPLES Example 1 Copper(I) bromide, pentamethyidiethylene ligand, an initiator having the structure, and 2-bromo-2-methyl-(2-hydroxyethyl)propanoate and monomer (IX) were added to THF solvent is a glass flask. The resulting solution was purged with nitrogen to remove oxygen. The flask was sealed and placed in an oil bath at 70° C. for 24 Hr. Samples were prepared for gel permeation chromatography by passing through a neutral aluminium oxide column to remove copper components. Analysis reveals the production of a polymer with a molecular weight of 20,000. A sample of this activated ester homopolymer was quenched with 1-aminopropanol, to give a water soluble polymer whose 1 H NMR spectrum was consistent with that of poly(HPMA). FIG. 1 compares the gel permeation chromatograms of HPMA homopolymer prepared from conventional free radical polymerization with that of 1-aminopropanol quenched poly(methacryloylsuccinimide) prepared using atom transfer radical polymerization. Example 2 Synthesis of narrow molecular weight distribution (MWD) homo-polymeric precursor 3. (A) Homopolymerization in dimethylsulfoxide (DMSO) and dimethylformamide (DMF) and (B) Polymerisation in tetrahydrofuran (THF) and acetone. Synthesis of Methacryloxysuccinimide 1 To N-hydroxysuccinimide (6.6 g, 57 mmol) in dichloromethane (12 ml) was added dropwise a dichloromethane (12 ml) solution of methacryloyl chloride (6.0 g, 57 mmol) simultaneously with a dichloromethane solution (12 ml) of triethylamine (5.8 g, 57 mmol) maintaining the temperature below 5° C. After complete addition the reaction mixture was further stirred for 1 h and then washed with aqueous sodium hydrogen carbonate (0.1 M) and water (×3). The organic phase was then isolated and dried with magnesium sulfate. The solvent was removed to leave a white solid product which was recrystalised from ethyl acetate:hexane. Mass 8 g, m.p.=102° C. ( 1 H, 500MHz, DMSO-d 6 ): 2.00 (3H, s, CH 3 ), 2.84 (4H, s, (CH 2 ) 2 ), 6.09 (1H, s, ═CH 2 ), 6.34 (1H, s, ═CH 2 ). (A) Homogeneous Polymerisation in DMSO: Synthesis of Homopolymeric Precursor—Poly(methacryloxysuccinimide) (1→3). In a typical copper mediated polymerisation using DMSO as solvent at the preferred weight concentration of 56% in monomer 1, copper(I)bromide (31.3 mg, 0.2 mmol), 2-2′-bipyridine (Bpy) (68.3 mg, 0.4 mmol) and monomer 1 (2.00 g, 10.9 mmol) were added to a round bottomed flask which was then sealed with a septum. Into the flask was then injected DMSO (1.3 g). The resulting brown mixture was gently heated until a solution had formed and then purged with argon for approximately 5 min. An argon purged solution of 2-bromo-2-methyl-(2-hydroxyethyl)propanoate 2 (46.1 mg, 0.2 mmol) in DMSO (0.2 g) was then injected into the mixture and the flask was heated to 100° C. in an oil bath. The reaction mixture became viscous after a few minutes and was removed from the heat after 10-15 minutes and rapidly cooled. The polymeric product was isolated by addition of 7-8 ml of DMSO to dissolve the crude product mixture which was slowly added to a stirred solution of acetone (100 ml) to precipitate homopolymeric precursor 3 as a white solid. The acetone solution turned a green colour during the precipitation of polymer 3 due to the dissolution of copper species and the ligand. Atomic absorption analysis indicated the copper content in polymer 3 when at a concentration of 28.0 mg/ml in DMF to be 0.153 ppm. Precipitation of polymer 3 from the DMSO reaction solution into acetone may offer a viable alternative to alumina chromatography which has been typically used in copper mediated polymerisations to remove of copper from the product polymer. The isolated yield of polymer 3 was 1.78 g (89%). The number average molecular weight was 22,700 g/mol and polydispersity index was 1.20. Apparent molecular weights and molecular weight distributions for poly(methacryloxy succinimide) 3 were determined using Waters Styragel HR4 and HR3 (7.3×300 mm) columns coupled to a Gibson 133 refractive index detector, poly(methyl methacrylate) PMMA calibration standards and DMF with 0.1% LiCl eluent. Polymerisations were conducted with different ratios of monomer 1 and initiator 2 to give narrow MWD homopolymeric precursors 3 with different molecular weights. These experiments are listed in Table 1 and have been conducted on reaction scales ranging from 26 g in methacryloxysuccinimide 1. Note also these homogeneous polymerisation conditions in DMSO gave the polymer 3 in a matter of minutes (e.g. experiment 6 in Table 1 was quenched after 2 minutes to give a significant yield of narrow MWD polymer 3. Polymerisations were conducted at temperatures ranging from 80-130° C. to maintain solution homogeneity at methacryloxysuccinimide 1 to solvent weight ratios spanning 33-91%. The preferred solvent was DMSO, but similiar results were obtained with DMF. The weight ratio of monomer 1 to polar solvent (DMSO or DMF) was critical for the outcome of the polymerization. In DMSO at weight ratios less than 56% monomer 1 (e.g. 50 and 41%) resulted in lower yields of polymer (52 and 40% respectively). At weight concentrations higher than 60% monomer 1 in DMSO, the polymerisation solution solidified. Likewise in DMF, the weight concentration of monomer was critical for the outcome of the polymerisation reaction, however the maximal yield in DMF was less than in DMSO. A 50% yield of polymer 3 was isolated at monomer 1:DMF weight ratio of 61%. No polymer was isolated when the reaction was conducted at a monomer 1 weight ratio of 33%. At higher monomer weight concentrations (above 75%), the reaction mixture solidified. TABLE 1 Experiment 1:2:CuBr:Bpy a T, ° C. Yield, % {overscore (M)} n {overscore (M)} w /{overscore (M)} n 1  10:1:1:2 100 85 12500 1.17 2  20:1:1:2 80 92 16800 1.15 3  50:1:1:2 100 89 22700 1.20 4 100:1:1:2 100 96 29000 1.14 5 150:1:1:2 110 80 40700 1.13 6 b 100:1:1:2 100 49 23330 1.15 (a) Ratio of initial monomer and initiator concentrations. (b) Reaction stopped after 2.5 minutes by dilution with DMSO and rapid cooling. (B) Polymerisation in THF and Acetone Copper mediated polymerisations of monomer 1 in solvents such as THF, ethyl acetate and acetone also gave narrow MWD polymer 3. Yields ranged from 10-95% depending on the polymer molecular weight. At molecular weights above 10,000 g/mo the yields which was less than that observed when the polymerisation was conducted in DMSO or DMF. The lower yields occured because of premature precipitation of polymer 3. Exemplary copper mediated polymerisations using 0.5 g in monomer 1 were conducted in THF over a 16 h time period at 70° C. The copper chelating ligand used in these THF reactions was N,N,N′,N″,N″-pentamethyidiethylenetriamine (PMDETA). TABLE 2 Experiment 1:2:CuBr:PMDETA a {overscore (M)} n {overscore (M)} w /{overscore (M)} n 1 100:1:1:1.2 14800 1.1 2 200:1:1:1.2  1800 1.12 3 100:1:0.3:1.2 13100 1.09 (a) Ratio of initial monomer and initiator concentrations. Copper mediated polymerisation in acetone gave a 95% yield of polymer 3 when a 1:2:CuBr:Bpy ratio of 55:1:1:2 was used. When this ratio was changed to 100:1:1:2 a 30% yield of polymer 3 was obtained. Example 3 Hydrolysis of the Narrow MWD Homopolymeric Precursor 3 to give Narrow MWD Poly(methacrylic acid) PMAA Sodium Salt 4 Determination of the absolute molecular weight of PMM 4 by GPC-this gives the degree of polymerisation (DP) which can be used to give the absolute molecular weight of the homopolymeric precursor 3 and polymers derived from precursor 3. A sample of the polymeric precursor, poly(methacryloxysuccinimide) 3 (apparent number average molecular weight of 24,800 g/mol; polydispersity index of 1.20; determined by GPC using DMF eluent and PMMA calibration standards) was hydrolyzed to poly(methacrylic acid) (PMM) sodium salt 4 to demonstrate how the precursor 3 can be utilised to prepare narrow MWD PMM sodium salt 4 and to obtain a better indication of the absolute molecular weight of 3. It is critical to obtain knowledge of the absolute molecular weight of the precursor 3 because it is possible then to know the absolute molecular weight of any polymer derived from precursor 3. Poly(methacryloxysuccinimide) 3 (1 g) was dissolved in DMF (5 ml) and aqueous sodium hydroxide (0.66 g, 3 ml H 2 O) was added dropwise causing precipitation of the polymer. The reaction vessel quickly became warm and a homogeneous solution followed. Water (3 ml) was added to the reaction solution and this was then heated at 70° C. for 24 h after which time further water (approx. 50 ml) was added. The solution was dialysed using regenerated cellulose membrane (SpectraPor, MWCO 2000) against water. Lyophilization of the dialysed solution gave a white solid product 4 (0.3 g) which had an infrared spectrum identical with a commercial sample of narrow MWD PMAA sodium salt. The molecular weight of PMAA sodium salt 4 was determined by GPC with phosphate buffer solution at pH 8.5 as eluent and PMAA sodium salt calibration standards. Since GPC calibration standards were the same as PMAA sodium salt 4 isolated by the hydrolysis of the precursor 3, the molecular weight which was obtained was an absolute molecular weight for polymer 4. The absolute number average molecular weight of PMAA 4 for this example was 22,000 with a polydispersity index of 1.20. This value can be used to determine the degree of polymerization (DP) to know the number of repeat units for any polymer derived from 3. Since the repeat unit molecular weight of PMAA sodium salt 4 is 108, the DP for this sample was approximately 203 (i.e. 22,000 g/mol ÷108 g/mol). This means the DP for the precursor 3 is 203, and since the molecular weight of the repeat unit of precursor 3 is 183 g/mol, then the absolute number average molecular weight of precursor 3 in this example was 37,149 g/mol (i.e. 183 g/mol '203). The value of 203 for the DP of precursor 3 can be used in an analogous fashion to determine the absolute molecular weight of polymers derived from 3. Example 4 Conjugation of Amine to Narrow MWD Homopolymeric Precursor 3 to Produce Narrow MWD Polymethacrylamides. Reaction of Precursor 3 with 1-amino-2-propanol to Give Polymethacrylamide 5. To poly(methacryloxysuccinimide) 3 (0.2 g, polydispersity index 1.2, GPC, DMF eluent, PMMA calibration standards) in DMF (3 ml) was added 1-amino-2-propanol (0.16 ml, 2.1 mmol) drop-wise under stirring at 0° C. The solution was allowed to warm to room temperature and then heated to 50° C. for 16 hr. The reaction mixture was cooled to room temperature and slowly added to acetone (20 ml) to precipitate a solid product. The product was further purified by a second precipitation from methanol into 60:40 (v/v) acetone:diethyl ether to give the water soluble polymethacrylamide 5 as a white solid (polydispersity index 1.3; GPC, phosphate buffer eluent, poly(ethylene glycol) calibration standards). The reaction of 1-amino-2-propanol was followed by IR. Shown in FIG. 1 is the are superimposed IR spectra showing the active ester IR band at 1735 cm −1 in narrow MWD homopolymeric precursor 3 which disappears upon the addition of of 1-amino-2-propanol to give polymethacrylamide 5. FIG. 3 shows the GPC elutagramme of the narrow MWD polymethacrylamide 5 as obtained in this example from narrow MWD homopolymeric precursor 3 and is superimposed with the GPC elutagramme for polymethacrylamide 5 which was produced by conventional free radical polymerisation of 6. It is known that polymethacrylamide 5 when prepared from monomer 6 by conventional free radical polymerisation is not cytotoxic. FIG. 4 confirms that narrow MWD polymethacrylamide 5 prepared from precursor 3 is also not cytotoxic. Both polymethacrylamide 5 samples do not display cyctoxicity in this assay compared to polylysine which is used as a cytotoxic control. Dextran is used as a noncytotoxic control. Different amines including diethyl amine, propyl amine, and methyl esters of amino acids have been conjugated to narrow MWD homopolymeric precursor 3 to make homopolymeric narrow MWD polymethacrylamides. It is also possible to effectively conjugate less than an equivalent of the amine to give copolymers like 7 which is shown in FIG. 5 by a corresponding decrease of the IR band for the active ester in the precursor 3 at 1735 cm−1 as a function of the stoichiometry of the added amine (in the example shown below, glycine methyl ester). FIG. 5 shows superimposed IR spectra in the absorbance mode for the sequence of reactions to produce narrow MWD copolymer conjugate 7 derived from the reaction of narrow MWD homopolymeric precursor 3 with the different the stoichiometries that are shown of glycine methyl ester. Actual active ester peak height reductions at 1735 cm −1 were 25.7, 53.7 and 74.7% corresponding to the increasing stoichiometries of 0.25, 0.50 and 0.75 equivalents respectively of glycine methyl ester. This experiment demonstrates the ability to monitor the conjugation of different stoichiometries of amines to narrow MWD homopolymer precursor 3. The experiment below demonstrates the ability to use the narrow the MWD homopolymeric precursor 3 to prepare narrow MWD copolymeric poly(methacrylic acid co methacrylamides) 9. Procedure To an argon purged vial containing the narrow MWD homopolymeric precursor, poly(methacryloxy succinimide) 3 (0.3 g, 1.6 mmol of reactive groups) in DMSO (1 ml) was added 1-amino-2-propanol (In three separate reactions; 0.25 eq, 32 ml, 4.1 mmol; 0.5 eq., 63 ml, 8.2 mmol and 0.75 eq., 95 ml, 12.2 mmol) dropwise under stirring. The vials were then heated at 50° C. for 3 hr and a FT-IR spectrum taken of each reaction solution to confirm that the expected amount of 1-amino-2-propanol was conjugated to precursor 3 to give the copolymeric intermediate 8 (FIG. 6 ). To the reaction solution was then added aqueous NaOH (1.6 ml, 1N). The solution became warm upon addition and soon became less viscous. Hydrolysis was confirmed by the disappearance of the active ester band at 1735 cm −1 by IR spectroscopy. After 5 h of stirring, water (approx. 50 ml) was added and the solution was dialysed using regenerated cellulose membrane (SpectraPor, MWCO 2000) against water. Lyophilization of the dialysed solution gave the narrow MWD copolymeric poly(methacrylic acid co methacrylamides) 9 as white solid products. Mass=0.22 g, 0.23 g and 0.2 g respectively. FIG. 6 shows superimposed IR spectra in the absorbance mode for the sequence of reactions to produce the intermediate narrow MWD copolymer conjugate 8 derived from the reaction of narrow MWD homopolymeric precursor 3 with the different the stoichiometries that are shown of 1-amino-2-propanol. Actual active ester peak height reductions at 1735 cm −1 were 26.0, 52.9 and 76.4% corresponding to the increasing stoichiometries of 0.25, 0.50 and 0.75 equivalents respectively of 1-amino-2-propane. This figure also shows the reduction of the active ester band from the addition of 1 equivalent of 1-amino-2-propanol. The actual reduction was 99.9%. This experiment again demonstrates the ability to monitor the conjugation of different stoichiometries of amines to narrow the MWD homopolymer precursor 3 with the added advantage of being able to chemically functionalise copolymeric intermediates 8 to give functionalised narrow MWD poly(methacrylic acid co methacrylamides) 9. Example 5 Use of Narrow MDW Homopolymeric Precursor 3 to Prepare Water Soluble Copolymeric Conjugates The preparation of water soluble conjugate 12. The letter G in structures 11 and 12 is the conventional single letter abbreviation for glycine. Poly(methacryloxysuccinimide) 3 (100 mg, 0.55 mmol of reactive groups), the model drug derivative, H-Gly-Gly-β-napthylamide HBr0.6H 2 O 10 (19 mg, 0.06 mmol, 0.1 eq., 10% loading) and a magnetic flea were added to a 1.5 ml vial. The vial was sealed with a septum centred screw cap lid and purged with argon for approximately 2 min. DMSO (0.4 ml) was then injected into the vial under argon and the vial was placed onto a magnetic stirrer. Once a solution had formed, a small sample of the solution was removed by syringe under argon for immediate FT-IR spectroscopy. Triethylamine (15.2 ml, 0.11 mmol, 2 salt eq.) was then added under argon to the vial and the vial was placed in an oil bath at 50° C. for 2 h 30 min. After cooling, a sample of the solution was removed from the vial under argon for immediate FT-IR spectroscopy to confirm the addition of 10 by ensuring the corresponding 10% reduction in the active ester peak at 1735 cm −1 had occurred. To the reaction solution containing the copolymer intermediate 11 was added 1-amino-2-propanol (82 mg, 1.1 mmol, 2 eq.) and the solution heated at 50° C. for 1 h 15 min. The water soluble copolymeric conjugate 12 was isolated by precipitation of the DMSO reaction solution into acetone:diethyl ether (50:50 v/v) and further purified by precipitation from methanol into acetone:diethyl ether (50:50 v/v). Shown in FIG. 7 are the superimposed IR spectra to display the changes in the active ester peak during this sequence of reactions to prepare conjugate 12. These 3 IR spectra display the reduction of the height of the active ester band at 1735 cm −1 and the evolution of the amide I and II peaks. Spectrum (A) is the starting precursor 3, spectrum (B) shows the 10% reduction in the height active ester band after addition of 10, and spectrum (C) shows the complete disappearance of the active ester band after the addition of 1-amino-2-propanol to give the narrow MWD copolymeric conjugate 12 with 10% loading of 10. Shown in FIG. 8 are the superimposed IR spectra for the same reaction sequence to prepare conjugate 12. This experiment demonstrated the ability to use the same narrow MWD homopolymeric precursor 3 to prepare conjugates with different loadings of the drug component. In this experiment 0.25 equivalents of amine 10 were used instead of 0.1 equivalents and the peak at 1735 cm −1 displayed a height reduction of approximately 25%. To confirm there was essentially no competing hydrolysis reactions, the intermediate reaction solution was allowed to continue stirring a further 12 hours at 50° C. to ensure no further reduction of the active ester peak occurred. FIG. 8 shows the preparation of narrow MWD conjugate 12 at 25% loading of 10. Spectrum (A) is the starting precursor 3, spectrum (B) shows the 25% reduction in the height active ester band at 1735 cm 31 after addition of 10, spectrum (C) shows there is no further reduction in the height active ester band when the intermediate reaction mixture of 11 was stirred a further 12 h at 50° C. and spectrum (D) shows the complete disappearance of the active ester band after the addition of 1-amino-2-propanol to give the narrow MWD copolymeric conjugate 12 with a 25% loading of 10. The sequence of reactions for example 5 was also carried out using a different amine for the second step. This exemplifies the concept that using the same narrow MWD homopolymeric precursor 3 it is possible to conjugate different property modifying pendent chain molecules to give conjugates that will have different solution properties. The two reaction sequences shown below used aminoethanol and 1-amino-2,3-propane-diol respectively instead of 1-amino-2-propanol for the second conjugation reaction in the sequence. FIGS. 9-10 show the superimposed IR spectra that were obtained to monitor each reaction sequence. FIG. 9 shows the preparation of narrow MWD conjugate 13 at 25% loading of 10. Spectrum (A) is the starting precursor 3, spectrum (B) shows the 25% reduction in the height active ester band after addition of 10, spectrum (C) shows there is no further reduction in the height active ester band at 1735 cm −1 when the intermediate reaction mixture of 11 was stirred a further 12 h at 50° C. and spectrum (D) shows the complete disappearance of the active ester band after the addition of ethanolamine to give the narrow MWD copolymeric conjugate 13 with a 25% loading of 10. FIG. 10 . Preparation of narrow MWD conjugate 14 at 25% loading of 10. Spectrum (A) is the starting precursor 3, spectrum (B) shows the 25% reduction in the height active ester band after addition of 10, spectrum (C) shows there is no further reduction in the height active ester band at 1735 cm −1 when the intermediate reaction mixture of 11 was stirred a further 12 h at 50° C. and spectrum (D) shows the complete disappearance of the active ester band after the addition of ethanolamine to give the narrow MWD copolymeric conjugate 14 with a 25% loading of 10. One experiment with one equivalent of amine 10 (100% loading) to produce narrow MWD conjugate 15 was conducted as a further example to demonstrate that since the narrow MWD homopolymeric precursor 3 has a reactive center on each repeat unit, conjugation of bioactive agents using precursor 3 is efficient. This experiment also demonstrates that the reaction of an amine once 95% incorporation has occurred may have a slower rate because there are relatively few reactive sites remaining. This is why it is important for the conjugation reactions to make narrow MWD, water soluble copolymer conjugates (such as for example 12, 14 and 15) that the second amine be added in excess. The superimposed IR spectra obtained to monitor the reaction to prepare the narrow MWD homopolymeric conjugate 15 are shown in FIG. 11 . FIG. 11 shows the preparation of narrow MWD conjugate 15 at 100% loading of 10. Spectrum (A) is the starting precursor 3, spectrum (B) shows the approximately 95% reduction in the height active ester band after addition of 10 after 1 h, spectra (C, D and E) shows the continued further reduction in the height active ester band at 1735 cm −1 as reaction stirred a total of 2, 3.5 and 4.5 h respectively at 50° C. and spectrum (E) shows the complete disappearance of the active ester band after the reaction mixture stirred a total of 16 h at 50° C. to give the narrow MWD homopolymeric conjugate 15 with a 100% loading of 10. Example 6 Chain Extension Reaction. Synthesis of Poly(methacryloxy succiminde-co-methacryloxy Succinimide) 16. A prerequisite for preparing block copolymers by copper mediated polymerisation is to demonstrate that the dormant chain end groups will initiate a further polymerisation reaction that gives a narrow MWD block without addition of initiator (e.g. 2). Into an argon purged vessel containing copper(I)bromide (4.8 mg, 0.03 mmol), bipyridine (10.4 mg, 0.06 mmol), methacryloxy succinimide 1 (1 g, 5.5 mmol) and poly(methacryloxy succinimide) 3 (0.5 g, number average molecular weight of 33,800 g/mol; polydispersity index 1.15, GPC, DMF eluent, PMMA calibration standards), which had previously been prepared by copper mediated polymerisation, was added DMSO (0.25 g, previously degassed by argon purge). The vessel was stoppered and heated at 130° C. for approximately 10 minutes. After cooling, more DMSO (approx. 7 ml) was added to dissolve the contents which were then slowly added to a solution of acetone to precipitate the block copolymer 16 which was collected and dried in vacuum to give a white solid (1.1 g, 73%). GPC analysis indicated the extension of the starting polymer had occured to give a new second block to produce poly(methacryloxy succiminde-co-methacryloxy succinimide) 16 with a number average molecular weight of 96,500 g/mol with a polydispersity index of 1.1 (DMF eluent, PMMA calibration standards). In separate experiments to probe for possible competing thermal initiation, monomer 1 was stirred alone in DMF at 80 and 110° C. over 8-24 hours. This resulted in the formation of some polymer with a high polydispersity index (>2.5). Example 2 has already established that the copper mediated polymerisation of monomer 1 quickly comes to completion. The reaction (1+3→16) of this example is also appears to be very fast (10 minutes) and gives a narrow MWD block copolymer confirming the presence of dormant chain end group required for polymer block formation. FIG. 12 shows the GPC for narrow MWD poly(methacryloxy succinimide) 3 (Labelled “A ”) that was used as the starting polymer in the chain extension reaction described in example 6. The GPC labelled “B” displays the chain extension reaction to give poly(methacryloxy succiminde-co-methacryloxy succinimide) 16.
A polymer comprising the unit (I) wherein R is selected form the group consisting of hydrogen, C 1 -C 18 alkyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl, carboxylic acid, carboxy-C 1-6 alkyl, or any one of the C 1 -C 18 alkyl, C 1 -C 18 alkenyl, C 1 -C 18 aralkyl, C 1 -C 18 alkaryl substituted with a heteroatom within, or attached to, the carbon backbone; R 1 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl groups; X is an acylating agent and wherein the polymer has a polydispersity of less than 1.4, preferably less than 1.2 and a molecular weight (Mw) of less than 100,000, the polymer is preferably made by controlled radical polymerization and is useful in the production of polymer drug conjugates with desirable biological profiles.
2
BACKGROUND OF THE INVENTION AND RELATED ART STATEMENT [0001] The present invention relates to an inflator, and in particular, to a hybrid inflator constructed to release a gas generated from a gas-generating chemical and a pressurized gas stored in a gas storage chamber. In addition, the present invention relates to an airbag apparatus provided with the inflator. [0002] A hybrid inflator includes a gas-generating chemical ignited by an initiator and a pressurized gas storage chamber charged with a pressurized gas. When the chemical starts to react by the initiator, a reaction gas flows into the gas storage chamber. Then, the gas ruptures a sealing member separating the gas storage chamber and a gas outlet, and a mixed gas of a gas stored in the gas storage chamber (storage gas) and the reaction gas is released from the gas outlet. [0003] Japanese Patent Publication (Kokai) No. 2003-226219 discloses an inflator that releases a reaction gas from a hole of a perforated cap and collides the reaction gas against an inner wall of a cylindrical gas storage chamber at one end thereof to stick combustion residues in the reaction gas to a chamber wall. A gas outlet is provided at the other end of the gas storage chamber. [0004] Patent Document: Japanese Patent Publication (Kokai) No. 2003-226219 [0005] In the inflator disclosed in Japanese Patent Publication (Kokai) No. 2003-226219, the reaction gas generated by the reaction chemicals is not sufficiently mixed with the storage gas in the gas storage chamber. Specifically, when the chemicals start to react and the reaction gas flows into the gas storage chamber, the reaction gas tends to form a bulk portion at one end of the gas storage chamber. Accordingly, the storage gas is pushed and released by the bulk gas, and then the reaction gas is released. When the reaction gas is not sufficiently mixed with the storage gas, a temperature of the released gas becomes high when a gas containing the reaction gas is released. Therefore, an airbag is required to have heat-resistant to maintain strength enough to endure the high temperature gas upon contacting the high temperature gas. [0006] Japanese Patent Publication (Kokai) No. 2003-226219 also discloses a configuration having no perforated cap. In this case, the gas released from the initiator flows straight into the gas storage chamber and reaches the gas outlet. Thus, the storage gas is not sufficiently mixed with the reaction gas, and the temperature of the released gas becomes high. [0007] In view of the problems described above, an object of the present invention is to provide an inflator constructed to release a reaction gas generated by chemical after the reaction gas is sufficiently mixed with gas in a storage chamber. [0008] Further objects ad advantages of the invention will be apparent from the following description of the invention. SUMMARY OF THE INVENTION [0009] In order to attain the objects described above, according to the present invention, an inflator is a hybrid inflator comprising a gas storage chamber filled with pressurized gas; a chemical chamber filled with a gas-generating chemical; an initiator for igniting the chemical; a gas outlet; and a sealing plate for separating the gas outlet from the gas storage chamber. The chemical reacts to generate gas by the initiator, and the gas flows into the gas storage chamber and ruptures the sealing plate. Accordingly, the gas in the pressurized gas storage chamber and the gas generated from the chemicals are released from the gas outlet. The inflator further comprises a swirl forming device for swirling the gas generated from the chemical and flowing into the gas storage chamber. [0010] According to the present invention, it is preferable that the swirl forming device is a guide member for guiding the gas to swirl. [0011] According to the present invention, an airbag apparatus includes the inflator described above and an airbag expanded by the gas from the inflator. [0012] In the present invention, the gas generated from the reaction of the chemical swirls and flows into the gas storage chamber. Thus, the reaction gas and the storage gas are sufficiently mixed with each other. Therefore, the temperature of the released gas becomes constant. As a result, heat resistance required for the airbag can be decreased. [0013] The gas guide member with a simple configuration is suitable for the swirl forming device for swirling the gas. BRIEF DESCRIPTION OF THE DRAWING [0014] FIGS. 1 ( a ) to 1 ( e ) are views showing an inflator according to an embodiment of the present invention, wherein FIG. 1 ( a ) is a longitudinal sectional view, FIG. 1 ( b ) is an enlarged cross-sectional view of a gas guide member taken along line 1 ( b )- 1 ( b ) in FIG. 1 ( c ), FIG. 1 ( c ) is a right side view of the gas guide member viewed from line 1 ( c )- 1 ( c ) in FIG. 1 ( b ), FIG. 1 ( d ) is a cross-sectional view taken along line 1 ( d )- 1 ( d ) in FIG. 1 ( c ), and FIG. 1 ( e ) is a cross-sectional view taken along line 1 ( e )- 1 ( e ) in FIG. 1 ( c ); [0015] FIGS. 2 ( a ) to 2 ( c ) are views showing a guide member in an inflator according to another embodiment of the present invention, wherein FIG. 2 ( a ) is a cross-sectional view of the gas guide member taken along line 2 ( a )- 2 ( a ) in FIG. 2 ( b ), FIG. 2 ( b ) is a side view of the gas guide member viewed from line 2 ( b )- 2 ( b ) in FIG. 2 ( a ), and FIG. 2 ( c ) is a perspective view of the guide member; [0016] FIGS. 3 ( a ) and 3 ( b ) are views showing a guide member in an inflator according to a further embodiment of the present invention, wherein FIG. 3 ( a ) is a front view of the guide member viewed from line 3 ( a )- 3 ( a ) in FIG. 3 ( b ), and FIG. 3 ( b ) is a cross-sectional view thereof taken along line 3 ( b )- 3 ( b ) in FIG. 3 ( a ); and [0017] FIGS. 4 ( a ) and 4 ( b ) are views showing a guide member in an inflator according to a still further embodiment of the present invention, wherein FIG. 4 ( a ) is a perspective view of the guide member, and FIG. 4 ( b ) is a perspective view of semi-elliptic plates. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS [0018] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. FIG. 1 ( a ) is a longitudinal sectional view thereof; FIG. 1 ( b ) is an enlarged cross-sectional view of a gas guide member taken along line 1 ( b )- 1 ( b ) in FIG. 1 ( c ); FIG. 1 ( c ) is a right side view of the gas guide member viewed from line. 1 ( c )- 1 ( c ) in FIG. 1 ( b ); FIG. 1 ( d ) is a cross-sectional view taken along line 1 ( d )- 1 ( d ) in FIG. 1 ( c ); and FIG. 1 ( e ) is a cross-sectional view taken along line 1 ( e )- 1 ( e ) in FIG. 1 ( c ). FIGS. 2 ( a )- 2 ( c ) to 4 ( a )- 4 ( b ) show configurations of a guide member in an inflator according to embodiments, respectively. [0019] As shown in FIG. 1 ( a ), an inflator 1 comprises a substantially cylindrical pressure-proof vessel 2 (vessel); a head block 3 fixed at one end of the vessel 2 ; gas-generating chemicals 4 charged in the head block 3 , an initiator 5 for igniting the chemicals 4 ; a first sealing plate 6 separating the interior of the head block 3 from one end of a gas storage chamber 8 ; a guide member 7 as a swirl forming device; and a second sealing plate 9 separating the other end of the gas storage chamber 8 from a gas outlet 10 . [0020] The vessel 2 is made of steel and the like, and the gas storage chamber 8 is charged with a gas, for example, nitrogen, argon, or helium at a pressure of 10,000 to 70,000 kPa. The head block 3 made of steel and the like is fixed to one end of the vessel 2 by welding. The head block 3 has a thick cylindrical shape, and an inner hole 3 a as a chemical chamber is charged with the chemicals 4 . A portion of the inner hole 3 a at the vessel 2 side is sealed by the first sealing plate 6 . [0021] The first sealing plate 6 is made of, for example, a stainless sheet, and is fixed to the end surface of the head block 3 at the vessel 2 side by welding. The first sealing plate 6 is provided with a substantially hemispheric bulging portion entering the inner hole 3 a to endure the pressure of gas from the gas storage chamber 8 . The bulging portion may be provided with a rupture-promoting groove. [0022] The initiator 5 is disposed to face a portion of the inner hole 3 a opposite to the vessel 2 . The initiator 5 includes igniting chemicals and an ignition device such as a resistance heating element for igniting the igniting chemicals. In the initiator 5 , when power is applied to the ignition device, the igniting chemicals react to generate a high-temperature gas. The initiator 5 is held in an end sleeve 3 b of the head block 3 by an initiator holder 11 . [0023] The other end of the vessel 2 is provided with a guide hole 12 , and the gas outlet 10 is disposed at the end of the guide hole 12 . The second sealing plate 9 is provided so as to seal the inflow end of the guide hole 12 . A hemispheric bulging portion provided at the second sealing plate 9 enters the guide hole 12 . The sealing plate 9 is fixed to the circumferential edge of the inflow end of the guide hole 12 . The gas storage chamber 8 is formed between the sealing plates 6 and 9 . A filter (not shown) may be provided in the guide hole 12 to collect combustion residues of the chemicals 4 . [0024] Next, a configuration of the guide member 7 will be described with reference to FIGS. 1 ( b ) to 1 ( e ). The guide member 7 is substantially disc-shaped, and a circular recessed part 7 a is formed in a surface of the guide member 7 facing the first sealing plate 6 . Two nozzles 14 and 15 are provided for communicating a bottom surface 7 b of the recessed part 7 a with a rear surface 7 c of the guide member 7 . The respective nozzles 14 and 15 extend linearly, and their axes have a twisted relationship to each other. [0025] The nozzle 14 is located at one half with respect to a plane (a plane taken along C-C line in FIG. 1 ( c )) passing through both the nozzles 14 and 15 and including the axis of the disc-shaped guide member 7 . The nozzle 15 is located at the other half with respect to the plane. With the nozzles 14 and 15 thus arranged, the gas passing through the nozzles 14 and 15 forms a swirl like an arrow G in FIG. 1 ( a ). [0026] An operation of the inflator constructed as described above is as follows. When the initiator 5 is supplied with power, the initiator 5 generates a high-temperature gas, and then a large amount of reaction gas is generated by the chemicals 4 contacting the high-temperature gas. The pressure of the high-temperature gas ruptures the first sealing plate 6 , and the reaction gas passes through the nozzles 14 and 15 of the guide member 7 and flows into the gas storage chamber 8 while forming a swirl G. As the gas pressure of the gas storage chamber 8 increases, the second sealing plate 9 is ruptured, and the gas is released from the guide hole 12 via the gas outlet 10 . Then, the gas rapidly expands an airbag. [0027] In the inflator 1 , the reaction gas of the chemicals 4 forms a swirl G. Accordingly, the reaction gas is sufficiently mixed with the storage gas and released from the gas outlet 10 . Therefore, the temperature of the releasing-gas is almost constant. That is, the hot reaction gas is not localized and released from the gas outlet 10 . Therefore, the airbag expanded by the inflator 1 does not, need to have high heat resistance. [0028] Other examples of guide members that can be used in the inflator of the present invention will be described with reference to FIGS. 2 ( a )- 2 ( c ) to 4 ( a )- 4 ( b ). A guide member 20 shown in FIGS. 2 ( a )- 2 ( c ) is substantially disc-shaped, and a spiral nozzle 23 is provided to communicate one face 21 of the guide member 20 with the other face 22 thereof. The gas passes through the spiral nozzle 23 disposed in the vessel, thereby forming a swirl G as shown in FIG. 2 ( c ). FIG. 2 ( a ) is a cross-sectional view of the guide member 20 taken along an axis thereof and line 2 ( a )- 2 ( a ) in FIG. 2 ( b ). FIG. 2 ( b ) is a view seen from line 2 ( b )- 2 ( b ) in FIG. 2 ( a ), and FIG. 2 ( c ) is a perspective view of the guide member 20 . [0029] As shown in FIGS. 3 ( a ) and 3 ( b ), a guide member 30 includes a lot of nozzles 33 (nine nozzles in the figure). Each nozzle 33 communicates a face 31 of the substantially disc-shaped guide member 30 with a face 32 thereof. Every nozzle 33 is inclined in the same direction around the axis of the guide member 30 . The gas passes through the nozzles 33 of the guide member 30 disposed in the vessel 2 , thereby forming a swirl. FIG. 3 ( a ) is a front view of the guide member 30 viewed from line 3 ( a )- 3 ( a ) in FIG. 3 ( b ), and FIG. 3 ( b ) is a cross-sectional view thereof taken along line 3 ( b )- 3 ( b ) in FIG. 3 ( a ). In order to make the configuration clear, the hatching of the cross-section is omitted in FIG. 3 ( b ). [0030] As shown in FIG. 4 , a guide member 40 includes two pieces of semi-elliptic plates 42 and 43 in a cylindrical casing 41 . The circumferential edges of the semi-elliptic plates 42 and 43 touch the inner circumferential face of the casing 41 and are fixed thereto by welding. Chords 42 a and 43 a of the semi-elliptic plates 42 and 43 are connected to each other at their longitudinal intermediate portions. The plate faces of the semi-elliptic plates 42 and 43 intersect each other. The gas passes through the guide member 40 disposed in the vessel 2 , thereby forming a swirl G as shown in FIG. 4 ( a ). FIG. 4 ( a ) is a perspective view of the guide member 40 , and FIG. 4 ( b ) is a perspective view of the semi-elliptic plates 42 and 43 . [0031] The embodiments described above are just examples of the present invention, and the present invention can be modified from those illustrated in the drawings. For example, the guide member 7 is disposed in the vessel 2 in the embodiment, and a guide bane for forming a swirl may be provided at the inner circumferential edge of the vessel 2 . [0032] The inflator of the present invention can be applied to various kinds of airbag apparatus such as those for a front passenger, a head-protection, a knee-protection, a driver, and a rear passenger. [0033] The disclosure of Japanese Patent Application No. 2004-183877, filed on Jun. 22, 2004, is incorporated in the application. [0034] While the invention has been explained with reference to the specific embodiments of the invention, the explanation is illustrative and the invention is limited only by the appended claims.
A hybrid inflator includes a gas storage chamber filled with a pressurized gas, a chemical chamber filled with a gas generating chemical, and an initiator attached to the chemical chamber for igniting the chemical to generate a reaction gas. A gas outlet is formed to eject the pressurized gas and the reaction gas from the gas storage chamber, and a sealing plate is disposed in the gas storage chamber for separating the gas outlet from the gas storage chamber. A swirl forming device is disposed between the gas storage chamber and the chemical chamber for swirling the reaction gas from the chemical chamber and guiding the reaction gas into the gas storage chamber.
1
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority to U.S. Provisional Application Nos. 60/875,508 filed on Dec. 18, 2006 and 60/957,554 filed on Aug. 23, 2007. Both applications are incorporated by reference herein in their entireties for all purposes. FIELD OF THE INVENTION [0002] The present invention relates generally to packages for containing various products. More particularly, the present invention relates to a package for containing and dispensing products such as confectionery products including candy and gum, and which has a self-closing opening that can be repeatedly opened and closed. BACKGROUND OF THE INVENTION [0003] The art has seen a wide variety of packages for containing and dispensing products, particularly confectionery products such as candy and gum. Quite often, one or multiple pieces of candy or gum are packaged in a single package. The consumer would open the package to dispense the individual products or portions of a single product. When a consumer uses less than all of the contents contained in the package, a problem arises with respect to reclosing the package. This problem is particularly evident where small packages such as bags or wrappers are employed. Moreover, where the products are candy or gum pieces and are contained in the package in an unwrapped condition, reclosing of the package once opened becomes a significant concern. [0004] Many of the packages containing candy and gum include sealed ends which initially contain and protect the products. However, once one of the sealed ends is opened to dispense some of the contents, it is difficult to provide an effective closure for that end. Moreover, when dispensing a plurality of products it is often necessary to repeatedly open and close the package. [0005] It is, therefore, desirable to provide a simple, cost effective and useful technique to reclose the end of a previously sealed package in a manner which will allow repeated opening and closing of the package to dispense additional product. SUMMARY OF THE INVENTION [0006] The present invention provides a package for containing and dispensing product having an end which may be repeatedly opened and reclosed. [0007] The present invention also provides a package for containing and dispensing product having a package body and a band for permitting an opened end to be repeatedly opened and closed. [0008] The present invention further provides a package including a package body having closed ends, at least one of the closed ends being openable. A reclosable member including a continuous band disposed on the package body, the band being adjacent to and encircling the openable closed end. The reclosable member maintains the at least one of the openable end in a closed condition after opening thereof. The openable end is selectively and repeatedly openable and reclosable upon manipulation of the package body. [0009] The present invention still further provides a package for confectionery products including a package body having closed ends, at least one of the closed ends being detachably sealed. A continuos resilient band encircling the package inwardly adjacent the detachably sealed closed end. The resilient band maintaining the one closed end in a closed condition after detachment of the detachable seal and being openable under manual squeeze pressure to open the package, and reclosable after release of the manual squeeze pressure. [0010] The present invention still yet further provides a package for confectionery products including a package body having closed ends, at least one of the closed ends being openable. A reclosable member is provided which includes a band of pressure sensitive adhesive material disposed on an inner surface of the package body. The band is inwardly adjacent to and encircling the openable closed end. The reclosable member maintains the at least one of the openable end in a closed condition after opening thereof. The openable end is selectively and repeatedly openable and reclosable upon manipulation of the package body. BRIEF DESCRIPTION OF THE DRAWINGS [0011] FIG. 1 shows a package of the present invention. [0012] FIG. 2 shows the package of FIG. 1 including one sealed end detached therefrom. [0013] FIG. 3 shows a package of FIG. 1 in an open condition to dispense product. [0014] FIG. 4 shows a package of FIG. 1 in a reclosed condition. [0015] FIG. 5 shows an alternative embodiment of the present invention. [0016] FIG. 6A shows a perspective view of one embodiment of the package of the present invention. [0017] FIG. 6B shows a perspective view of an alternative embodiment of the package of the present invention. [0018] FIG. 7 shows an alternative embodiment of a package of the present invention. [0019] FIG. 8 shows the package of FIG. 7 including one sealed end detached therefrom and the product being dispensed. [0020] FIG. 9 is a cross-sectional view taken through line 9 - 9 of FIG. 8 . [0021] FIG. 10 shows a package of FIG. 7 in a reclosed condition. [0022] FIG. 11 is a cross-sectional view taken through line 11 - 11 of FIG. 10 . [0023] FIG. 12 shows an alternative embodiment of the present invention. [0024] FIG. 13 shows a film for forming the package of FIG. 7 . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0025] The present invention provides a package for containing and dispensing product. In particular, the present invention may be used for containing and dispensing confectionery products such as gum pieces. While the particular embodiment shown herein is employed to contain gum pieces, it may be appreciated that the package may contain any type of product. Such product may also include other confectionery products such as gum in various sizes and shapes such as sticks, slabs, pillows, pellets and the like as well as other confectionery products such as candy, chocolate and the like. Non-confectionery products may also be employed. [0026] Referring to FIGS. 1-4 , one embodiment is shown. A package 10 is used to contain and dispense a plurality of product pieces 12 which may be in the form of gum pieces that are contained in loose orientation within the package 10 . The gum pieces may be any size, shape, or configuration including slabs, pellets and sticks. While individual discrete gum pellets are shown, it is contemplated that the package may contain one or more products having portions thereof that can be broken away or detached for use. Moreover, while unwrapped gum pieces are shown, the package may contain individually wrapped gum pieces. The package 10 includes a generally elongate tubular body 11 which may be formed of a of a thin-film flexible material. Body 11 may be formed of wide variety of conventional materials such as polypropylene. The package 10 includes opposed closed ends 14 and 16 which are sealed closed. Various conventional techniques are known for sealably closing the ends 14 and 16 of package 10 . These techniques may include crimp-sealing the ends, as well as heat-sealing the ends. The seals are such that they hermetically seal the package, thereby protecting the gum pieces 12 contained therein during shipping and prior to use. While one preferred embodiment is shown, it may be appreciated that any package configuration such as a bag or wrapper may be employed. [0027] One of the ends 14 or 16 may be detached from the package 10 to open the package to permit dispensing of the gum pieces 12 therefrom. As shown in FIG. 2 , end 14 may be detached from the body 11 providing an open end 18 ( FIG. 3 ) through which the gum pieces 12 may be dispensed. Alternatively, the end may be opened and not detached from the package. End 14 may integrally formed with the package body and removed by tearing the end 14 from the remainder of the package 10 . It is also contemplated that the end 14 may include a frangible line 20 therearound which assists in tearing the end 14 from the body 11 of the package 10 . The line 20 may be a score line or a laser cut line which assists in removing the end therefrom. The line 20 may also provide tamper indication. The line 20 may be any shape or configuration. [0028] As may be appreciated, once the end 14 is removed from the package 10 , the interior 22 of the package is opened and in communication with opening 18 . Typically during use, less than all of the contents are dispensed at one time. Therefore, it is desirable to effectively close the open end 18 so that the package 10 can retain the remainder of the contents. A reclosable member 24 is provided about open end 18 which reseals the open end in the closed position. [0029] As shown in the figures, reclosable member 24 may include a resilient band 30 which circumscribes the tubular package body 11 about opening 18 . The band 30 may be a continuous member formed of one piece. The band 30 is positioned inwardly adjacent sealed end 14 . The resilient band 30 may be formed of a wide variety of materials such as polypropylene and has sufficient spring rigidity to be maintained in a closed condition as shown in FIG. 1 , yet it is flexibly openable under manual squeeze pressure as shown in FIG. 3 . [0030] Band 30 may be secured to package 10 by a wide variety of techniques including the use of adhesive, heat or ultrasonic welding. The band 30 , which may be applied to the inside ( FIG. 1 ) or outside ( FIG. 6A ) of the package, is positioned inwardly adjacent end 14 a sufficient distance so as to permit easy tearing of the end 14 from the package to dispense the gum pieces 12 . Once the end 14 is removed, the band 30 may be opened by manual squeeze pressure. Preferably, the band is opened by a user applying a force to opposed ends 31 of the band as shown in FIG. 3 . This forms opening 18 through which one or more of the gum pieces 12 may be dispensed. Once the desired number of gum pieces is dispensed, the manual squeeze pressure on the band 30 may be released and as shown in FIG. 4 . The band 30 then returns to its original condition under spring action of the band to such that the opposes sides 33 of the band engage each other closing the opening 18 preventing the remaining gum pieces 12 from exiting the package. [0031] As shown in FIG. 5 , it is further contemplated that multiple frangible lines 20 may be provided at spaced locations along the length of the package 10 ′. This would allow an individual product or groups of products in the package to be separately sealed therealong. At each sealed location, a resilient band 30 may be provided so that when each location is in turn opened the band at that location may provide for the reclosing of the package thereat. [0032] Two arrangements of the present invention are shown in FIGS. 6A and 6B . The first arrangement shown in FIG. 6A includes an elongate tubular package 50 which is designed to hold a plurality of gum pieces 52 in a single longitudinal array. The arrangement of FIG. 6 includes a package 54 is designed to support a plurality of gum pieces 56 in plural rows. Accordingly, it is within the contemplation of the present invention that the package may be formed in a variety of configurations in order to accommodate an arrangement or shape of the contents. [0033] A further preferred embodiment is shown in FIGS. 7-13 . With specific reference to FIGS. 7-12 , package 110 may contain and dispense product pieces 112 . Package 110 may be generally formed in a manner similar to package 10 described above having a generally tubular body 111 with ends 114 and 116 which are sealed closed. One of the ends 114 or 116 may be opened to permit dispensing of the product pieces 112 therefrom. In one embodiment, the end may be detached from the package 110 to open it. Alternatively, the end may be opened and not detached from the package. As shown in FIGS. 8 and 10 , end 114 may be detached from the body 111 providing an open end 118 through which the product pieces 112 may be dispensed. End 114 may be removed by tearing it from the remainder of the package 110 . End 114 may include a frangible line 120 ( FIG. 7 ) therearound which assists in tearing the end 114 from the body 111 of the package 110 . The line 120 may be a score line or a laser cut line of any shape or configuration which assists in removing the end therefrom. [0034] As shown in FIGS. 8 and 9 , when the end 114 is removed from the package 110 , the package interior 122 is open and in communication with opening 118 . If the entire product is not dispensed from the package 110 , the open end 118 may be reclosed so that the package 110 can retain the remainder of the contents. A reclosable member 124 is provided about opening 118 . [0035] In this embodiment, reclosable member 124 preferably includes a band 130 of material which circumscribes the body 111 of tubular package 110 about opening 118 . The band 130 is positioned inwardly from the sealed end 114 and inwardly from frangible line 120 . The band 130 may be formed of an adhesive material that will adhere to itself forming a seal. The seal may be opened and reclosed repeatedly to permit a user to dispense a portion of the contents and then reseal the package. The seal may be a cold seal that permits repeatable sealing. With reference to FIGS. 10 and 11 , the seal is effected by the application of moderate pressure by a user such that opposing surfaces of the band, 130 a and 130 b , engage each other and adhere, thereby sealing the opening 118 . [0036] The band 130 may be formed of an adhesive that bonds when exposed to pressure, such as a pressure sensitive adhesive tape that is applied to the packaging. The adhesive preferrably forms a bond that is strong enough to keep the surfaces 130 a and 130 b secured together, but also allows the surfaces to be pulled apart and separated without tearing or damaging the package 110 . The surfaces 130 a and 130 b may then be brought together to reseal the package. Such adhesives may include solid microsphere adhesives and silicone gel adhesives. Alternatively, the adhesive may be formed of a wax such as vegetable or fruit wax. The adhesive may be of a type which has a low tack surface but forms a solid bond with itself, such that when the opposing surfaces are brought together a seal is made. However, since the tackiness of the surface is low, it does not restrict the passage of the product when it is dispensed through the open end 118 . When the packaging is used with a comestible, the adhesives would be those which are FDA approved for use with food. [0037] With reference to FIG. 7 , the reclosable member 124 , which may be applied to the inside of the package, is positioned inwardly from end 114 a sufficient distance so as to permit easy tearing of the end 114 from the package to dispense the gum pieces 112 . The reclosable member 124 may be spaced a distance “d” inwardly from the frangible line 120 . This leaves a section of packaging which is un-adhered outward of the reclosable member 124 , which provides a gripping area 126 for a user to manipulate in order to assist in overcoming the reclosable member and reopen the package. This forms opening 118 through which one or more of the product pieces 112 may be dispensed. Once the desired number of product pieces is dispensed, the opposed surfaces of the packaging close the opening 118 , preventing the remaining product pieces 112 from exiting the package. The seal may also protect the product from contamination and moisture. [0038] With reference to FIG. 12 , it is further contemplated that multiple frangible locations 120 may be provided at spaced locations along the length of the package 110 ′. This would allow an individual product or groups of products 112 in the package to be separately sealed therealong. At each sealed location, a reclosable member 124 may be provided so that when each location is in turn opened the reclosable member 124 at that location may provide for the resealing of the package thereat. [0039] With reference to FIG. 13 , the packaging of the present invention may be formed of a film 150 which is taken off a roll 152 . The film 150 may be parted forming a blank 151 and treated at the perimeter 154 with a sealing material 156 . Preferably, the film may be pretreated with the perimeter sealing material. The sealing material 156 may be a cold seal or heat seal type, which results in a permanent seal. The blank 151 may also be coated adjacent one end with a resealable material 158 , such as a cold seal adhesive, to form the reclosable member 124 . The frangible line 120 may be formed between the end 114 and the resealable material 158 . A blank central portion 160 may form the front panel of the package. Side panels 162 may longitudinally bound the central portion 160 and form the sides of the package. Adjacent to the side panels 162 are back panels 166 which form the back of the package. The blank 151 may then be folded along its longitudinal axis, L-L, such that the treated perimeter edges meet to form the package 110 . One end, 114 , may be left unsealed to permit the package to be filled. The package may be filled with the product pieces 112 after which the open end may be permanently sealed. It is within the contemplation of the present invention that the package 110 may be formed in a variety of manners as is known in the art. [0040] Various changes to the foregoing described and shown structures would now be evident to those skilled in the art. Accordingly, the particularly disclosed scope of the invention is set forth in the following claims.
A package including a package body having closed ends, at least one of the closed ends being openable. A reclosable member including a band disposed on the package body, the band being adjacent to and encircling the openable closed end. The reclosable member maintains the at least one of the openable end in a closed condition after opening thereof. The openable end is selectively and repeatedly openable and reclosable upon manipulation of the package body.
1
FIELD OF THE INVENTION The present invention relates to sports goals and ball return devices for sports and, more particularly, to a combination multi-sports net and rebounder. BACKGROUND OF THE INVENTION Various types of netted enclosures for use as sports goals or capture devices are known in the art. Such devices typically include a loose fitting net which is draped about a frame to create an enclosure which is open to the front. Balls are directed into the enclosure during game play or practice drills. Other devices for rebounding balls are also known in the art. These devices typically include an elastic net which is stretched taut about a frame, creating a rebound or “pitchback” effect when balls are directed into the net. An improved system which functions as both a ball capture device and a rebounder is desired. SUMMARY OF THE INVENTION According to one aspect, the present disclosure includes a ball sports practice device comprising a forward facing ball capture enclosure and a rear facing ball rebound structure. The capture enclosure comprises a first frame having a substantially rectangular front opening to an interior capture area. The interior capture area is defined by a substantially vertical rear capture surface and two vertical side capture surfaces extending outward on opposing sides of said rear capture surface. The rebound structure is arranged on the device on the side opposite the capture area of said first frame and comprises a second frame attached to the first frame and a rebound net stretched across the second frame. The capture enclosure and the rebound structure define an angle between them which may be adjusted to support the device at a plurality of use positions on a support surface. Preferably the ball sports practice device can be used as a soccer or other ball sport goal or as a ball rebound device. It is an object of the invention to provide an improved sports ball capture and rebound device. Further objects, features and advantages of the present invention shall become apparent from the detailed drawings and descriptions provided herein. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 . is a front right-side perspective view of an embodiment of the present invention. FIG. 2 is a front left-side perspective view of the embodiment of FIG. 1 . FIG. 3 is a front left-side perspective view of the embodiment of FIG. 1 with targets. FIG. 4 is a rear perspective view of the embodiment of FIG. 1 in an upright position. FIG. 5 is a rear perspective view of the embodiment of FIG. 1 in a lowered position. FIG. 6 is a side view of the embodiment of FIG. 1 in an upright position. FIG. 7 is an enlarged view of the front wheel portion of the embodiment of FIG. 1 in the upright position. FIG. 8 is a side view of the embodiment of FIG. 1 in the transport position. FIG. 9 is an enlarged view of the front wheel portion of the embodiment of FIG. 1 in the transport position. DESCRIPTION OF PREFERRED EMBODIMENTS For the purposes of promoting an understanding of the principles of the disclosure, reference will now be made to the embodiments illustrated and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations, modifications, and further applications of the principles being contemplated as would normally occur to one skilled in the art to which the invention relates. FIGS. 1-9 depict an example embodiment of a ball sports practice device, denoted generally by the numeral 100 , comprising a front ball capture enclosure 110 and a rear rebound structure 204 . The enclosure 110 and rebound structure 204 are supported by a front frame 114 and a rear frame 206 , respectively. The front frame 114 and rear frame 206 are adjustable, for example via a pivotal connection using upper hinges 118 and 120 . The hinges 118 and 120 allow the angle θ between the axis 211 of rebound structure 204 and axis 213 of enclosure 110 (see FIG. 6 ) to be adjusted. In some embodiments, support arms 240 and 242 extend downward from the approximate vertical midpoints of sidemembers 212 and 214 of the rear frame 206 as shown. Adjustable locking hinges 244 and 246 connect the support arms 240 and 242 to the sidemembers 212 and 214 . The angle of the support arms 240 and 242 maintains or limits the angle θ when the device 100 is in a use position as shown in FIGS. 1-6 . The front and rear frames 114 and 206 may be constructed from metal, plastic, composite, or any other suitably rigid material. The term “surface” as used herein with respect to components of the device 100 shall be understood to mean any continuous or non-continuous boundary material, including, but not limited to, fabric, mesh, netting, chain link, or the like. It shall be understood that the terms “front,” “forward,” and “rear” as used herein are for convenient reference only and do not define an overall placement or orientation of the device 100 with respect to a user. As shown in FIGS. 1 and 2 , the front frame 114 includes sidemembers 140 , 142 , 144 , 146 , 148 and 150 . Sidemembers 140 and 142 are generally vertical and orthogonally connected to the front ends 141 and 143 of horizontal sidemembers 148 and 150 , respectively. Sidemember 144 is connected at an angle between sidemembers 140 and 148 as shown, thereby creating a generally triangular side area 160 . Likewise, sidemember 146 is connected at an angle between sidemembers 142 and 150 as shown, to create a generally triangular side area 162 . Upper and lower horizontal crossmembers 152 and 154 are orthogonally connected between the upper and lower ends of sidemembers 140 and 142 , respectively, as shown. The individual members 140 , 142 , 144 , 146 , 148 and 150 may be permanently attached together (e.g., by welding or forming as a unitary piece) or attached together using appropriate fasteners for easier packaging and storage. Netted portions 180 and 182 are wrapped around the generally triangular side areas 160 and 162 , respectively to create side capture surfaces 184 and 186 respectively. In addition, fabric portion 188 extends between the sidemembers 144 and 146 to create a rear capture surface 190 . Together, the capture surfaces 184 , 186 and 190 define an interior capture area 191 . In a preferred embodiment, the side capture surfaces 184 and 186 comprise an open net material and the rear capture surface 190 comprises a heavier tarp material which is loosely fitted to allow captured balls to drop down instead of forcefully rebounding. However, the capture surfaces 184 , 186 and 190 may also be constructed of other materials including netting, fabric, plastic, wood, metal and the like. As the incoming balls drop down after striking the rear capture surface 190 , they will be directed outward toward the user due to the downward and outward angle of the rear capture surface 190 and the sidemembers 144 and 146 . In certain embodiments, the capture side capture surfaces 184 and 186 and rear capture surface 190 are sewn or otherwise attached together as a single unit. This allows the front edges of the side capture surfaces 184 and 186 to be attached to the sidemembers 140 and 142 , respectively, thereby eliminating the need to attach the rear capture surface 190 directly to the sidemembers 144 and 146 . In other embodiments, the capture surfaces 184 , 186 and 190 may be provided as separate pieces and attached to the front frame 114 individually. The side capture surfaces 184 and 186 are preferably attached to the sidemembers 140 and 142 using sleeves 181 and 183 . In one embodiment, the sleeves 181 and 183 include hook-and-loop fasteners, buttons, ties, or other appropriate securing devices which enable the sleeves 181 and 183 to be wrapped around the sidemembers 140 and 142 and secured as shown. In other embodiments, where the sidemembers 140 and 142 are separable from the front frame 114 , the sleeves 181 and 183 may be slid onto the sidemembers 140 and 142 prior to installation. A slack curtain 194 may be optionally included to further dampen the force of incoming balls as they enter the capture area 110 . The slack curtain 194 is preferably attached to the upper cross member 152 using sleeve 197 and hangs freely as shown FIG. 2 . When not in use, the slack curtain 194 may be lifted up and laid over the top of rebound structure 204 as shown in FIGS. 1 and 6 . This also has the effect of creating a top capture surface 198 to assist in capturing incoming balls. The slack curtain 194 is preferably constructed from a heavy fabric or tarp material to increase the damping effect, although other lighter or heavier materials may be utilized depending on the degree of damping desired. It shall be understood that the slack curtain 194 may be constructed as a continuous piece or as a mesh or net. As shown in FIG. 3 , one or more targets 195 may be optionally included to provide further guidance for the user when kicking or throwing balls into the capture enclosure 110 . In one embodiment, the targets 195 are suspended from the upper crossmember 152 . In other embodiments, the targets 195 may be attached to the slack curtain 194 or to the rear capture surface 190 . As shown in FIG. 4 , the rebound structure 204 comprises a rebound surface 205 stretched about the rear frame 206 . The rebound surface 205 preferably comprises netting, although other types of materials may be used, such as woven fabric. Rear frame 206 comprises sidemembers 212 and 214 , and upper and lower crossmembers 216 and 218 . The upper ends 220 and 222 of sidemembers 212 and 214 are connected to the rear ends 149 and 151 of sidemembers 148 and 150 by hinges 118 and 120 respectively. The rebound surface 205 is preferably attached to rear frame 206 using hooks 230 inserted into holes 231 . The rebound surface 205 is sized such that when attached to the frame 206 , it will become rigid or taut to create a forceful rebound effect on incoming balls. In the illustrated embodiment, elastic cording 232 is woven taut between the outer edges of the rebound surface 205 and the hooks 230 as shown to increase the rebound effect. As mentioned above, support arms 240 and 242 extend downward from the approximate vertical midpoints of sidemembers 212 and 214 , respectively, with lower crossmember 243 connecting the support arms 240 and 242 for stability as shown. In a preferred embodiment, hinges 244 and 246 connect the support arms 240 and 242 to the sidemembers 212 and 214 . The hinges 244 and 246 may also be configured to lock at one more selected angles, for example using locking pins. It shall be understood that other types of adjustable locking hinges or angle locking mechanisms may also be used to adjust, maintain or limit the angle of support arms 240 and 242 relative to rear frame 206 . Wheels 260 and 262 are preferably attached to the lower ends of the sidemembers 212 and 214 to allow the bottom of the rear frame 206 to move freely as the angle of the rebound structure 204 is transitioned between use positions, for example from an upright use position (as shown in FIG. 4 ) to a more horizontal use position (as shown in FIG. 5 ) and vice versa. Due to the action of hinges 118 and 120 , gravitational force will tend to spread the bottom of rear frame 206 and the bottom of front frame 114 laterally further apart (thereby increasing the angle θ between axis 213 and axis 211 as shown in FIG. 6 ). The support arms 240 and 242 , when angularly fixed relative to the rear frame 214 , will only allow the spreading to occur until a point at which the bottom of the support arms 240 and 242 make contact with the support surface 10 , such as the ground or floor. It shall be understood that other mechanisms may be used to control or limit the spreading action. For example, instead of contacting the ground, the lower ends of the support arms 240 and 242 may be attached directly to the sidemembers 140 and 142 , respectively. In other embodiments, adjustable chains, straps, or bars may be connected between the front frame 114 and the rear frame 206 . Wheels 141 and 143 may be optionally provided near the lower ends of the sidemembers 140 and 142 of the front frame 114 . However, unlike wheels 260 and 262 , wheels 141 and 143 are preferably positioned such that there is a vertical gap 12 (as shown in FIGS. 6 and 7 ) between the bottom edge 149 of the front frame 114 and the wheels 141 and 143 when the device 100 is in a use position. Therefore, the bottom edge 149 of the front frame 114 will be in contact with the support surface 10 to provide stability and help prevent the device 100 from laterally sliding during use. When installed on a natural grass or dirt support surface, the lower edge 149 may sink slightly into the support surface 10 , allowing the wheels 141 and 143 to contact the support surface 10 , however the bottom edge 149 of the front frame 114 will still provide stability and prevent the wheels 141 and 143 from rolling. To transport the device 100 , the user pulls forward on the upper portion of the front frame 114 until the wheels 141 and 143 make contact with the support surface 10 as shown in FIG. 8 . As the front frame 114 tilts forward, the rear frame 206 will collapse into the front frame 114 , further reducing the amount of force required for the user to tilt the device 100 into the transport position. Due to the location of the wheels 141 and 143 relative to the lower edge 149 of the front frame 114 , the lower edge 149 will raise off the ground 10 as wheels 141 and 143 make contact with the support surface 10 as shown in FIG. 8 . Once supported by the wheels 141 and 143 , the device 100 can be safely rolled along the support surface 10 for transport. In certain embodiments, the lower end of the sidemembers 140 and 142 may include knee portions 145 and 147 which are angled downward and rearward from the sidemembers 140 and connect to the bottom ends of the sidemembers 144 and 146 as shown. The angle of the knee portions provides clearance and allows the wheels 141 and 143 to be raised above the support surface when the device 100 is in use. Yet the knee portions provide the effect of decreasing the degree to which the user must tilt the front frame 114 in order for the wheels 141 and 143 to be lowered into contact with the support surface 10 for transport. The use of the knee portions 145 and 147 also allows for the lower portions of the side capture surfaces 184 and 186 to be increased, providing a more effective capture effect for balls directed to the lower portions of the enclosure 110 . While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only the preferred embodiment has been shown and described and that all changes and modifications that come within the spirit of the invention are desired to be protected.
A ball sports practice device is disclosed having a forward facing ball capture enclosure and a rear facing rebound structure. The angle between the ball capture enclosure and the rebound structure may be adjusted to support the device to a plurality of use positions on a support surface. An optional support arm may be included to maintain or limit the angle between the capture enclosure and the rebound structure.
0
FIELD OF INVENTION This invention relates to a method for reducing the level of dissolved oxygen or other elements from solid metals, metal compounds and semi-metal compounds and alloys. In addition, the method relates to the direct production of metal from metal oxides or other compounds. BACKGROUND TO THE INVENTION Many metals and semi-metals form oxides, and some have a significant solubility for oxygen. In many cases, the oxygen is detrimental and therefore needs to be reduced or removed before the metal can be fully exploited for its mechanical or electrical properties. For example, titanium, zirconium and hafnium are highly reactive elements and, when exposed to oxygen-containing environments rapidly form an oxide layer, even at room temperature. This passivation is the basis of their outstanding corrosion resistance under oxidising conditions. However, this high reactivity has attendant disadvantages which have dominated the extraction and processing of these metals. As well as oxidising at high temperatures in the conventional way to form an oxide scale, titanium and other elements have a significant solubility for oxygen and other metalloids (e.g. carbon and nitrogen) which results in a serious loss of ductility. This high reactivity of titanium and other Group IVA elements extends to reaction with refractory materials such as oxides, carbides etc. at elevated temperatures, again contaminating and embrittling the basis metal. This behaviour is extremely deleterious in the commercial extraction, melting and processing of the metals concerned. Typically, extraction of a metal from the metal oxide is achieved by heating the oxide in the presence of a reducing agent (the reductant). The choice of reductant is determined by the comparative thermodynamics of the oxide and the reductant, specifically the free energy balance in the reducing reactions. This balance must be negative to provide the driving force for the reduction to proceed. The reaction kinetics are influenced principally by the temperature of reduction and additionally by the chemical activities of the components involved. The latter is often an important feature in determining the efficiency of the process and the completeness of the reaction. For example, it is often found that although this reduction should in theory proceed to completion, the kinetics are considerably slowed down by the progressive lowering of the activities of the components involved. In the case of an oxide source material, this results in a residual content of oxygen (or another element that might be involved) which can be deleterious to the properties of the reduced metal, for example, in lower ductility, etc. This frequently leads to the need for further operations to refine the metal and remove the final residual impurities, to achieve high quality metal. Because the reactivity of Group IVA elements is high, and the deleterious effect of residual impurities serious, extraction of these elements is not normally carried out from the oxide, but following preliminary chlorination, by reducing the chloride. Magnesium or sodium are often used as the reductant. In this way, the deleterious effects of residual oxygen are avoided. This inevitably leads, however, to higher costs which make the final metal more expensive, which limits its application and value to a potential user. Despite the use of this process, contamination with oxygen still occurs. During processing at high temperatures, for example, a hard layer of oxygen-enriched material is formed beneath the more conventional oxide scale. In titanium alloys this is often called the “alpha case”, from the stabilising effect of oxygen on the alpha phase in alpha-beta alloys. If this layer is not removed, subsequent processing at room temperature can lead to the initiation of cracks in the hard and relatively brittle surface layer. These can then propagate into the body of the metal, beneath the alpha case. If the hard alpha case or cracked surface is not removed before further processing of the metal, or service of the product, there can be a serious reduction in performance, especially of the fatigue properties. Heat treatment in a reducing atmosphere is not available as a means of overcoming this problem because of the embrittlement of the Group IVA metals by hydrogen and because the oxide or “dissolved oxygen” cannot be reduced or minimised. The commercial costs of getting round this problem are significant. In practice, for example, metal is often cleaned up after hot working by firstly removing the oxide scale by mechanical grinding, grit-blasting, or using a molten salt, followed by acid pickling, often in HNO 3 /HF mixtures to remove the oxygen-enriched layer of metal beneath the scale. These operations are costly in terms of loss of metal yield, consumables and not least in effluent treatment. To minimise scaling and the costs associated with the removal of the scale, hot working is carried out at as low a temperature as is practical. This, in itself, reduces plant productivity, as well as increasing the load on the plant due to the reduced workability of the material at lower temperatures. All of these factors increase the costs of processing. In addition, acid pickling is not always easy to control, either in terms of hydrogen contamination of the metal, which leads to serious embrittlement problems, or in surface finish and dimensional control. The latter is especially important in the production of thin materials such as thin sheet, fine wire, etc. It is evident therefore, that a process which can remove the oxide layer from a metal and additionally the dissolved oxygen of the sub-surface alpha case, without the grinding and pickling described above, could have considerable technical and economic benefits on metal processing, including metal extraction. Such a process may also have advantages in ancillary steps of the purification treatment, or processing. For instance, the scrap turnings produced either during the mechanical removal of the alpha case, or machining to finished size, are difficult to recycle due to their high oxygen content and hardness, and the consequent effect on the chemical composition and increase in hardness of the metal into which they are recycled. Even greater advantages might accrue if material which had been in service at elevated temperatures and had been oxidised or contaminated with oxygen could be rejuvenated by a simple treatment. For example, the life of an aero-engine compressor blade or disc made from titanium alloy is constrained, to a certain extent, by the depth of the alpha case layer and the dangers of surface crack initiation and propagation into the body of the disc, leading to premature failure. In this instance, acid pickling and surface grinding are not possible options since a loss of dimension could not be tolerated. A technique which lowered the dissolved oxygen content without affecting the overall dimensions, especially in complex shapes, such as blades or compressor discs, would have obvious and very important economic benefits. Because of the greater effect of temperature on thermodynamic efficiency these benefits would be compounded if they allowed the discs to operate not just for longer times at the same temperature, but also possibly at higher temperatures where greater fuel efficiency of the aeroengine can be achieved. In addition to titanium, a further metal of commercial interest is Germanium, which is a semi-conducting metalloid element found in Group IVA of the Periodic Table. It is used, in a highly purified state, in infra-red optics and electronics. Oxygen, phosphorus, arsenic, antimony and other metalloids are typical of the impurities which must be carefully controlled in Germanium to ensure an adequate performance. Silicon is a similar semiconductor and its electrical properties depend critically on its purity content. Controlled purity of the parent silicon or germanium is fundamentally important as a secure and reproducible basis, onto which the required electrical properties can be built up in computer chips, etc. U.S. Pat. No. 5,211,775 discloses the use of calcium metal to deoxidise titanium. Okabe, Oishi and Ono (Met. Trans B. 23B (1992):583, have used a calcium-aluminium alloy to deoxidise titanium aluminide. Okabe, Nakamura, Oishi and Ono (Met. Trans B. 24B (1993):449) deoxidised titanium by electrochemically producing calcium from a calcium chloride melt, on the surface of titanium. Okabe, Devra, Oishi, Ono and Sadoway (Journal of Alloys and Compounds 237 (1996) 150) have deoxidised yttrium using a similar approach. Ward et al, Journal of the Institute of Metals (1961) 90:6-12, describes an electrolytic treatment for the removal of various contaminating elements from molten copper during a refining process. The molten copper is treated in a cell with barium chloride as the electrolyte. The experiments show that sulphur can be removed using this process. However, the removal of oxygen is less certain, and the authors state that spontaneous non-electrolytic oxygen loss occurs, which may mask the extent of oxygen removal by this process. Furthermore, the process requires the metal to be molten, which adds to the overall cost of the refining process. The process is therefore unsuitable for a metal such as titanium which melts at 1660° C., and which has a highly reactive melt. SUMMARY OF INVENTION According to the present invention, a method for removing a substance (X) from a solid metal or semi-metal compound (M 1 X) by electrolysis in a melt of M 2 Y, comprises conducting the electrolysis under conditions such that reaction of X rather than M 2 deposition occurs at an electrode surface, and that X dissolves in the electrolyte M 2 Y. According to one embodiment of the invention, M 1 X is a conductor and is used as the cathode. Alternatively, M 1 X may be an insulator in contact with a conductor. In a separate embodiment, the electrolysis product (M 2 X) is more stable than M 1 X. In a preferred embodiment, M 2 may be any of Ca, Ba, Li, Cs or Sr and Y is Cl. Preferably, M 1 X is a surface coating on a body of M 1 . In a separate preferred embodiment, X is dissolved within M 1 . In a further preferred embodiment, X is any of O, S, C or N. In a still further preferred embodiment, M 1 is any of Ti, Si, Ge, Zr, Hf, Sm, U, Al, Mg, Nd, Mo, Cr, Nb, or any alloy thereof. In the method of the invention, electrolysis preferably occurs with a potential below the decomposition potential of the electrolyte. A further metal compound or semi-metal compound (M N X) may be present, and the electrolysis product may be an alloy of the metallic elements. The present invention is based on the realisation that an electrochemical process can be used to ionise the oxygen contained in a solid metal so that the oxygen dissolves in the electrolyte. When a suitably negative potential is applied in an electrochemical cell with the oxygen-containing metal as cathode, the following reaction occurs: O+ 2 e − ≈O 2− The ionised oxygen is then able to dissolve in the electrolyte. The invention may be used either to extract dissolved oxygen from a metal, i.e. to remove the α case, or may be used to remove the oxygen from a metal oxide. If a mixture of oxides is used, the cathodic reduction of the oxides will cause an alloy to form. The process for carrying out the invention is more direct and cheaper than the more usual reduction and refining process used currently. In principle, other cathodic reactions involving the reduction and dissolution of other metalloids, carbon, nitrogen, phosphorus, arsenic, antimony etc. could also take place. Various electrode potentials, relative to E Na =O V, at 700° C. in fused chloride melts containing calcium chloride, are as follows: Ba 2 + 2e − = Ba −0.314 V Ca 2 + 2e − = Ca −0.06 V Hf 4+ + 4e − = Hf 1.092 V Zr 4+ + 4e − = Zr 1.516 V Ti 4+ + 4e − = Ti 2.039 V Cu + + e− = Cu 2.339 V Cu 2+ + 2e − = Cu 2.92 V O 2 + 4e − = 20 2− 2.77 V The metal, metal compound or semi-metal compound can be in the form of single crystals or slabs, sheets, wires, tubes, etc., commonly known as semi-finished or mill-products, during or after production; or alternatively in the form of an artefact made from a mill-product such as by forging, machining, welding, or a combination of these, during or after service. The element or its alloy can also be in the form of shavings, swarf, grindings or some other by-product of a fabrication process. In addition, the metal oxide may also be applied to a metal substrate prior to treatment, e.g. TiO 2 may be applied to steel and subsequently reduced to the titanium metal. DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic illustration of the apparatus used in the present invention; FIG. 2 illustrates the hardness profiles of a surface sample of titanium before and after electrolysis at 3.0 V and 850° C.; and FIG. 3 illustrates the difference in currents for electrolytic reduction of TiO 2 pellets under different conditions. DESCRIPTION OF THE INVENTION In the present invention, it is important that the potential of the cathode is maintained and controlled potentiostatically so that only oxygen ionisation occurs and not the more usual deposition of the cations in the fused salt. The extent to which the reaction occurs depends upon the diffusion of the oxygen in the surface of the metal cathode. If the rate of diffusion is low, the reaction soon becomes polarised and, in order for the current to keep flowing, the potential becomes more cathodic and the next competing cathodic reaction will occur, i.e. the deposition of the cation from the fused salt electrolyte. However, if the process is allowed to take place at elevated temperatures, the diffusion and ionisation of the oxygen dissolved in the cathode will be sufficient to satisfy the applied currents, and oxygen will be removed from the cathode. This will continue until the potential becomes more cathodic, due to the lower level of dissolved oxygen in the metal, until the potential equates to the discharge potential for the cation from the electrolyte. This invention may also be used to remove dissolved oxygen or other dissolved elements, e.g. sulphur, nitrogen and carbon from other metals or semi-metals, e.g. germanium, silicon, hafnium and zirconium. The invention can also be used to electrolytically decompose oxides of elements such as titanium, uranium, magnesium, aluminium, zirconium, hafnium, niobium, molybdenum, neodymium, samarium and other rare earths. When mixtures of oxides are reduced, an alloy of the reduced metals will form. The metal oxide compound should show at least some initial metallic conductivity or be in contact with a conductor. An embodiment of the invention will now be described with reference to the drawing, where FIG. 1 shows a piece of titanium made in a cell consisting of an inert anode immersed in a molten salt. The titanium may be in the form of a rod, sheet or other artefact. If the titanium is in the form of swarf or particulate matter, it may be held in a mesh basket. On the application of a voltage via a power source, a current will not start to flow until balancing reactions occur at both the anode and cathode. At the cathode, there are two possible reactions, the discharge of the cation from the salt or the ionisation and dissolution of oxygen. The latter reaction occurs at a more positive potential than the discharge of the metal cation and, therefore, will occur first. However, for the reaction to proceed, it is necessary for the oxygen to diffuse to the surface of the titanium and, depending on the temperature, this can be a slow process. For best results it is, therefore, important that the reaction is carried out at a suitably elevated temperature, and that the cathodic potential is controlled, to prevent the potential from rising and the metal cations in the electrolyte being discharged as a competing reaction to the ionisation and dissolution of oxygen into the electrolyte. This can be ensured by measuring the potential of the titanium relative to a reference electrode, and prevented by potentiostatic control so that the potential never becomes sufficiently cathodic to discharge the metal ions from the fused salt. The electrolyte must consist of salts which are preferably more stable than the equivalent salts of the metal which is being refined and, ideally, the salt should be as stable as possible to remove the oxygen to as low as concentration as possible. The choice includes the chloride salts of barium, calcium, cesium, lithium, strontium and yttrium. The melting and boiling points of these chlorides are given below: Melting Point (° C.) Boiling Point (° C.) BaCl 2 963 1560 CaCl 2 782 >1600   CsCl 645 1280 LiCl 605 1360 SrCl 2 875 1250 YCl 3 721 1507 Using salts with a low melting point, it is possible to use mixtures of these salts if a fused salt melting at a lower temperature is required, e.g. by utilising a eutectic or near-eutectic mixture. It is also advantageous to have, as an electrolyte, a salt with as wide a difference between the melting and boiling points, since this gives a wide operating temperature without excessive vaporisation. Furthermore, the higher the temperature of operation, the greater will be the diffusion of the oxygen in the surface layer and therefore the time for deoxidation to take place will be correspondingly less. Any salt could be used provided the oxide of the cation in the salt is more stable than the oxide of the metal to be purified. The following Examples illustrate the invention. In particular, Examples 1 and 2 relate to removal of oxygen from an oxide. EXAMPLE 1 A white TiO 2 pellet, 5 mm in diameter and 1 mm in thickness, was placed in a titanium crucible filled with molten calcium chloride at 950° C. A potential of 3V was applied between a graphite anode and the titanium crucible. After 5 h, the salt was allowed to solidify and then dissolved in water to reveal a black/metallic pellet. Analysis of the pellet showed that it was 99.8% titanium. EXAMPLE 2 A strip of titanium foil was heavily oxidised in air to give a thick coating of oxide (c.50 mm). The foil was placed in molten calcium chloride at 950° C. and a potential of 1.75V applied for 1.5 h. On removing the titanium foil from the melt, the oxide layer had been completely reduced to metal. Examples 3-5 relate to removal of dissolved oxygen contained within a metal. EXAMPLE 3 Commercial purity (CP) titanium sheets (oxygen 1350-1450 ppm, Vickers Hardness Number 180) were made the cathode in a molten calcium chloride melt, with a carbon anode. The following potentials were applied for 3 h at 950° C. followed by 1.5 h at 800° C. The results were as follows: Vickers Hardness Oxygen V (volt) Number Content 3 V 133.5 <200 ppm 3.3 V 103   <200 ppm 2.8 V 111   <200 ppm 3.1 V 101   <200 ppm The 200 ppm was the lowest detection limit of the analytical equipment. The hardness of titanium is directly related to the oxygen content, and so measuring the hardness provides a good indication of oxygen content. The decomposition potential of pure calcium chloride at these temperatures is 3.2 V. When polarisation losses and resistive losses are considered, a cell potential of around 3.5V is required to deposit calcium. Since it is not possible for calcium to be deposited below this potential, these results prove that the cathodic reaction is: O+2 e − =O 2− This further demonstrates that oxygen can be removed from titanium by this technique. EXAMPLE 4 A sheet of commercial purity titanium was heated for 15 hours in air at 700° C. in order to form an alpha case on the surface of the titanium. After making the sample the cathode in a CaCl 2 melt with a carbon anode at 850° C., applying a potential of 3V for 4 hours at 850° C., the alpha case was removed as shown by the hardness curve (FIG. 2 ), where VHN represents the Vicker's Hardness Number. EXAMPLE 5 A titanium 6 Al 4V alloy sheet containing 1800 ppm oxygen was made the cathode in a CaCl 2 melt at 950° C. and a cathodic potential of 3V applied. After 3 hours, the oxygen content was decreased from 1800 ppm to 1250 ppm. Examples 6 and 7 show the removal of the alpha case from an alloy foil. EXAMPLE 6 A Ti-6A1-4V alloy foil sample with an alpha case (thickness about 40 μm) under the surface was electrically connected at one end to a cathodic current collector (a Kanthal wire) and then inserted into a CaCl 2 melt. The melt was contained in a titanium crucible which was placed in a sealed Inconel reactor that was continuously flushed with argon gas at 950° C. The sample size was 1.2 mm thick, 8.0 mm wide and ˜50 mm long. Electrolysis was carried out in a manner of controlled voltage, 3.0V. It was repeated with two different experimental times and end temperatures. In the first case, the electrolysis lasted for one hour and the sample was immediately taken out of the reactor. In the second case, after 3 hours of electrolysis, the temperature of the furnace was allowed to cool naturally while maintaining the electrolysis. When the furnace temperature dropped to slightly lower than 800° C., the electrolysis was terminated and the electrode removed. Washing in water revealed that the 1 hour sample had a metallic surface but with patches of brown colour, whilst the 3 hour sample was completely metallic. Both samples were then sectioned and mounted in a bakelite stub and a normal grinding and polishing procedure was carried out. The cross section of the samples was investigated by microhardness test, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The hardness test showed that the alpha case of both samples disappeared, although the 3 hour sample showed a hardness near the surface much lower than that at the centre of the sample. In addition, SEM and EDX detected insignificant changes in the structure and elemental composition (except for oxygen) in the deoxygenated samples. EXAMPLE 7 In a separate experiment, Ti-6A1-4V foil samples as described above (1.2 mm thick, 8 mm wide and 25 mm long) were placed at the bottom of the titanium crucible which functioned as the cathodic current collector. The electrolysis was then carried out under the same conditions as mentioned in Example 6 for the 3-hour sample except that the electrolysis lasted for 4 hours at 950° C. Again using microhardness test, SEM and EDX revealed the successful removal of the alpha case in all the three samples without altering the structure and elemental composition except for oxygen. Example 8 shows a slip-cast technique for the fabrication of the oxide electrode. EXAMPLE 8 A TiO 2 powder (anatase, Aldrich, 99.9+% purity; the powder possibly contains a surfactant) was mixed with water to produce a slurry (TiO 2 :H 2 O=5:2 wt) that was then slip-cast into a variety of shapes (round pellets, rectangular blocks, cylinders, etc) and sizes (from millimeters to centimeters), dried in room/ambient atmosphere overnight and sintered in air, typically for two hours at 950° C. in air. The resultant TiO 2 solid has a workable strength and a porosity of 40˜50%. There was notable but insignificant shrinkage between the sintered and unsintered TiO 2 pellets. 0.3 g˜10 g of the pellets were placed at the bottom of a titanium crucible containing a fresh CaCl 2 melt (typically 140 g). Electrolysis was carried out at 3.0V (between the titanium crucible and a graphite rod anode) and 950° C. under an argon environment for 5-15 hours. It was observed that the current flow at the beginning of the electrolysis increased nearly proportionally with the amount of the pellets and followed roughly a pattern of 1 g TiO 2 corresponding to 1A initial current flow. It was observed that the degree of reduction of the pellets can be estimated by the colour in the centre of the pellet. A more reduced or metallised pellet is grey in colour throughout, but a lesser reduced pellet is dark grey or black in the centre. The degree of reduction of the pellets can also be judged by placing them in distilled water for a few hours to overnight. The partially reduced pellets automatically break into fine black powders while the metallised pellets remain in the original shape. It was also noticed that even for the metallised pellets, the oxygen content can be estimated by the resistance to pressure applied at room temperature. The pellets became a grey powder under the pressure if there was a high level of oxygen, but a metallic sheet if the oxygen levels were low. SEM and EDX investigation of the pellets revealed considerable difference in both composition and structure between metallised and partially reduced pellets. In the metallised case, the typical structure of dendritic particles was always seen, and no or little oxygen was detected by EDX. However, the partially reduced pellets were characterised by crystallites having a composition of Ca x Ti y O z as revealed by EDX. EXAMPLE 9 It is highly desirable that the electrolytic extraction be performed on a large scale and the product removed conveniently from the molten salt at the end of the electrolysis. This may be achieved for example by placing the TiO 2 pellets in a basket-type electrode. The basket was fabricated by drilling many holes (˜3.5 mm diameter) into a thin titanium foil (˜1.0 mm thickness) which was then bent at the edge to form a shallow cuboid basket with an internal volume of 15×45×45 mm 3 . The basket was connected to a power supply by a Kanthal wire. A large graphite crucible (140 mm depth, 70 mm diameter and 10 mm wall thickness) was used to contain the CaCl 2 melt. It was also connected to the power supply and functioned as the anode. Approximately 10 g slip-cast TiO 2 pellets/blobs (each was about 10 mm diameter and 3 mm maximum thickness) were placed in the titanium basket and lowered into the melt. Electrolysis was conducted at 3.0V, 950° C., for approximately 10 hours before the furnace temperature was allowed to drop naturally. When the temperature reached about 800° C., the electrolysis was terminated. The basket was then raised from the melt and kept in a water-cooled upper part of the Inconel tube reactor until the furnace temperature dropped to below 200° C. before being taken out for analysis. After acidic leaching (HCl, pH<2) and washing in water, the electrolysed pellets exhibited the same SEM and EDX features as observed above. Some of the pellets were ground into a powder and analysed by thermo-gravitmetry and vacuum fusion elemental analysis. The results showed that the powder contained about 20,000 ppm oxygen. SEM and EDX analysis showed that, apart from the typical dendritic structure, some crystallites of CaTiO x (x<3) were observed in the powder which may be responsible for a significant fraction of the oxygen contained in the product. If this is the case, it is expected that upon melting the powder, purer titanium metal ingot can be produced. An alternative to the basket-type electrode is the use of a “lolly” type TiO 2 electrode. This is composed of a central current collector and on top of the collector a reasonably thick layer of porous TiO 2 . In addition to a reduced surface area of the current collector, other advantages of using a lolly-type TiO 2 electrode include: firstly, that it can be removed from the reactor immediately after electrolysis, saving both processing time and CaCl 2 ; secondly, and more importantly, the potential and current distribution and therefore current efficiency can be improved greatly. EXAMPLE 10 A slurry of Aldrich anatase TiO 2 powder was slip cast into a slightly tapered cylindrical lolly (˜20 mm length) comprising a titanium metal foil (0.6 mm thickness, 3 mm width and ˜40 mm length) in the centre. After sintering at 950° C., the lolly was connected electrically at the end of the titanium foil to a power supply by a Kanthal wire. Electrolysis was carried out at 3.0V and 950° C. for about 10 hours. The electrode was removed from the melt at about 800° C., washed and leached by weak HCl acid (pH 1-2). The product was then analysed by SEM and EDX. Again, a typical dendritic structure was observed and no oxygen, chlorine and calcium could be detected by EDX. The slip-cast method may be used to fabricate large rectangular or cylindrical blocks of TiO 2 that can then be machined to an electrode with a desired shape and size suitable for industrial processing. In addition, large reticulated TiO 2 blocks, e.g. TiO 2 foams with a thick skeleton, can also be made by slip casting, and this will help the draining of the molten salt. The fact that there is little oxygen in a dried fresh CaCl 2 melt suggests that the discharge of the chloride anions must be the dominant anodic reaction at the initial stage of electrolysis. This anodic reaction will continue until oxygen anions from the cathode transport to the anode. The reactions can be summarised as follows: anode: Cl − ½Cl 2 i + e cathode: TiO 2 + 4e −  Ti + 20 2− total: TiO 2 + 4Cl −  Ti + 2Cl 2 i + 2O 2− When sufficient O 2− ions are present the anodic reaction becomes: O 2− ≈½O 2 +2 e − and the overall reaction: TiO 2 ≈Ti+O 2 ↑ Apparently the depletion of chloride anions is irreversible and consequently the cathodically formed oxygen anions will stay in the melt to balance the charge, leading to an increase of the oxygen concentration in the melt. Since the oxygen level in the titanium cathode is in a chemical equilibrium or quasi-equilibrium with the oxygen level in the melt for example via the following reaction: Ti + CaO ≈ TiO + Ca     K  ( 950  °     C . ) = 3.28 × 10 - 4 It is expected that the final oxygen level in the electrolytically extracted titanium cannot be very low if the electrolysis proceeds in the same melt with controlling the voltage only. This problem can be solved by (1) controlling the initial rate of the cathodic oxygen discharge and (2) reducing the oxygen concentration of the melt. The former can be achieved by controlling the current flow at the initial stage of the electrolysis, for example gradually increasing the applied cell voltage to the desired value so that the current flow will not go beyond a limit. This method may be termed “double-controlled electrolysis”. The latter solution to the problem may be achieved by performing the electrolysis in a high oxygen level melt first, which reduces TiO 2 to the metal with a high oxygen content, and then transferring the metal electrode to a low oxygen melt for further electrolysis. The electrolysis in the low oxygen melt can be considered as an electrolytic refining process and may be termed “double-melt electrolysis”. Example 11 illustrates the use of the “doublemelt electrolysis” principle. EXAMPLE 11 A TiO 2 lolly electrode was prepared as described in Example 10. A first electrolysis step was carried out at 3.0V, 950° C. overnight (˜12 hours) in re-melted CaCl 2 contained within an alumina crucible. A graphite rod was used as the anode. The lolly electrode was then transferred immediately to a fresh CaCl 2 melt contained within a titanium crucible. A second electrolysis was then carried out for about 8 hours at the same voltage and temperature as the first electrolysis, again with a graphite rod as the anode. The lolly electrode was removed from the reactor at about 800° C., washed, acid leached and washed again in distilled water with the aid of an ultrasonic bath. Again both SEM and EDX confirmed the success in extraction. Thermo-weight analysis was applied to determine the purity of the extracted titanium based on the principle of re-oxidation. About 50 mg of the sample from the lolly electrode was placed in a small alumina crucible with a lid and heated in air to 950° C. for about 1 hour. The crucible containing the sample was weighted before and after the heating and the weight increase was observed. The weight increase was then compared with the theoretical increase when pure titanium is oxidised to titanium dioxide. The result showed that the sample contained 99.7+% of titanium, implying less than 3000 ppm oxygen. EXAMPLE 12 The principle of this invention can be applied not only to titanium but also other metals and their alloys. A mixture of TiO 2 and Al 2 O 3 powders (5:1 wt) was slightly moistened and pressed into pellets (20 mm diameter and 2 mm thickness) which were later sintered in air at 950° C. for 2 hours. The sintered pellets were white and slightly smaller than before sintering. Two of the pellets were electrolysed in the same way as described in Example 1 and Example 3. SEM and EDX analysis revealed that after electrolysis the pellets changed to the Ti—Al metal alloy although the elemental distribution in the pellet was not uniform: the Al concentration was higher in the central part of the pellet than near the surface, varying from 12 wt % to 1 wt %. The microstructure of the Ti—Al alloy pellet was similar to that of the pure Ti pellet. FIG. 3 shows the comparison of currents for the electrolytic reduction of TiO 2 pellets under different conditions. It can be shown that the amount of current flowing is directly proportional to the amount of oxide in the reactor. More importantly, it also shows that the current decreases with time and therefore it is probably the oxygen in the dioxide that is ionising and not the deposition of calcium. If calcium was being deposited, the current should remain constant with time.
The present invention pertains to a method for removing a substance (X) from a solid metal or semi-metal compound (M 1 X) by electrolysis in a melt of M 2 Y, which comprises conducting the electrolysis under conditions such that reaction of X rather than M 2 deposition occurs at a electrode surface, and that X dissolves in the electrolyte M 2 Y. The substance X is either removed from the surface (i.e., M 1 X) or by means of diffusion extracted from the case material. The temperature of the fused salt is chosen below the melting temperature of the metal M 1 . The potential is chosen below the decomposition potential of the electrolyte.
2
RELATED APPLICATIONS [0001] This application is a continuation of U.S. application Ser. No. 10/656,360, filed on Sep. 5, 2003, pending, which is a continuation of U.S. application Ser. No. 10/006,624, filed on Nov. 30, 2001, now U.S. Pat. No. 6,680,315, which is a continuation-in-part of U.S. application Ser. No. 09/594,362, filed on Jun. 15, 2000, now U.S. Pat. No. 6,384,032, all of which are incorporated herein by reference in their entirety. BACKGROUND [0002] Interleukin-12 (IL-112) is a heterodimeric cytokine (p70) composed of two subunits (p35 and p40), and plays key roles in immune responses by bridging innate resistance and antigen-specific adaptive immunity. Trinchieri (1993) Immunol Today 14: 335. For example, it promotes type 1 T helper cell (Th1) responses and, hence, cell-mediated immunity. Chan et al. (1991) J Exp Med 173: 869; Seder et al. (1993) Proc Natl Acad Sci USA 90: 10188; Manetti et al. (1993) J Exp Med 177: 1199; and Hsieh et al. (1993) Science 260: 547. Overproduction of IL-12 causes excessive Th1 responses, and may result in inflammatory disorders, insulin-dependent diabetes mellitus, multiple sclerosis, rheumatoid arthritis, psoriasis, Crohn's disease, or sepsis. See, for example, Gately et al. (1998) Annu Rev Immunol. 16: 495; and Abbas et al. (1996) Nature 383: 787. Thus, inhibiting IL-12 overproduction is an approach to treat the just-mentioned diseases. Trembleau et al. (1995) Immunol. Today 16: 383; and Adorini et al. (1997) Chem. Immunol. 68: 175. For example, overproduction of IL-12 and the resultant excessive Th1 type responses can be suppressed by modulating IL-12 production. A compound that down-regulates IL-12 production can be used for treating inflammatory diseases. Ma et al. (1998) Eur Cytokine Netw 9: 54. SUMMARY [0003] This invention is based on the identification of new compounds from a library of 80,000 compounds, which were screened for their abilities to inhibit IL-12 overproduction. In one aspect, this invention features triazine compounds of formula (I) wherein R 1 is [referred to hereinafter as NC(R a R b )], aryl, or heteroaryl; each of R 2 , R 4 , and R 5 , independently, is R c , halogen, nitro, nitroso, cyano, azide, isothionitro, SR c , or OR c ; R 3 is R c , alkenyl, alkynyl, aryl, heteroaryl, cyclyl, heterocyclyl, OR c , OC(O)R c , SO 2 R c , S(O)R c , S(O 2 )NR c R d , SR c , NR c R d , NR c COR d , NR c C(O)OR c , NR c C(O)NR c R, NR c SO 2 R d , COR c , C(O)OR c , or C(O)NR c R d ; n is 0, 1, 2, 3, 4, 5, 6, or 7; X is O, S, S(O), S(O 2 ), or NR c ; Y is a covalent bond, CH 2 , C(O), C═N—R c , C═N—OR c , C═N—SR c , O, S, S(O), or S(O 2 ); Z is N; and W is O, S, S(O), S(O 2 ), NR c , or NC(O)R c ; in which each of R a and R b , independently, is H, alkyl, aryl, heteroaryl; and each of R c and R d , independently, is H, alkyl, or alkylcarbonyl. Note that the left atom shown in any substituted group described above is closest to the tirazine ring. Also note that when n is 2 or greater, the just-described triazine compound may have two or more different C(R 2 R 4 ) moieties. The same rule applies to other similar situations. [0004] Referring to formula (I), a subset of the triazine compounds of this invention is featured by that R 1 is NC(R a R b ). In these compounds, W can be 0; R 5 can be H or alkyl; X can be NR c ; R c can be H, methyl, ethyl, or acetyl; Y can be O or CH 2 , and n can be 0, 1, 2, 3, or 4. In some embodiments, R 3 is aryl, heteroaryl (e.g., pyridinyl), OR c , SR c , C(O)OR c , or C(O)NR c Rd. In other embodiments, R 3 is in which each of A and A′, independently, is O, S, or NH; each of R e and R f , independently, is H, alkyl, aryl, or heteroaryl; and m is 1 or 2. [0005] In this subset of triazine compounds, R a or R b , preferably, is in which B is NR i , O, or S; B′ is N or CR i ; R g is H, alkyl, or alkoxyl; R h is halogen, CN, hydroxyl, alkyl, aryl, heteroaryl, alkoxyl, aryloxyl, or heteroaryloxyl; R i is H, alkyl, or alkylcarbonyl; p is 0, 1, or 2; and q is 0, 1, 2, 3, or 4. Preferably, B is NR i ; B′ is CH; R g is H, methyl, ethyl, methoxy, or ethoxy; R h is F, Cl, CN, methoxy, methyl, or ethoxy; R i is H, methyl, ethyl, or acetyl; and q is 0, 1, or 2. [0006] Another subset of the triazine compounds of this invention is featured by that R 1 is aryl or heteroaryl. In these compounds, W can be 0; R 5 can be H or alkyl; X can be NR c ; R c can be H, methyl, ethyl, or acetyl; Y can be O or CH 2 , and n can be 0, 1, 2, 3, or 4. In some embodiments, R 3 is aryl, heteroaryl (e.g., pyridinyl), OR c , SR c , C(O)OR c , or C(O)NR c R d . In other embodiments, R 3 is in which each of A and A′, independently, is O, S, or NH; each of R e and R f , independently, is H, alkyl, aryl, or heteroaryl; and m is 1 or 2. [0007] In this second subset of triazine compounds, R 1 , preferably, is in which D is O, S, or NR m ; D′ is N or CR m ; R j is halogen, CN, hydroxyl, alkyl, aryl, heteroaryl, alkoxyl, aryloxyl, or heteroaryloxyl; R k is aryl or hetereoaryl; R l is H, alkyl, or alkylcarbonyl; R m is H, alkyl, or alkylcarbonyl; r is 0, 1, or 2; s is 0 or 1; t is 0, 1, 2, 3, or 4; and u is 0, 1, 2, 3, 4, or 5. Preferably, R 1 is and R j is methyl, ethyl, propyl, or benzyl; and r can be 1 or 2. [0008] In another aspect, this invention also features triazine compounds of formula (I), wherein R 1 is NC(R a R b ), aryl, or heteroaryl; each of R 2 , R 4 , and R 5 , independently, is R c , halogen, nitro, nitroso, cyano, azide, isothionitro, SR c , or OR c ; R 3 is R c , alkenyl, alkynyl, aryl, heteroaryl, cyclyl, heterocyclyl, OR c , OC(O)R c , SO 2 R c , S(O)R c , S(O 2 )NR c R d , SR c , NR c R d , NR c COR d , NR c C(O)OR d , NR c C(O)NR c R d , NRCSO 2 R d , COR c , C(O)OR c , or C(O)NR c R d ; n is 0, 1, 2, 3, 4, 5, 6, or 7; X is O, S, S(O), S(O 2 ), or NR c ; Y is a covalent bond, CH 2 , C(O), C═N—R c , C═N—OR c , C═N—SR c , O, S, S(O), S(O 2 ), or NR c ; Z is CH; and W is O, S, S(O), S(O 2 ), NR c , or NC(O)R c ; in which each of R a and R b , independently, is H, alkyl, aryl, heteroaryl; and each of R c and R d , independently, is H, alkyl, or alkylcarbonyl. A subset of the triazine compounds is featured by that R 1 is NC(R a R b ); and another subset is featured by that R 1 is aryl or heteroaryl. [0009] Alkyl, alkenyl, alkynyl, aryl, heteroaryl (e.g., pyridinyl), cyclyl, heterocyclyl mentioned herein include both substituted and unsubstituted moieties. The term “substituted” refers to one or more substituents (which may be the same or different), each replacing a hydrogen atom. Examples of substituents include, but are not limited to, halogen, hydroxyl, amino, alkylamino, arylamino, dialkylamino, diarylamino, cyano, nitro, mercapto, carbonyl, carbamido, carbamyl, carboxyl, thioureido, thiocyanato, sulfoamido, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 alkoxy, aryl, heteroaryl, cyclyl, heterocyclyl, wherein alkyl, alkenyl, alkoxy, aryl, heteroaryl cyclyl, and heterocyclyl are optionally substituted with C 1 -C 6 alkyl, aryl, heteroaryl, halogen, hydroxyl, amino, mercapto, cyano, or nitro. The term “aryl” refers to a hydrocarbon ring system having at least one aromatic ring. Examples of aryl moieties include, but are not limited to, phenyl, naphthyl, and pyrenyl. The term “heteroaryl” refers to a hydrocarbon ring system having at least one aromatic ring which contains at least one heteroatom such as O, N, or S. Examples of heteroaryl moieties include, but are not limited to, furyl, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, and indolyl. [0010] Set forth below are exemplary compounds (Compounds 1-12) of this invention: [0011] In still another aspect, this invention features a pharmaceutical composition that contains a pharmaceutically acceptable carrier and an effective amount of at least one of the above-described triazine compounds. [0012] In further another aspect, the present invention features a method for treating an IL-12 overproduction-related disorder (e.g., rheumatoid arthritis, sepsis, Crohn's disease, multiple Sclerosis, psoriasis, or insulin-dependent diabetes). The method includes administering to a subject in need thereof an effective amount of a triazine compound of formula (I), wherein R 1 is NC(R a R b ), aryl, or heteroaryl; each of R 2 , R 4 , and R 5 , independently, is R c , halogen, nitro, nitroso, cyano, azide, isothionitro, SR c , or OR c ; R 3 is R c , alkenyl, alkynyl, aryl, heteroaryl, cyclyl, heterocyclyl, OR c , OC(O)R c , SO 2 R c , S(O)R c , S(O 2 )NR c R d , SR c , NR c R d , NR c COR d , NR c C(O)OR d , NR c C(O)NR c R d , NR c SO 2 R d , COR c , C(O)OR c , or C(O)NR c R d ; n is 0, 1, 2, 3, 4, 5, 6, or 7; X is O, S, S(O), S(O 2 ), or NR c ; Y is a covalent bond, CH 2 , C(O), C═N—R c , C═N—OR c , C═N—SR c , O, S, S(O), S(O 2 ), or NR c ; Z is N or CH; and W is O, S, S(O), S(O 2 ), NR c , or NC(O)R c ; in which each of R a and R b , independently, is H, alkyl, aryl, heteroaryl; and each of R c and R d , independently, is H, alkyl, or alkylcarbonyl. [0013] The triazine compounds described above include the compounds themselves, as well as their salts and their prodrugs, if applicable. The salts, for example, can be formed between a positively charged substituent (e.g., amino) on a compound and an anion. Suitable anions include, but are not limited to, chloride, bromide, iodide, sulfate, nitrate, phosphate, citrate, methanesulfonate, trifluoroacetate, and acetate. Likewise, a negatively charged substituent (e.g., carboxylate) on a compound can form a salt with a cation. Suitable cations include, but are not limited to, sodium ion, potassium ion, magnesium ion, calcium ion, and an ammonium cation such as teteramethylammonium ion. Examples of prodrugs include esters and other pharmaceutically acceptable derivatives, which, upon administration to a subject, are capable of providing the triazine compounds described above. [0014] In addition, some of the just-described triazine compounds have one or more double bonds, or one or more asymmetric centers. Such compounds can occur as racemates, racemic mixtures, single enantiomers, individual diastereomers, diastereomeric mixtures, and cis- or trans- or E- or Z-double bond isomeric forms. [0015] Also within the scope of this invention are a composition containing one or more of the compounds described above for use in treating an IL-12 overproduction-related disorder, and the use of such a composition for the manufacture of a medicament for the just-described use. Other features or advantages of the present invention will be apparent from the following detailed description of several embodiments, and also from the appending claims. DETAILED DESCRIPTION [0016] The compounds described above can be prepared by methods well known in the art, as well as by the synthetic routes disclosed herein. For example, a triazine compound of this invention (e.g., Compound 1) can be prepared in a stepwise manner by using cyanuric chloride as a starting material and replacing its three chloro groups with various substitutes by the methods described above. Due to the symmetry of cyanuric chloride, the order of displacement is not of particular importance. For example, a chloro group of cyanuric chloride can be substituted with a nucleophile X—R 1 —H, wherein X is O or S, thus forming an ether linkage. In another example, a compound of formula (I), wherein Y is CH 2 (e.g., Compound 7), can be prepared by reacting the cyanuric chloride with a Grignard reagent, an organotin reagent, an organoboric acid, an organocopper reagent or an organozinc reagent in the presence of an organopalladium compound as a catalyst. If preferred, other types of linkages can be prepared by similar nucleophilic reactions. Sensitive moieties on the triazinyl intermediates and on the nucleophiles can be protected prior to coupling. For suitable protecting groups, see, e.g., Greene (1981) Protective Groups in Organic Synthesis , John Wiley & Sons, Inc., New York. A triazine compound thus synthesized can be further purified by flash column chromatography, high performance liquid chromatography, or crystallization. [0017] Also within the scope of this invention is a pharmaceutical composition that contains an effective amount of at least one triazine compound of this invention and a pharmaceutically acceptable carrier. Further, the present invention covers a method of administering an effective amount of one or more triazine compounds described in the “Summary” section to a subject in need of treatment of IL-12 overproduction related diseases (e.g., rheumatoid arthritis, sepsis, or Crohn's disease, multiple sclerosis, psoriasis, or insulin-dependent diabetes mellitus). “An effective amount” refers to the amount of the compound which is required to confer a therapeutic effect on the treated subject. The interrelationship of dosages for animals and humans (based on milligrams per meter squared of body surface) is described in Freireich et al., (1966) Cancer Chemother Rep 50: 219. Body surface area may be approximately determined from height and weight of the patient. See, e.g., Scientific Tables, Geigy Pharmaceuticals, Ardley, N.Y., 1970, 537. An effective amount of the compound of this invention can range from about 0.001 mg/Kg to about 1000 mg/Kg. Effective doses will also vary, as recognized by those skilled in the art, depending on the diseases treated, route of administration, excipient usage, and the possibility of co-usage with other therapeutic treatments such as use of other agents. [0018] To practice the method of the present invention, a triazine compound, as a component of a pharmaceutical composition, can be administered orally, parenterally, by inhalation spray, topically, rectally, nasally, buccally, vaginally or via an implanted reservoir. The term “parenteral” as used herein includes subcutaneous, intracutaneous, intravenous, intramuscular, intraarticular, intraarterial, intrasynovial, intrastemal, intrathecal, intralesional and intracranial injection or infusion techniques. [0019] A sterile injectable composition, for example, a sterile injectable aqueous or oleaginous suspension, can be formulated according to techniques known in the art using suitable dispersing or wetting agents (such as, for example, Tween 80) and suspending agents. The sterile injectable preparation can also be a sterile injectable solution or suspension in a non-toxic parenterally acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that can be employed are mannitol, water, Ringer's solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium (e.g., synthetic mono- or diglycerides). Fatty acids, such as oleic acid and its glyceride derivatives are useful in the preparation of injectables, as are natural pharmaceutically-acceptable oils, such as olive oil or castor oil, especially in their polyoxyethylated versions. These oil solutions or suspensions can also contain a long-chain alcohol diluent or dispersant, or carboxymethyl cellulose or similar dispersing agents. Other commonly used surfactants such as Tweens or Spans or other similar emulsifying agents or bioavailability enhancers which are commonly used in the manufacture of pharmaceutically acceptable solid, liquid, or other dosage forms can also be used for the purposes of formulation. A composition for oral administration can be any orally acceptable dosage form including, but not limited to, capsules, tablets, emulsions and aqueous suspensions, dispersions and solutions. In the case of tablets for oral use, carriers which are commonly used include lactose and corn starch. Lubricating agents, such as magnesium stearate, are also typically added. For oral administration in a capsule form, useful diluents include lactose and dried corn starch. When aqueous suspensions or emulsions are administered orally, the active ingredient can be suspended or dissolved in an oily phase combined with emulsifying or suspending agents. If desired, certain sweetening, flavoring, or coloring agents can be added. A nasal aerosol or inhalation composition can be prepared according to techniques well-known in the art of pharmaceutical formulation and can be prepared as solutions in saline, employing benzyl alcohol or other suitable preservatives, absorption promoters to enhance bioavailability, fluorocarbons, and/or other solubilizing or dispersing agents known in the art. A triazine compound can also be administered in the form of suppositories for rectal administration. [0020] The carrier in the pharmaceutical composition must be “acceptable” in the sense of being compatible with the active ingredient of the formulation (and preferably, capable of stabilizing it) and not deleterious to the subject to be treated. For example, solubilizing agents such as cyclodextrins, which form specific, more soluble complexes with the compounds of this invention, or one or more solubilizing agents, can be utilized as pharmaceutical excipients for delivery of a triazine compound. Examples of other carriers include colloidal silicon dioxide, magnesium stearate, cellulose, sodium lauryl sulfate, and D&C Yellow # 10. [0021] The biological activities of a triazine compound can be evaluated by a number of cell-based assays. One of such assays can be conducted using cells from human peripheral blood cells (PBMC) or human monocytic cell line (THP-1). The cells are stimulated with a combination of human interferon-γ and lipopolysaccharide or a combination of IFNγ and Staphylococcus aureus Cowan I in the presence of a test compound. The level of inhibition of IL-12 production can be measured by determining the amount of p70 by using a sandwich ELISA assay with anti-human IL-12 antibodies. IC 50 of the test compound can then be determined. Specifically, PBMC or THP-1 cells are incubated with the test compound. Cell viability was assessed using the bioreduction of MTS [3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium] (Promega, Madison, Wis.). [0022] A triazine compound can also be evaluated by animal studies. For example, one of such studies involves the ability of a test compound to treat adjuvant arthritis (i.e., a IL-12 overproduction related disorder) in rats. [0023] Without further elaboration, it is believed that the above description has adequately enabled the present invention. The following specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. All of the publications cited herein are hereby incorporated by reference in their entirety. EXAMPLE 1 Preparation of Compound 1: N-(1H-indol-3-ylmethylene)-N′-[4-morpholin-4-yl-6-(2-pyridin-2-yl-ethoxy)-[1,3,5]triazin-2-yl]-hydrazine [0024] Cyanuric chloride (13.66 g, 74 mmol) was dissolved in methylene chloride (100 mL) at −78° C., followed by the addition of diisopropylethylamine (12.9 mL, 74 mmol). The reaction mixture was stirred for 5 minutes. Morpholine (6.46 mL, 74 mmol) was added dropwise into the reaction mixture in 10 min. The resulting white precipitate was filtered, washed with water, and dried to afford the desired intermediate in quantitative yield (17 g, 100%). [0025] 2-(2-Hydroxyethyl)pyridine (2 g, 16.2 mmol) was dissolved in THF (20 mL) at 0° C. 6.5 mL of 2.5 M n-butyl lithium (16.2 mmol) was added into the pyridine solution dropwise in 5 min. The resulting solution was then added dropwise via cannula to a triazine dichloride solution (3.8 g, 16.2 mmol, in THF) at −78° C. The reaction was allowed to warm to room temperature for overnight to yield the triazine monochloride intermediate (2.8 g, 54%) as a white powder. Hydrazine (0.5 mL, 15.5 mmol) was dissolved in 10 mL ethanol at room temperature. The triazine monochloride intermediate (1 g, 3.11 mmol) was added to a solution of ethanol (20 mL) and heated to 60° C. before adding into the hydrazine solution. After stirring for 30 min, white crystals precipitated, which were then filtered, washed with water and air dried to yield the triazine hydrazine intermediate (781 mg, 78%) as a white powder. [0026] Indole-3-aldehyde (1.05 g, 7.25 mmol) and the triazine hydrazine intermediate (2.3 g, 7.25 mmol) were added to 30 mL of methanol at room temperature. 5 mL of acetic acid was added to the reaction mixture and was refluxed for 5 min. Upon cooling, a white precipitate was formed, which was filtered and washed with water to yield Compound 1 as a white powder (1.7 g, 52%). [0027] 1 H NMR (CDCl 3 ), δ (ppm): 3.28 (t, J=6.9, 2H); 3.7 (broad s, 4H); 3.86 (broad s, 4H); 4.73 (broad t, 2H); 7.14-7.24 (m, 2H); 7.27-7.30 (m, 3H); 7.37 (d, J=8.1, 1H); 7.45 (d, J=2.4, 1H); 7.59 (t, J=7.5, 1H); 8.14 (s, 1H); 8.42 (d, J=7.8, 1H); 8.49 (s, 1H); and 8.56 (d, J=8.5, 1H). [0028] MS (ESI): m/z 445.2 (M+H). EXAMPLE 2 Preparation of Compound 2: 2,3-dimethyl-1H-indol-5-yl)-[4-morpholin-4-yl-6-(2-pyridin-2-yl-ethoxy)-[1,3,5]triazin-2-yl]-amine [0029] To a solution of cyanuric chloride (0.922 g, 5.00 mmol, 1.00 equiv.) in 15 mL CH 2 Cl 2 at 0° C. was added slowly DIPEA (1.422 g, 11.00 mmol, 2.20 equiv.) during a period of 10 minutes. Ice bath was removed, and 2-(2-hydroxyethyl)pyridine (0.677 g, 5.50 mmol, 1.10 equiv.) was added, and the reaction mixture was stirred at room temperature for 15 minutes. 5-Amino-2,3-dimethylindole (0.641 g, 4.00 mmol, 0.80 equiv.) was then added, and stirred for 4 hours at room temperature. A light brown solid precipitated out after 10 mL of water was added to the reaction mixture and stirred for about 10 minutes. The light brown solid was collected by filtration, washed with 2×10 mL water, 5 mL EtOAc and dried (1.50 g, 3.80 mmol, 95%). This solid was then added to a solution of morpholine (0.827 g, 9.5 mmol, 2.50 equiv.) in 30 mL THF, and stirred at 60° C. for 4 hours. Usual workup and flash chromatography purification gave Compound 2 as an off-white solid (1.30 g, 2.92 mmol, 77%). [0030] 1 H NMR (300 MHz, DMSO-d 6 ), δ ppm: 10.50 (s, 1H); 9.29 (br s, 1H); 8.51 (d, J=4.8 Hz, 1H); 7.70-7.79 (m, 2H); 7.22-7.34 (m, 2H); 7.10 (s, 2H); 4.63 (t, J=6.9 Hz, 2H); 3.71 (br s, 4H); 3.63 (br s, 4H); 3.16 (t, J=6.9 Hz, 2H); 2.78 (s, 3H), 2.07 (br s, 3H); MS (ESI): m/z 446.2 (M+H) + . EXAMPLE 3 Preparation of Compound 3: N-(1H-indol-3-ylmethylene)-N′-[4-morpholin-4-yl-6-(2-pyridin-3-yl-ethoxy)-[1,3,5]triazin-2-yl]-hydrazine [0031] Compound 3 was prepared in a similar manner as described in Example 1. [0032] 1 H NMR (300 MHz, CDCl 3 ), δ ppm: 9.10 (br s, 1H); 8.55 (d, J=1.8 Hz, 1H); 8.47-8.49 (m, 2H); 8.34-8.41 (m, 1H); 8.07 (s, 1H); 7.60 (dt, J=1.8 Hz, 7.5 Hz, 1H); 7.34-7.39 (m, 2H); 7.14-7.25 (m, 3H); 4.58 (br s, 2H); 3.86 (br s, 4H); 3.75 (br s, 4H); 3.09 (t, J=7.2 Hz, 1H); MS (ESI): m/z 445.1 (M+H) + . EXAMPLE 4 Preparation of Compound 4: N-(3-Methoxy-benzylidene)-N′-[4-morpholin-4-yl-6-(2-pyridin-2-yl-ethoxy)-[1,3,5]triazin-2-yl]-hydrazine [0033] Compound 4 was prepared in a similar manner as described in Example 1. [0034] 1 H NMR (300 MHz, DMSO-d 6 ), δ ppm: 11.19 (s, 1H); 8.52 (dd, J=3.9 Hz, 0.9 Hz, 1H); 8.07 (s, 1H); 7.73 (m, 1H); 7.19-7.36 (m, 4H); 6.95 (dd, J=7.8 Hz, 2.4 Hz, 1H); 4.64 (t, J=6.3 Hz, 2H); 3.64-3.78 (m, 11H); 3.17 (t, J=6.3 Hz, 2H); MS (ESI): m/z 436.2 (M+H) + . EXAMPLE 5 Preparation of Compound 5: N-(3-methyl-benzylidene)-N′-[4-morpholin-4-yl-6-(2-pyridin-2-yl-ethoxy)-[1,3,5]triazin-2-yl]-hydrazine [0035] Compound 5 was prepared in a similar manner as described in Example 1. [0036] 1 H NMR (300 MHz, DMSO-d 6 ), δ ppm: 11.14 (s, 1H); 8.52 (dd, J=3.9 Hz, 0.9 Hz, 1H); 8.07 (s, 1H); 7.73 (m, 1H); 7.17-7.45 (m, 6H); 4.64 (t, J=6.3 Hz, 2H); 3.63-3.73 (m, 8H); 3.17 (t, J=6.3 Hz, 2H); 2.33 (s, 3H); MS (ESI): m/z 420.2 (M+H) + . EXAMPLE 6 Preparation of Compound 6: 4-{4-[N′-(1H-indol-3-ylmethylene)-hydrazino]-6-morpholin-4-yl-[1,3,5]triazin-2-yl}-butan-1-ol [0037] Compound 6 was prepared in a similar manner as described in Example 7. [0038] 1 H NMR (300 MHz, CDCl 3 +DMSO-d 6 , 8:1), δ ppm: 10.16 (br s, 1H); 9.17 (br s, 1H); 8.37-8.47 (m, 1H); 8.21 (s, 1H); 7.36-7.47 (m, 3H); 7.17-7.26 (m, 2H); 3.93 (br s, 4H); 3.77 (br s, 4H); 3.65 (t, J=6.3 Hz, 2H); 2.62 (br s, 2H); 1.84-1.92 (m, 2H); 1.62-1.71 (m, 2H); MS (ESI): m/z 396.2 (M+H) + . EXAMPLE 7 Preparation of Compound 7: N-{4-[3-(3,4-dimethoxy-phenyl)-propyl]-6-morpholin-4-yl-1,3,5-triazin-2-yl}-N′-[1-(1H-indol-3-yl)-meth-(E)-ylidene]-hydrazine [0039] To a solution of 3-(3,4-dimethoxyphenyl)-propyl iodide (1.224 g, 4.00 mmol, 1.00 equiv.) in 20 mL dry THF was added highly active zinc (suspension in THF, Rieke metal from Aldrich, 5.2 mL 0.05 g/mL, 4.00 mmol, 1.00 equiv.). The mixture was stirred at room temperature overnight. 2,4-dichloro-6-morpholin-4-yl-1,3,5-triazine (0.936 g, 4.0 mmol, 1.00 equiv.) and trans-benzyl-(chloro)-bis-(triphenylphosphine)palladium(II) (0.03 g, 0.04 mmol, 0.01 equiv.) were added, and the reaction mixture was stirred at room temperature for 8 hours. Usual workup and flash chromatography purification gave 4-chloro-2-[3-(3,4-dimethoxyphenyl)propyl]-6-morpholin-4-yl-1,3,5-triazine as a light yellow solid which was treated with hydrazine following the typical procedure to yield {4-[3-(3,4-Dimethoxy-phenyl)-propyl]-6-morpholin-4-yl-1,3,5-triazin-2-yl}-hydrazine as a white solid (0.85 g, 2.27 mmol, 57%). MS (ESI): m/z 375.2 (M+H) + . [0040] A mixture of {4-[3-(3,4-dimethoxy-phenyl)-propyl]-6-morpholin-4-yl-1,3,5-triazin-2-yl}-hydrazine (0.75 g, 2.00 mmol, 1.00 equiv.), indole-3-carboxaldehyde (0.29 g, 2.00 mmol, 1.00 equiv.), and AcOH (80 mg, cat.) in 15 mL MeOH was stirred at 75° C. for 4 hours. Solvent was removed and the residue was subjected to flash chromatography purification and crystallization in MeOH to yield Compound 7 as an off-white solid (0.72 g, 1.44 mmol, 72%). [0041] 1 H NMR (300 MHz, CDCl 3 ), δ ppm: 8.57 (br s, 1H); 8.45 (br s, 1H); 8.29-8.32 (m, 1H); 8.00 (s, 1H); 7.39-7.43 (m, 2H); 7.23-7.34 (m, 2H); 6.74-6.80 (m, 3H); 6.30 (s, 1H); 3.86 (s, 3H); 3.85 (s, 3H); 3.78-3.84 (m, 4H); 3.67-3.70 (m, 4H); 2.63-2.71 (m, 4H), 2.03-2.13 (m, 2H); MS (ESI): m/z 502.2 (M+H) + . EXAMPLE 8 Preparation of Compound 8: N-{4-[2-(2,2-Dimethyl-[1,3]dioxolan-4-yl)-ethoxy]-6-morpholin-4-yl-[1,3,5]triazin-2-yl}-N′-(1H-indol-3-ylmethylene)-hydrazine [0042] Compound 8 was prepared in a similar manner as described in Example 1. [0043] 1 H NMR (300 MHz, CD 3 Cl) δ (ppm): 8.50 (s, 1H), 8.42 (d, J=8.4 Hz, 1H), 8.24 (s, 1H), 8.09 (s, 1H), 7.44 (d, J=3.0 Hz, 1H), 7.38 (d, 1H, J=7.2 Hz), 7.20-7.26 (m, 2H), 4.55 (br., 2H), 4.28 (d, J=7.4 Hz, 1H) 3.84 (m, 4H), 3.71 (m, 4H), 3.60 (t, J=7.4 Hz, 2H), 2.03 (m, 2H), 1.42 (s, 3H), 1.35 (s, 3H). MS (ESI): m/z 468.3 (M+H) + . EXAMPLE 9 Preparation of Compound 9: N-[4-(4,5-dihydro-oxazol-2-ylmethoxy)-6-morpholin-4-yl-[1,3,5]triazin-2-yl]-N′-(1H-indol-3-ylmethylene)-hydrazine [0044] Compound 9 was prepared in a similar manner as described in Example 1. [0045] 1 H NMR (300 MHz, DMSO-d 6 ) δ (ppm): 11.40 (s, 1H), 10.91 (s, 1H), 8.32-8.28 (m, 2H), 7.68 (bs, 1H), 7.40-7.37 (m, 1H), 7.21-7.05 (m, 2H), 4.80-4.66 (m, 4H), 3.75-3.55 (m, 8H), 3.15 (s, 2H); MS (ESI): m/z 423.1. EXAMPLE 10 Preparation of Compound 10: {4-[N′-(1H-indol-3-ylmethylene)-hydrazino]-6-morpholin-4-yl-[1,3,5]triazin-2-yloxy}-acetic acid ethyl ester [0046] Compound 10 was prepared in a similar manner as described in Example 1. [0047] 1 H NMR (300 MHz, DMSO-d 6 ) δ (ppm): 8.62-8.60 (m, 1H), 8.42 (d, 1H, J=9.0 Hz), 8.09 (s, 1H), 7.45 (bs, 1H), 7.39-7.36 (m, 1H), 7.28-7.20 (m, 3H), 4.84 (s, 2H), 4.27-4.19 (m, 2H), 3.80-3.65 (m, 8H), 1.25 (t, 3H, J=7.2 Hz); MS (ESI): m/z 426.1. EXAMPLE 11 Preparation of Compound 11: N-(2-hydroxy-ethyl)-2-{4-[N′-(1H-indol-3-ylmethylene)-hydrazino]-6-morpholin-4-yl-[1,3,5]triazin-2-yloxy}-acetamide [0048] Compound 11 was prepared in a similar manner as described in Example 1. [0049] 1 H NMR (DMSO-d 6 ) 6 (Ppm): 11.40 (s, 1H), 10.92 (s, 1H), 8.32-8.28 (m, 2H), 8.00-7.93 (m, 1H), 7.69 (bs, 1H), 7.40-7.37 (m, 1H), 7.21-7.05 (m, 2H), 4.75-4.60 (m, 4H), 3.75-3.55 (m, 8H), 3.20-3.10 (m, 2H); MS (ESI): m/z 441.1. EXAMPLE 12 Preparation of Compound 12: 4-[4-(2,3-Dimethyl-1H-indol-5-ylamino)-6-morpholin-4-yl-[1,3,5]triazin-2-yloxy]-benzonitrile [0050] Compound 11 was prepared in a similar manner as described in Example 2. [0051] 1 H-NMR (300 MHz, DMSO-d 6 ), δ (ppm): 1.93 (s, 1H), 2.08 (s, 2H), 2.27 (s, 3H), 3.74-3.27 (m, 8H), 6.99 (s, 1H), 7.09 (s, 1H), 7.46 (d, J=8.7 Hz), 7.79 (s, 1H), 7.91 (d, J=8.7 Hz), 9.46 (s, 1H), 10.51 (s, 1H). MS (ESI): m/z 441.2 (M+H) + . EXAMPLE 13 In Vitro Assays [0052] Reagents. Staphylococcus aureus Cowan I (SAC) was obtained from Calbiochem (La Jolla, Calif.), and lipopolysaccharide (LPS, Serratia marscencens) was obtained from Sigma (St. Louis, Mo.). Human and mouse recombinant IFNγ were purchased from Boehringer Mannheim (Mannheim, Germany) and Pharmingen (San Diego, Calif.), respectively. [0053] Human In Vitro Assay. Human PBMC were isolated by centrifugation using Ficoll-Paque (Pharmacia Biotech, Uppsala, Sweden) and prepared in RPMI medium supplemented with 10% fetal calf serum (FCS), 100 U/mL penicillin, and 100 μg/mL streptomycin. PBMC were plated in wells of a 96-well plate at a concentration of 5×10 5 cells/well, and primed by adding IFNγ (30 U/mL) for 22 h and stimulated by adding LPS (1 μg/mL), or by adding IFNγ (100 U/mL) and then stimulated by adding SAC (0.01%). A test compound was dissolved in DMSO, and added to wells of the 96 well plate. The final DMSO concentration was adjusted to 0.25% in all cultures, including the compound-free control. Human THP-1 cells were plated in wells, primed by adding IFNγ (100 U/mL) for 22 h and stimulated by adding SAC (0.025%) in the presence of different concentrations of the test compound. Cell-free supernatants were taken 18 h later for measurement of cytokines. Cell viability was assessed using the bioreduction of MTS. Cell survival was estimated by determining the ratio of the absorbance in compound-treated groups versus compound-free control. [0054] The supernatant was assayed for the amount of IL-112p40, IL-12p70, or IL-10 by using a sandwich ELISA with anti-human antibodies, i.e., a Human IL-12 p40 ELISA kit from R&D Systems (Berkeley, Calif.), and a Human IL-12 p70 or IL-10 ELISA kit from Endogen (Cambridge, Mass.). Assays were based on the manufacturer's instructions. [0055] Murine In Vitro Assay. Balb/c mice (Taconic, Germantown, N.Y.) were immunized with Mycobacterium tuberculosis H37Ra (Difco, Detroit, Mich.). The splenocytes were harvested 5 days and prepared in RPMI medium supplemented with 10% FCS and antibiotics in a flat bottom 96-well plate with 1×10 6 cells/well. The splenocytes were then stimulated with a combination of IFNγ (60 ng/mL) and SAC (0.025%) [or LPS (20 μg/mL)] in the presence of a test compound. Cell-free supernatants were taken 24 h later for the measurement of cytokines. The preparation of compound and the assessment of cell viability were carried out as described above. Mouse IL-12 p70, IL-10, IL-1β, and TNFα were measured using ELISA kits from Endogen, according to the manufacturer's instructions. [0056] The biological activities of triazine compounds were tested on human PBMC or THP-1 cells. At least 240 compounds have IC 50 values of at least 5 μM. Unexpectedly, some of the test compounds have IC 50 values as low as <1 nM. EXAMPLE 14 In Vivo Assays [0057] Treatment of adjuvant arthritis in rats: Adjuvant arthritis (AA) was induced in female Lewis rats by the intracutaneous injection (base of the tail) of 0.1 mL of a 10 mg/mL bacterial suspension made from ground, heat-killed Mycobacterium tuberculosis H37Ra suspended in incomplete Freund's adjuvant. Rats were given a test compound orally once a day for 12 days, starting the day following the induction. The development of polyarthritis was monitored daily by macroscopic inspection and assignment of an arthritis index to each animal, during the critical period (days 10 to 25 post-immunization). [0058] The intensity of polyarthritis was scored according to the following scheme: (a) Grade each paw from 0 to 3 based on erythema, swelling, and deformity of the joints: 0 for no erythema or swelling; 0.5 if swelling is detectable in at least one joint; 1 for mild swelling and erythema; 2 for swelling and erythema of both tarsus and carpus; and 3 for ankylosis and bony deformity. Maximum score for all 4 paws was thus 12. (b) Grade for other parts of the body: for each ear, 0.5 for redness and another 0.5 if knots are present; 1 for connective tissue swelling (saddle nose); and 1 for the presence of knots or kinks in the tail. The highest possible arthritic index was 16. [0059] Experiments with the AA model were repeated four times. Oral administration of triazine compounds described above (e.g., Compounds 1 and 2) reproducibly reduced the arthritic score and delayed the development of polyarthritis in a dose-dependent manner. The arthritis score used in this model was a reflection of the inflammatory state of the structures monitored and the results therefore show the ability of the test compound to provide relief for this aspect of the pathology. [0060] Treatment of Crohn's disease in dinitrobenzene sulfonic acid-induced inflammatory bowel syndrome model rats: Wistar derived male or female rats weighing 200±20 g and fasted for 24 hours were used. Distal colitis was induced by intra-colonic instillation of 2,4-dinitrobenzene sulfonic acid (DNBS, 25 mg in 0.5 mL ethanol 30%) after which air (2 mL) was gently injected through the cannula to ensure that the solution remained in the colon. A test compound and/or vehicle was administered orally 24 and 2 hours before DNBS instillation and then daily for 5 days. One control group was similarly treated with vehicle alone while the other is treated with vehicle plus DNBS. The animals were sacrificed 24 hours after the final dose of test compound administration and each colon was removed and weighed. Colon-to-body weight ratio was then calculated for each animal according to the formula: Colon (g)/BW×100. The “Net” increase in ratio of Vehicle-control+DNBS group relative to Vehicle-control group was used as a base for comparison with test substance treated groups and expressed as “% Deduction.” Triazine compounds described above (e.g., Compounds 1 and 2) reproducibly had about 30% deduction. A 30% or more reduction in colon-to-body weight ratio, relative to the vehicle treated control group, was considered significant. [0061] Rats treated with test substance orally showed a marked reduction in the inflammatory response. These experiments were repeated three times and the effects were reproducible. [0062] Treatment of Crohn's disease in CD4 + CD45Rb high T cell-reconstituted SCID colitis model mice: Spleen cells were prepared from normal female BALB/c mice. For cell purification, the following anti-mouse antibodies were used to label non-CD4 + T cells: B220 (RA3-6B2), CD11b (M1/70), and CD8 cc (53-6.72). All antibodies were obtained from BioSource (Camarillo, Calif.). M450 anti-rat IgG-coated magnetic beads (Dynal, Oslo, Norway) were used to bind the antibodies and negative selection was accomplished using an MPC-1 magnetic concentrator. The enriched CD4 + cells were then labeled for cell sorting with FITC-conjugated CD45RB (16A, Pharmingen, San Diego, Calif.) and PE-conjugated CD4 (CT-CD4, Caltag, Burlingame, Calif.). CD4 + CD45RBhigh cells were operationally defined as the upper 40% of CD45Rb-staining CD4 + cells and sorted under sterile conditions by flow cytometry. Harvested cells were resuspended at 4×10 6 /mL in PBS and injected 100 μL intraperitoneally into female C.B-17 SCID mice. Triazine compounds described above (e.g., Compounds 1 and 2) and/or vehicle was orally administered once a day for 5 days per week, starting the day following the transfer. The transplanted SCID mice were weighed weekly and their clinical condition was monitored. [0063] Colon tissue samples were fixed in 10% buffered formalin and embedded in paraffin. [0064] Sections (4 μm) collected from ascending, transverse, and descending colon were cut and stained with hematoxylin and eosin. The severity of colitis was determined based on histological examination of the distal colon sections, whereby the extent of colonic inflammation was graded on a scale of 0-3 in each of four criteria: crypt elongation, cell infiltration, depletion of goblet cells, and the number of crypt abscesses. [0065] LP lymphocytes were isolated from freshly obtained colonic specimens. After removal of payer's patches, the colon was washed in Ca/Mg-free HBSS, cut into 0.5 cm pieces and incubated twice in HBSS containing EDTA (0.75 mM), DTT (1 mM), and antibiotics (amphotericin 2.5 μg/mL, gentamicin 50 μg/mL from Sigma) at 37° C. for 15 min. Next, the tissue was digested further in RPMI containing 0.5 mg/mL collagenase D, 0.01 mg/mL DNase I (Boehringer Manheim), and antibiotics at 37° C. LP cells were then layered on a 40-100% Percoll gradient (Pharmacia, Uppsala, Sweden), and lymphocyte-enriched populations were isolated from the cells at the 40-100% interface. [0066] To measure cytokine production, 48-well plates were coated with 10 μg/mL murine anti-CD3ε antibody (145-2C11) in carbonate buffer (PH 9.6) overnight at 4° C. 5×10 5 LP cells were then cultured in 0.5 ml of complete medium in precoated wells in the presence of 1 μg/mL soluble anti-CD28 antibody (37.51). Purified antibodies were obtained from Pharmingen. Culture supernatants were removed after 48 h and assayed for cytokine production. Murine IFNγ was measured using an ELISA kit from Endogen (Cambridge, Mass.), according to the manufacturer's instructions. [0067] Histological analysis showed that oral administration of triazine compounds described above (e.g., Compounds 1 and 2) reduced colonic inflammation as compared to vehicle control. The suppressive effect was dose-dependent with a substantial reduction at a dose of 10 mg/kg. The calculated colon-to-body weight ratio was consistent with the histological score, showing attenuation by treatment with the test compound. Furthermore, analysis of cytokines from LP cells in response to anti-CD3 antibody and anti-CD28 antibody demonstrated that LP cells from vehicle control produced an augmented level of IFNγ and treatment with test substance greatly diminished the production. These results clearly demonstrated the potential of the test substance in treatment of inflammatory bowel disease represented by Crohn's disease. Other Embodiments [0068] All of the features disclosed in this specification may be combined in any combination. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features. [0069] From the above description, one skilled in the art can easily ascertain the essential characteristics of the present invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. For example, compounds structurally analogous a triazine compound described in the specification also can be made, screened for their inhibiting IL-12 activities, and used to practice this invention. Thus, other embodiments are also within the claims.
This invention relates to triazine compounds of formula (I): R 1 is aryl, or heteroaryl; each of R 2 , R 4 , and R 5 , independently, is R c , halogen, nitro, nitroso, cyano, azide, isothionitro, SR c , or OR c ; R 3 is R c , alkenyl, alkynyl, aryl, heteroaryl, cyclyl, heterocyclyl, OR c , OC(O)R c , SO 2 R c , S(O)R c , S(O 2 )NR c R d , SR c , NR c R d , NR c COR d , NR c C(O)OR d , NR c C(O)NR c R d , NR c SO 2 , COR c , C(O)OR c , or C(O)NR c R d ; n is 0, 1, 2, 3, 4, 5, 6, or 7; X is O, S, S(O), S(O 2 ), or NR c ; Y is a covalent bond, CH 2 , C(O), C═N—R c , C═N—OR c , C═N—SR c , O, S, S(O), or S(O 2 ); Z is N; and W is O, S, S(O), S(O 2 ), NR c , or NC(O)R c ; in which each of R a and R b , independently, is H, alkyl, aryl, heteroaryl; and each of R c and R d , independently, is H, alkyl, or alkylcarbonyl.
2
This is a continuation of U.S. Ser. No. 08/394,319 filed on Feb. 23, 1995, now abandoned. FIELD OF THE INVENTION The field of the present invention is that of belt restraint seat systems for seated occupants in automotive vehicles and methods of utilization thereof. BACKGROUND OF THE INVENTION Most belt restraint seat systems are designed mainly to minimize injuries resulting from frontal, side or rear impacts. SUMMARY OF THE INVENTION The present invention brings forth a restraint seat system which attempts to minimize injuries resultant from rollover accidents beyond that offered by present belt restraint systems. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front elevational view with portions of the vehicle in section exposing a vehicle floor, door section and roof as well as a B-pillar and a vehicle seat restraint system according to the present invention which is inclusive of a lap and shoulder restraint belt wrench pretensioner and seat belt retractor. FIG. 2 is a view taken along line 2--2 of FIG. 1. FIG. 3 is an enlargement of a portion of FIG. 2 with portions sectioned for clarity of illustration. FIG. 4 is a view taken along line 4--4 of FIG. 1. FIG. 5 is an enlarged view partially sectioned of a portion shown in FIG. 4. FIG. 6 is an exploded view of an alternate preferred embodiment of the present invention. FIG. 7 is a view taken along line 7-7 of FIG. 6. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIGS. 1 through 7, a vehicle seat system 7 according to the present invention has a resilient seat bun or cushion 10 which normally supports the buttocks and thigh region 12 of a vehicle seat occupant 14 at a given height 15 above the vehicle floor 16. Joined to the vehicle floor 16 is a door section 18, a B-pillar 20 and a roof 22 along with a side roof reinforcement frame 24. Prior studies have indicated that many head and neck region injuries suffered by vehicle seat occupants in rollover conditions occur from contact of the head and neck region 26 of the vehicle occupant with the roof 22 or roof frame reinforcement 24. Such injuries occur even when the structural integrity of the roof 22 and roof reinforcement 24 are almost totally maintained or with the addition of roll bar structures. Therefore, to additionally minimize injuries to region 26 of a seated occupant, structural integrity of the roof and roof reinforcement 24 must be supplemented by additional measures. Reliance upon structural integrity of the roof and roof reinforcement 24 does not guarantee elimination of injuries to the head and neck region 26. A belt restraint 28 has a lap portion 30 having a first end 32 and a second end 34. Integrally continuous with the lap belt 30 is a shoulder restraint belt 35 having a first end 82 and a second end 36. In another embodiment (not shown), the belt and shoulder restraints will terminate. The shoulder restraint 35 passes through a loop (not shown) positioned on the B-pillar 20 and is then connected to a web grabbing-type belt retractor 38 which automatically by inertia and/or activation by a signal locks the second end 36 of the belt in an accident condition. Tensionally associated with the first end 32 of a lap restraint portion of the belt is a pyrotechnic rotary belt wrench 40. The belt wrench 40 has a cylindrical housing 42 which sealably mounts a piston screw 44. Piston screw 44 has a head portion 46 joined to a screw portion 48. The piston portion 46 has a shank 50 which passes through a geometrically matching noncircular sleeve 52 to prevent the piston 44 from rotating. The rotary wrench at one end has a sealed end plate 54 which mounts a fuse 56 which is electrically connected to a sensor controller 60. The sensor controller 60 senses a displacement of the vehicle floor 16 indicative of a rollover condition and sends a signal to the fuse 56 in response thereto. The variable of displacement sensed can be lateral acceleration or rotational velocity of the vehicle or derivatives or integrals thereof. The piston 44 also has an inner cavity 62 which mounts an explosive charge 64. Partially threadably penetrated by the screw portion 48 of the piston is a dram reel 66. The drum reel 66 is rotatably mounted by a rotor thrust bearing 68. When the rotary wrench 40 is actuated, the fuse 56 lights the charge 64, causing the piston 44 to move rightward (as shown in FIG. 5), causing the rotary wheel 66 to rotate to pull the first end 32 of the lap belt with a tunable force typically between 500 and 1800 pounds force. The rotary action of the drum reel 66 will cause up to a 300 mm length of the belt restraint to be pulled, causing the buttocks of the seated occupant to move downwardly to a height 70 as best shown in FIG. 1 and in a similar fashion cause a commensurate 50 mm to 120 mm displacement of the head region of the vehicle seat occupant, causing the buttocks and head region of the seated occupant to come closer to the vehicle floor 16. Thus, in a rollover condition, the head of the vehicle seat occupant is further removed from the roof 22 or roof reinforcement 24, thereby minimizing the chance of injury. Pressure in the rotary belt wrench 40 from the expanded gas keeps the belt wrench 40 from unreeling (typically in the neighborhood of a few minutes) until the rollover event stops. If necessary, a locking ratchet (not shown) can be added to the belt wrench to prevent retraction. Experimental data has indicated typically the maximum rotational velocity of a vehicle in a rollover situation is in the neighborhood of 0.8 to 1 revolution per second. Therefore, the sensor need not signal the belt wrench 40 to actuate until 200 milliseconds into a rollover occurrence. The time of operation of the belt wrench 40 is approximately 250 to 300 milliseconds. Referring in particular to FIGS. 1, 2 and 3, the second end 34 of the lap restraint 30 hooks through a loop 80 to integrally connect to a first end 82 of the shoulder restraint 35. (In another embodiment not shown, the lap restraint and the shoulder restraint terminate with the loop 80.) The loop 80 latches into a seat belt buckle 84 which is connected to a pretensioner cable 86. The pretensioner cable 86 loops around a pulley wheel 88 to where it is connected to a pyrotechnic pretensioner 90. The pyrotechnic pretensioner 90 can be a spring loaded or as shown pyrotechnic type and has a cylindrical body 92 capped at one end by a explosive chamber 94 which has a small hole for entry of a cable 86 at its left end wall 96. The cable is connected to a piston 98 which is slidably sealably mounted within the cylindrical portion 92. The piston 98 typically has some kind of clutch mechanism (not shown) preventing it from being backdriven once it is pushed rightwardly (as shown in FIGS. 2 and 3). Observation by the sensor 60 of a rollover condition will cause an electronic signal (simultaneous with the signal to the belt wrench 40) to be sent to the pretensioner 90, causing a pyrotechnic charge 100 to be ignited, pressurizing an expansion chamber 102 and thereby moving the piston 98 rightwardly. This will cause a rapid (in the neighborhood of 10 milliseconds) pull on the cable 86 which will take up any slack in the belt restraint 28 from the retractor 38 all the way to the rotary pyrotechnic wrench 40 by pulling down on the latch 84. The rapid action of the pretensioner 90 minimizes the amount of belt that must be wrapped around the rotary wheel 66 of the belt wrench before a force increases on the lap of occupant 14 to the extent where it pulls the seated occupant 14 down into the seat bun 10. From the activation of the pretensioner 90 and the belt wrench 40, approximately 10 milliseconds, the retractor 38 will lock and only one-half revolution of belt will be pulled from it before the belt will be taut. The retractor 38 receives a signal at the same time as the belt wrench 40. Referring to FIGS. 6 and 7, the present inventive seat system is augmented by additionally having a dual methodology collapsible seat cushion bun 110. Seat cushion bun 110 has a fluid filled bladder 112 which may be pneumatically filled or hydraulically filled which is releasably valved by valve 132 via line 130 to evacuate after receiving a signal of an impending rollover condition. The above allows the seat occupant 14 to be drawn down further and therefore brings the head region 26 further away from the roof and reinforcement structure. The seat cushion 110 also has a collapsible suspension 114 which is tightened on one end by a group of springs 116 and on the other end by a flexible tension member 118 which is then anchored to a roller 120. Upon being signalled of an impending rollover condition, an actuator 122 pulls on a rod 124, pivoting lever 126 to a release position allowing the roller 120 to freely rotate in an unwinding fashion, thereby collapsing seat suspension to allow the seat occupant to be brought down further into the seat. In still another embodiment not shown, the seat suspension and/or bladder can be released (failed) by use of a rapid deflagrating cord material. (Deflagrating cord is a cord material with a very rapid linear burn rate.) While this invention has been described in terms of a preferred embodiment thereof, it will be appreciated that other forms could readily be adapted by one skilled in the art. Accordingly, the scope of this invention is to be considered limited only by the following claims.
A vehicle seat system for a vehicle seat mounted on the vehicle floor is provided including a resilient vehicle seat bun for normally supporting a seated occupant at a given height above the vehicle floor; a lap restraint to cross over the seated occupant to restrain the occupant in the vehicle seat; a belt wrench tensionally associated with the lap restraint to tension the lap restraint to an extent to significantly pull down toward the vehicle floor the seated occupant into the seat bun such that the seated occupant's head is brought closer to the floor; and a sensor to activate the belt wrench when the vehicle undergoes a displacement condition indicative of a vehicle rollover condition.
1
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The pending application claims priority to U.S. Provisional Application No. 60/578,021 filed on Jun. 7, 2004 and to U.S. Provisional Application No. 60/672,919 filed on Apr. 18, 2005, which are hereby incorporated by reference in their entirety. FIELD OF THE INVENTION [0002] The present invention relates to ablation devices for medical therapies. In particular, the present invention relates to ablation instrument systems that use energy to ablate internal bodily tissues, and methods for using such systems for the treatment of diseases. Even more particularly, the systems and methods of the present invention can be used, for example, in the treatment of cardiac conditions such as cardiac arrhythmias. BACKGROUND OF THE INVENTION [0003] Cardiac arrhythmias, e.g., fibrillation, are irregularities in the normal beating pattern of the heart and can originate in either the atria or the ventricles. For example, atrial fibrillation is a form of arrhythmia characterized by rapid randomized contractions of the atrial myocardium, causing an irregular, often rapid ventricular rate. The regular pumping function of the atria is replaced by a disorganized, ineffective quivering as a result of chaotic conduction of electrical signals through the upper chambers of the heart. Atrial fibrillation is often associated with other forms of cardiovascular disease, including congestive heart failure, rheumatic heart disease, coronary artery disease, left ventricular hypertrophy, cardiomyopathy or hypertension. [0004] Atrial arrhythmia may be treated using several methods. Pharmacological treatment of atrial fibrillation, for example, is initially the preferred approach, first to maintain normal sinus rhythm, or secondly to decrease the ventricular response rate. Other forms of treatment include drug therapies, electrical cardioversion, and radio frequency catheter ablation of selected areas determined by mapping. In the more recent past, other surgical procedures have been developed for atrial fibrillation, including left atrial isolation, transvenous catheter or cryosurgical ablation of His bundle, and the Corridor procedure, which have effectively eliminated irregular ventricular rhythm. However, these procedures have for the most part failed to restore normal cardiac hemodynamics, or alleviate the patient's vulnerability to thromboembolism because the atria are allowed to continue to fibrillate. More effective surgical treatment was thus required to cure medically refractory atrial fibrillation of the heart. [0005] Accordingly, more effective surgical techniques have been proposed to treat medically refractory atrial fibrillation of the heart. Although these procedures were originally performed with a scalpel, these techniques may also use ablation (also referred to as coagulation). One such technique is strategic ablation of the atrial tissues through ablation catheters that treat the tissue, generally with heat or cold, to cause tissue necrosis (i.e., cell destruction). The destroyed muscle cells are replaced with scar tissue which cannot conduct normal electrical activity within the heart. [0006] For example, the pulmonary vein has been identified as one of the origins of errant electrical signals responsible for triggering atrial fibrillation. In one known approach, circumferential ablation of tissue within the pulmonary veins or at the ostia of such veins has been practiced to treat atrial fibrillation. Similarly, ablation of the region surrounding the pulmonary veins as a group has also been proposed. By ablating the heart tissue (typically in the form linear or curved lesions) at selected locations, electrical conductivity from one segment to another can be blocked and the resulting segments become too small to sustain the fibrillatory process on their own. Ablation procedures are often performed during coronary artery bypass and mitral valve replacement operations because of a heightened risk of arrhythmias in such patients and the opportunity that such surgery presents for direct access to the heart. [0007] Several types of ablation devices have recently been proposed for creating lesions to treat cardiac arrhythmias, including devices which employ electrical current (e.g., radio-frequency “RF”) heating or cryogenic cooling. Such ablation devices have been proposed to create elongated lesions that extend through a sufficient thickness of the myocardium to block electrical conduction. [0008] These devices, however, are not without their drawbacks. When cardiac surgery is performed “on pump,” the amount of time necessary to form a lesion becomes a critical factor. Because these devices rely upon resistive and conductive heating (or cooling), they must be placed in direct contact with the heart and such contact must be maintained for a considerable period of time to form a lesion that extends through the entire thickness of the heart muscle. The total length of time to form the necessary lesions can be excessive. This is particularly problematic for procedures that are performed upon a “beating heart” patient. In such cases the heart itself continues to beat and, hence, is filled with blood, thus providing a heat sink (or reservoir) that works against conductive and/or resistive ablation devices. As “beating heart” procedures become more commonplace (in order to avoid the problems associated with arresting a patient's heart and placing the patient on a pump), the need for better ablation devices will continue to grow. [0009] Moreover, devices that rely upon resistive or conductive heat transfer can be prone to serious post-operative complications. In order to quickly perform an ablation with such “contact” devices, a significant amount of energy must be applied directly to the target tissue site. In order to achieve transmural penetration, the surface that is contacted will experience a greater degree of heating (or freezing). For example, in RF heating of the heart wall, a transmural lesion requires that the tissue temperature be raised to about 50° C. throughout the thickness of the wall. To achieve this, the contact surface will typically be raised to at least 80° C. Charring of the surface of the heart tissue can lead to the creation of blood clots on the surface which can lead to post-operative complications, including stroke. Even if structural damage is avoided, the extent of the lesion (i.e., the width of the ablated zone) on the surface that has been contacted will typically be greater than necessary. [0010] Ablation devices that do not require direct contact have also been proposed, including acoustic and radiant energy. Acoustic energy (e.g., ultrasound) is poorly transmitted into tissue (unless a coupling fluid is interposed). Laser energy has also been proposed but only in the context of devices that focus light into spots or other patterns. When the light energy is delivered in the form of a focused spot, the process is inherently time consuming because of the need to expose numerous spots to form a continuous linear or curved lesion. [0011] In addition, existing instruments for cardiac ablation also suffer from a variety of design limitations. The shape of the heart muscle adds to the difficulty in accessing cardiac structures, such as the pulmonary veins which are located on the posterior surface of the heart. Further, the presence of epicardial fat limits the depth of ablative penetration for many ablative energy sources. [0012] Accordingly, there exists a need for better surgical ablation instruments that can form lesions with minimal overheating and/or damage to collateral tissue. Moreover, instruments that are capable of creating lesions uniformly, rapidly and efficiently would satisfy a significant need in the art. SUMMARY OF THE INVENTION [0013] The present invention provides surgical ablation instrument systems for creating lesions in tissue, especially cardiac tissue for treatment of arrhythmias and other cardiac conditions. The hand held instruments are especially useful in open chest or port access cardiac surgery for rapid and efficient creation of curvilinear lesions to serve as conduction blocks. The instruments can be applied to form either endocardial or epicardial ablations, and are designed to create lesions in the atrial tissue in order to electrically decouple tissue segments on opposite sides of the lesion. [0014] In one aspect of the invention, surgical ablation instruments are disclosed that are well adapted for use in or around the intricate structures of the heart. In one embodiment, the distal end of the instrument can have a malleable shape so as to conform to the surgical space in which the instrument is used. The instruments can include at least one malleable strip element disposed within the distal end of the instrument body or housing so that the distal end can be conformed into a desired shape. In addition, the instruments can also include a clasp to form a closed loop after encircling a target site, such as the pulmonary veins. Such instruments can be used not only with penetrating energy devices but also with other ablation means, such as RF heating, cryogenic cooling, ultrasound, microwave, ablative fluid injection and the like. In still another embodiment, the distal end of the instrument can include a translatory mechanism for disposing the tip of the instrument in a variety of configurations. [0015] In one embodiment, the surgical ablation instrument includes a housing or flexible elongate member having a proximal end, a distal end and a longitudinal lumen extending therebetween. An energy emitting element having a proximal end and a distal end can be slidably disposed within the lumen for transmitting energy to the distal end of the elongate member. The housing can comprise a plurality of interconnected links, or can include cutout portions such as grooves on its outer surface to facilitate flexion. The housing can also be formed from a flexible strip or flexible bellows. [0016] In another aspect of the invention, the housing can include a profile that provides for longitudinal flexibility as well as torsional strength. In one embodiment, the housing includes a shaped inner lumen for containing a complementarily shaped light delivering element. The specific geometries of the lumen and element are such that twisting or rotation of the light delivering element within the inner lumen is prevented, and the orientation of the light delivering element with respect to the housing is ensured. In another embodiment, the housing can include reinforcement such as shape memory wire or polymeric supports to prevent the housing from twisting when positioned on tortuous anatomical surfaces. [0017] In one aspect of the invention, hand-held and percutaneous instruments are disclosed that can achieve rapid and effective photoablation through the use of penetrating radiation, especially distributed radiant energy. It has been discovered that radiant energy, e.g., diffuse infrared radiation, can create lesions in less time and with less risk of the adverse types of tissue destruction commonly associated with prior art approaches. Unlike instruments that rely on thermal conduction or resistive heating, controlled penetrating radiant energy can be used to simultaneously deposit energy throughout the full thickness of a target tissue, such as a heart wall, even when the heart is filled with blood. Distributed radiant energy can also produce better defined and more uniform lesions. [0018] It has also been discovered that infrared radiation is particularly useful in forming photoablative lesions. In one preferred embodiment the instruments emit radiation at a wavelength in a range from about 800 nm to about 1000 nm, and preferably emit at a wavelength in a range of about 915 nm to about 980 nm. Radiation at a wavelength of 915 nm or 980 nm is commonly preferred, in some applications, because of the optimal absorption of infrared radiation by cardiac tissue at these wavelengths. In the case of ablative radiation that is directed towards the epicardial surface, light at a wavelength about 915 nm can be particularly preferably. [0019] In another aspect of the invention, surgical ablation instruments are disclosed that are well adapted for use in or around the intricate structures of the heart. In one embodiment, the distal end of the instrument can have a malleable shape so as to conform to the surgical space in which the instrument is used. Optionally, the distal end of the instrument can be shaped into a curve having a radius between about 5 millimeters and about 25 millimeters. The instruments can include at least one malleable strip element disposed within the distal end of the instrument body or housing so that the distal end can be conformed into a desired shape. In addition, the instruments can also include a clasp to form a closed loop after encircling a target site, such as the pulmonary veins. [0020] In yet another aspect of the invention, surgical ablation instruments are disclosed having a housing with at least one lumen therein and having a distal portion that is at least partially transmissive to photoablative radiation. The instruments further include a light delivery element within the lumen of the housing that is adapted to receive radiation from a source and deliver radiant energy through a transmissive region of the housing to a target tissue site. The radiant energy is delivered without the need for contact between the light emitting element and the target tissue because the instruments of the present invention do not rely upon conductive or resistive heating. [0021] In other aspects of the invention, ablation instruments are provided having a sufficient length to create a full encircling path around the pulmonary veins. The instruments can be configured to emit varying amounts of ablative energy along its length. In one embodiment, the ablation device includes an energy emitting element that comprises a plurality of segments, each segment having a different diameter than an adjacent segment to collectively form an elongate energy emitting element having variable diameters along its length. The energy emitting element can also be provided with a tapered profile along its length, in order to vary the amount of ablative energy emitted. The instrument can be used to provide an ablative path around both pairs of pulmonary veins, or an individual pair of pulmonary veins. [0022] In another embodiment, the instrument can include an inflatable elongate balloon that resides within the housing along with the light delivering element. An inflation controller in communication with the balloon and an inflation source, e.g., an air, gas or fluid pump, can be provided to enable the selective inflation of the balloon. Upon inflation, the balloon urges against the light delivering element and effects the angular orientation of the element with respect to the longitudinal axis of the housing. This allows the surgeon to change the angle of the light delivering element by controlling the inflation of the balloon, and consequently the energy emitting pathway along the length of the light delivering element. [0023] In yet another embodiment, the instrument can include a plurality of light delivering elements of varying lengths, each element being configured to emit a dose of ablative energy at a specific position with respect to the length of the housing. Each of the light delivering elements can have a different length than the other elements. A selection mechanism can be provided with the ablation instrument so that the surgeon can select any one of the plurality of light delivering elements for activation. Preferably, each of the light delivering elements includes a diffuser tip at a distal end. The instrument can include a housing that has a portion transparent to emitted energy. [0024] The light delivering element can be a light transmitting optical fiber adapted to receive ablative radiation from a radiation source and a light emitting tip at a distal end of the fiber for emitting diffuse or defocused radiation. The light delivering element can be slidably disposed within the inner lumen of the housing and the instrument can further include a translatory mechanism for disposing the tip of the light delivering element at one or more of a plurality of locations with the housing. Optionally, a lubricating fluid can be disposable between the light delivery element and the housing. This fluid can be a physiologically compatible fluid, such as saline, and the fluid can also be used for cooling the light emitting element or for irrigation via one or more exit ports in the housing. [0025] In one embodiment of the invention, the ablation device comprises a housing having a proximal end, a distal end and a longitudinal lumen extending therebetween. An ablation element is disposed within the lumen of the housing to ablate tissue at a target site. Also included is an irrigation cap at the distal end of the ablation element. A fluid source connected to the housing provides fluid to the ablation element during delivery of the ablation energy. The fluid can be introduced via a fluid inlet on the irrigation cap to be delivered between the ablation element and the irrigation cap. A cutout portion formed within the irrigation cap forms a fluid carrying cavity for delivering the fluid to the ablation element. In one particular aspect, the irrigation cap is formed as a pair of jaws, with the free ends of the jaws having surface features such as teeth, grooves, etc. for enhanced gripping. The fluid can comprise a material which cools the ablation element during delivery of ablative energy, and can include lubricating fluids, and/or physiologically compatible fluids such as saline. [0026] The light emitting tip can include a hollow tube having a proximal end joined to the light transmitting optical fiber, a closed distal end, and an inner space defining a chamber therebetween. The light scattering medium disposed within the chamber can be a polymeric or liquid material having light scattering particles, such as alumina, silica, or titania compounds or mixtures thereof, incorporated therein. The distal end of the tube can include a reflective end and, optionally, the scattering medium and the reflective end can interact to provide a substantially uniform axial distribution of radiation over the length of the housing. [0027] Alternatively, the light emitting tip can include at least one reflector for directing the radiation through the transmissive region of the housing toward a target site and, optionally can further include a plurality of reflectors and/or at least one defocusing lens for distributing the radiation in an elongated pattern. [0028] The light emitting tip can further include at least one longitudinal reflector or similar optical element such that the radiation distributed by the tip is confined to a desired angular distribution. In one embodiment, the reflector is configured to selectively block a portion of the energy emitting element from emitting ablative energy. The reflector can be configured to seat around the energy emitting element, and can include a window or cutout portion for emitting energy. The window can be adjustably positioned along the length of the reflector. Alternatively, or in addition, the size of the window can also be adjustable. [0029] The hand held instruments can include a handle incorporated into the housing. An inner lumen can extend through the handle to received the light delivering element. The distal end of the instrument can be resiliently deformable or malleable to allow the shape of the ablation element to be adjusted based on the intended use. [0030] In one embodiment, a hand held cardiac ablation instrument is provided having a housing with a curved shape and at least one lumen therein. A light delivering element is disposable within the lumen of the housing for delivering ablative radiation to form a curved lesion at a target tissue site adjacent to the housing. [0031] In another aspect of the invention, the light delivering element can be slidably disposed within the inner lumen of the housing, and can include a light transmitting optical fiber adapted to receive ablative radiation from a radiation source and a light diffusing tip at a distal end of the fiber for emitting radiation. The instrument can optionally include a handle joined to the housing and having an inner lumen though which the light delivering element can pass from the radiation source to the housing. [0032] In yet another aspect of the present invention, the light diffusing tip can include a tube having a proximal end mated to the light transmitting optical fiber, a closed distal end, and an inner chamber defined therebetween. A light scattering medium is disposed within the inner chamber of the tube. The distal end of the tube can include a reflective end surface, such as a mirror or gold coated surface. The tube can also include a curved, longitudinally-extending, reflector that directs the radiant energy towards the target ablation site. The reflective surfaces and the light scattering medium interact to provide a substantially uniform axial distribution of radiation of the length of the housing. [0033] In other aspects of the present invention, a hand held cardiac ablation instrument is provided having a slidably disposed light transmitting optical fiber, a housing in the shape of an open loop and having a first end adapted to receive the slidably disposed light transmitting optical fiber, and at least one diffuser chamber coupled to the fiber and disposed within the housing. The diffuser chamber can include a light scattering medium disposed within the housing and coupled to the slidably disposed light transmitting optical fiber. [0034] In yet another aspect, a percutaneous cardiac ablation instrument in the form of a balloon catheter with an ablative light projecting assembly is provided. The balloon catheter instrument can include at least one expandable membrane disposed about a housing. This membrane is generally or substantially sealed and serves as a balloon to position the device within a lumen. The balloon structure, when filled with fluid, expands and is engaged in contact with the tissue. The expanded balloon thus defines a staging from which to project ablative radiation in accordance with the invention. The instrument can also include an irrigation mechanism for delivery of fluid at the treatment site. In one embodiment, irrigation is provided by a sheath, partially disposed about the occluding inner balloon, and provides irrigation at a treatment site (e.g. so that blood can be cleared from an ablation site). The entire structure can be deflated by applying a vacuum which removes the fluid from the inner balloon. Once fully deflated, the housing can be easily removed from the body lumen. [0035] The present invention also provides methods for ablating tissue. One method of ablating tissue comprises positioning a distal end of a penetrating energy instrument in proximity to a target region of tissue, the instrument including a source of penetrating energy disposed within the distal end. The distal end of the instrument can be curved to permit the distribution of penetrating energy in elongated and/or arcuate patterns. The method further including activating the energy element to transmit penetrating energy to expose the target region and induce a lesion; and, optionally, repeating the steps of positioning and exposing until a composite lesion of a desired shape is formed. [0036] In another method, a device is provided having a light delivering element coupled to a source of photoablative radiation and configured in a curved shape to emit an arcuate pattern of radiation. The device is positioned in proximity to a target region of cardiac tissue, and applied to induce a curvilinear lesion. The device is then moved to the second position and reapplied to induce a second curvilinear lesion. The steps of positioning and reapplying can be repeated until the lesions are joined together to create a composite lesion (e.g., a closed loop encircling one or more cardiac structures). [0037] In another embodiment, methods of ablating cardiac tissue are provided. A device is provided having a housing in the shape of a hollow ring or partial ring having at least one lumen therein and at least one open end, and a light delivering element slidably disposed within the lumen of the housing for delivering ablative radiation to form a circular lesion at a target region adjacent the housing. The methods includes the steps of positioning the device in proximity to the target region of cardiac tissue, applying the device to the target region to induce a curvilinear lesion, advancing the light delivering element to a second position, reapplying the device to the target region to induce a second curvilinear lesion, and repeating the steps of advancing and applying until the lesions are joined together to create a composite circumferential lesion. BRIEF DESCRIPTION OF THE DRAWINGS [0038] The invention will be more fully understood from the following detailed description taken in conjunction with the accompanying drawings, in which like reference numerals designate like parts throughout the figures, and wherein: [0039] FIG. 1 is a schematic, perspective view of a hand held surgical ablation instrument in accordance with this invention; [0040] FIG. 1A is a partially cross-sectional view of the hand held surgical ablation instrument of FIG. 1 ; [0041] FIG. 1B is a perspective view of the handle and light delivering element of the hand held surgical ablation instrument of FIG. 1A ; [0042] FIG. 2 is a schematic, perspective view of another embodiment of a hand held surgical ablation instrument in accordance with this invention; [0043] FIG. 2A is a partially cross-sectional view of the hand held surgical ablation instrument of FIG. 2 ; [0044] FIG. 3 is a schematic, side perspective view of a tip portion of an ablation instrument in accordance with another embodiment of the invention illustrating a light delivery element; [0045] FIG. 3A is a schematic, side perspective view of a tip portion of another ablation instrument in accordance with the invention; [0046] FIG. 4 is a schematic, cross sectional view of the light delivery element of FIG. 3 ; [0047] FIG. 4A is a schematic, cross sectional view of another embodiment of a light delivery element; [0048] FIG. 4B is a schematic, cross sectional view along the length of an irrigation cap and light delivery element of another embodiment the present invention; [0049] FIG. 4C is a schematic, cross sectional side view of the irrigation cap and light delivery element of FIG. 4B ; [0050] FIG. 5 is a schematic, cross sectional view of another embodiment of a light delivery element surrounded by a malleable housing; [0051] FIG. 6 is a perspective view of another embodiment of a flexible housing; [0052] FIG. 6A is an enlarged, perspective view of the flexible housing of FIG. 6 ; [0053] FIG. 6B is an exploded view of the flexible housing of FIG. 6 ; [0054] FIG. 7A is a schematic, cross sectional view of another embodiment of an ablation element of the present invention; [0055] FIG. 7B is a schematic, cross sectional view of another embodiment of an ablation element of the present invention; [0056] FIG. 7C is a schematic, cross sectional view of another embodiment of an ablation element of the present invention; [0057] FIG. 7D is a schematic, cross sectional view of another embodiment of an ablation element of the present invention; [0058] FIG. 7E is a schematic, cross sectional view of another embodiment of an ablation element of the present invention; [0059] FIG. 7F is a schematic, cross sectional view of another embodiment of an ablation element of the present invention; [0060] FIG. 8 illustrates an ablation element in position around the pulmonary veins of a heart; [0061] FIG. 8A is a perspective side view of one embodiment of the ablation element of FIG. 8 ; [0062] FIG. 8B is a perspective cross sectional view of a reflector of the ablation element of FIG. 8A ; [0063] FIG. 8C is a perspective side view of another embodiment of the ablation element of FIG. 8 ; [0064] FIG. 8D is a perspective cross sectional view of a reflector of the ablation element of FIG. 8C ; [0065] FIG. 8E is a perspective side view of yet another embodiment of the ablation element of FIG. 8 ; [0066] FIG. 8F is a perspective cross sectional view of a reflector of the ablation element of FIG. 8E ; [0067] FIG. 8G is a perspective side view of even still another embodiment of the ablation element of FIG. 8 ; [0068] FIG. 8H is a perspective cross sectional view of a reflector of the ablation element of FIG. 8G ; [0069] FIG. 9 is a perspective view of another embodiment of an ablation element of the present invention; [0070] FIG. 10 is a schematic, cross sectional top view of a surgical ablation element of according to the invention, illustrating the different ablating positions of the light delivering element; [0071] FIG. 11 is a schematic, perspective view of a human heart and an instrument according to the invention, showing one technique for creating epicardial lesions; [0072] FIG. 12 is a schematic, perspective view of a human heart and an instrument according to the invention, showing one technique for creating endocardial lesions; [0073] FIG. 13 is a schematic, perspective view of a human heart and an instrument according to the invention, showing another technique for creating endocardial lesions; [0074] FIG. 14A is a perspective cross sectional view of yet another embodiment of an ablation element of the present invention; [0075] FIG. 14B is a perspective cross sectional view still yet another embodiment of an ablation element of the present invention; [0076] FIG. 14C is a perspective cross sectional view of another embodiment of an ablation element of the present invention; [0077] FIG. 14D is a perspective cross sectional view of still another embodiment of an ablation element of the present invention; [0078] FIG. 15 is an exploded schematic view of another embodiment of an ablation instrument of the present invention; [0079] FIG. 16 is a schematic, perspective view of a human heart and an instrument according to the invention, showing yet another technique for creating endocardial lesions; [0080] FIG. 17A is a perspective view of a flexible guidewire of the present invention; [0081] FIG. 17B is a perspective side view of an ablation instrument of the present invention; [0082] FIG. 17C is another perspective side view of the ablation instrument of FIG. 17B ; [0083] FIG. 17D is yet another a perspective side view of the ablation instrument of 17 B; [0084] FIG. 18A is a perspective view of a flexible guidewire of the present invention; [0085] FIG. 18B is a perspective side view of an ablation instrument of the present invention; [0086] FIG. 18C is another perspective side view of the ablation instrument of FIG. 18B ; [0087] FIG. 18D is yet another a perspective side view of the ablation instrument of 18 B; [0088] FIG. 19 is a perspective view of yet another embodiment of a cardiac ablation instrument of the present invention; [0089] FIG. 19A is a cross-sectional view of the ablation instrument of FIG. 19 ; [0090] FIG. 19B is an exploded view of the ablation instrument of FIG. 19 ; [0091] FIG. 20A is an exploded view of the guide or tip of the instrument of FIG. 19 ; [0092] FIG. 20B is a perspective exterior view of the guide or tip of the instrument of FIG. 19 ; [0093] FIG. 20C is a perspective cross-sectional view of the guide or tip of FIG. 20B ; [0094] FIG. 21A is an exploded view of the extension to sheath assembly of FIG. 19 ; [0095] FIG. 21B is a cross-sectional view of the extension to sheath assembly of FIG. 19 ; [0096] FIG. 22 is an exploded view of the handle portion of FIG. 19 ; [0097] FIG. 22A is an enlarged detailed view of the indexing button of FIG. 22 ; [0098] FIG. 22B is a cross-sectional view of the handle portion of FIG. 22 ; and [0099] FIG. 23 is cross-sectional view of another embodiment of the ablation instrument shown in FIG. 19 . DETAILED DESCRIPTION OF THE INVENTION [0100] The present invention provides hand held surgical ablation instruments that are useful for treating patients with cardiac conditions such as, for example, atrial arrhythmia. Turning now to the drawings and particularly to FIG. 1 , an exemplary embodiment of a hand held cardiac ablation instrument 10 in accordance with the present invention is shown. Ablation instrument 10 generally includes a handle 12 having a proximal end 14 and a distal end 16 , an ablation element 20 mated to or extending distally from the distal end 16 of the handle 12 , and a penetrating energy source 50 . The energy source 50 can be, for example, a laser source of radiation, e.g., coherent light, which can be efficiently and uniformly distributed to the target site while avoiding harm or damage to surrounding tissue. In use, the instrument 10 can be applied either endocardially or epicardially, and is effective to uniformly irradiate a target ablation site. [0101] The handle 12 of the ablation instrument 10 is effective for manually placing the ablation element 20 proximate to a target tissue site. While the handle 12 can have a variety of shapes and sizes, preferably the handle 12 is generally elongate with at least one inner lumen extending therethrough. The proximal end 14 of the handle 12 can be adapted for coupling with a source of radiant energy 50 , and the distal end of the handle 16 is mated to or formed integrally with the ablation element 20 . In a preferred embodiment, the handle 12 is positioned substantially coaxial with the center of the ablation element 20 . The handle 14 can optionally include an on-off switch 18 for activating the laser energy source 50 . [0102] As shown in more detail in FIG. 1A , the ablation element 20 can include an outer housing 22 having an inner lumen extending therethrough, and a light delivering element 32 disposed within the inner lumen of the outer housing 22 . The outer housing 22 can be flexible, and is preferably malleable to allow the shape of the outer housing 22 to conform to various anatomical shapes as needed. The light delivering element 32 which is disposed within the outer housing 22 includes a light transmitting optical fiber 34 and a light diffusing tip 36 . The light transmitting optical fiber 34 is adapted to receive ablative energy from a penetrating energy source 50 and is effective for delivering radiant energy from the laser energy source 50 to the light diffusing tip 36 , wherein the laser energy is diffused throughout the tip 36 and delivered to the target ablation site. [0103] The light delivering element 32 can be slidably disposed within the outer housing 22 to allow the light diffusing tip 36 to be positioned with respect to the target ablation site. A lever 52 or similar translatory mechanism can be provided for slidably moving the light delivering element 32 with respect to the handle 12 . As shown in FIGS. 1A and 1B (which shows the handle 12 with the light delivering element 32 slidably contained therein without the outer housing 22 ), the lever 52 can be mated to the light delivering element 32 and can protrude from a distally extending slot 54 formed in the handle 12 . In this configuration, translatory movement of the lever 52 effects advancement or sliding of the light delivering element 32 to selectively place the light delivering element 32 at a discrete position within the outer housing 22 and proximate to the tissue surface to be ablated. Markings can also be provided on the handle 12 for determining the distance moved and the length of the lesion formed. A person skilled in the art will readily appreciate that a variety of different mechanisms can be employed to slidably move the light delivering element 32 with respect to the handle 12 . [0104] The outer housing 22 can optionally include a connecting element for forming a closed-loop circumferential ablation element 20 . By non-limiting example, FIG. 1A illustrates a connecting element 30 extending from the leading, distal end 24 of the outer housing 22 . The connecting element 30 has a substantially u-shape and is adapted for mating with the trailing end 26 of the outer housing 22 or the distal end 16 of the handle 12 . The connecting element 30 can optionally be adapted to allow the size of the circumferential ablation element 20 to be adjusted once positioned around the pulmonary veins. For example, the connecting element 30 can be positioned around the trailing end 26 of the outer housing 22 after the circumferential ablation element 20 is looped around the pulmonary veins, and the handle 12 can then be pulled to cause the ablation element 20 to tighten around the pulmonary veins. While FIG. 1A illustrates a U-shaped connecting element, a person having ordinary skill in the art will appreciate that a variety of different connecting elements or clasps 30 can be used such as, for example, a hook, a cord, a snap, or other similar connecting device. [0105] Another embodiment of the surgical ablation instrument 10 A is shown in FIG. 2 , where a rotatable lever 82 can be used to control the positioning of a light delivery element in the distal tip of the instrument. The lever 82 turns a translatory mechanism 80 , as shown in more detail in FIG. 2A . In this embodiment, a portion 84 of the handle is separated from the rest of the housing 88 such that it can rotate, and preferably sealed by O-rings 90 and 91 , or the like. The rotatable segment 84 has internal screw threads 92 . Within this segment of the handle, the light delivering fiber 32 A is joined to a jacket 93 that has an external screw thread 94 . The threads 94 of jacket 93 mate with the threads 92 of rotatable segment 84 . The lever 82 is affixed to rotatable segment 84 (e.g., by set screw 86 ) such that rotation of knob 82 causes longitudinal movement of the fiber 32 A relative to the housing 88 . [0106] The outer housing 22 A can be preshaped to function as a guide device to guide the light delivering element 32 A along the ablation path. The cooperation between the light delivering element 32 A and the inner lumen, as the element 32 A is advanced through the inner lumen, positions the ablative element in a proper orientation to facilitate ablation of the targeted tissue during the advancement. Thus, once the outer housing 22 A is stationed relative to the targeted tissue site, the light delivering element 32 A can be easily advanced along the ablation path to generate the desired tissue ablations. [0107] As shown in FIG. 2 , the outer housing 22 A can be in the shape of a hollow ring (or partial ring) forming an opening loop having leading and trailing ends 24 A, 26 A. The open loop-shape allows the circumferential ablation element 20 A to be positioned around one or more pulmonary veins. While an open loop shape is illustrated, the outer housing 22 A can also be formed or positioned to create linear or other shaped lesions. The slidable passing of the light delivering element can be performed by incrementally advancing the light delivering element 32 A along a plurality of positions on the ablation path to produce a substantially continuous lesion. [0108] The inner lumen of the outer housing 22 , 22 A in FIGS. 1 and 2 can optionally contain a lubricating or irrigating fluid to assist the light delivering element 32 , 32 A as it is slidably moved within the outer housing 22 , 22 A. The fluid can also cool the light delivering element 32 , 32 A during delivery of ablative energy. Fluid can be introduced using techniques known in the art, but is preferably introduced through a port and lumen formed in the handle. The distal end 24 , 24 A of the outer housing 22 , 22 A can include a fluid outflow port 28 , 28 A for allowing fluid to flow therethrough. [0109] As shown in FIG. 3 , which illustrates a portion of ablation instrument 10 , the fluid travels between the light delivering element 32 toward the leading, distal end 26 of the outer housing 22 and exits the fluid outflow port 28 . Since the port 28 is positioned on the distal end 26 of the outer housing 22 , the fluid does not interfere with the ablation procedure. While FIG. 3 illustrates the fluid outflow port 28 disposed on the distal end 24 of the outer housing 22 , a person skilled in the art will readily appreciate that the fluid outflow port 28 can be disposed anywhere along the length of the outer housing 22 . [0110] In FIG. 3A another embodiment of a light delivery element according to the invention is shown in which fiber 34 A terminates in a series of partially reflective elements 35 A- 35 G. A person skilled in the art should be appreciated that the number of reflective elements can vary depending on the application and the choice of six is merely for illustration. The transmissivity of the various segments can be controlled such that, for example, segment 35 A is less reflective than segment 35 B, which in turn is less reflective than 35 C, etc., in order to achieve uniform diffusion of the light. The reflective elements of FIG. 3A can also be replaced, or augmented, by a series of light scattering elements having similar progressive properties. FIG. 3A also illustrates another arrangement of exit ports 28 ′ in housing 22 A′ for fluid release, whereby the fluid can be used to irrigate the target site. [0111] With reference again to FIG. 3 , the light transmitting optical fiber 34 generally includes an optically transmissive core surrounded by a cladding and a buffer coating (not shown). The optical fiber 34 should be flexible to allow the fiber 34 to be slidably moved with respect to the handle 12 . In use, the light transmitting optical fiber 34 conducts light energy in the form of ultraviolet light, infrared radiation, or coherent light, e.g., laser light. The fiber 34 can be formed from glass, quartz, polymeric materials, or other similar materials which conduct light energy. [0112] The light diffusing tip 36 extends distally from the optical fiber 34 and is formed from a transmissive tube 38 having a light scattering medium 40 disposed therein. For additional details on construction of light diffusing elements, see, for example, U.S. Pat. No. 5,908,415 issued Jun. 1, 1999. [0113] The scattering medium 40 disposed within the light diffusing tip 36 can be formed from a variety of materials, and preferably includes light scattering particles. The refractive index of the scattering medium 40 is preferably greater than the refractive index of the housing 22 . In use, light propagating through the optical fiber 34 is transmitted through the light diffusing tip 36 into the scattering medium 40 . The light is scattered in a cylindrical pattern along the length of the light diffusing tip 36 and, each time the light encounters a scattering particle, it is deflected. At some point, the net deflection exceeds the critical angle for internal reflection at the interface between the housing 22 and the scattering medium 40 , and the light exits the housing 22 to ablate the tissue. [0114] Preferred scattering medium 40 includes polymeric material, such as silicone, epoxy, or other suitable liquids. The light scattering particles can be formed from, for example, alumina, silica, or titania compounds, or mixtures thereof. Preferably, the light diffusing tip 36 is completely filled with the scattering medium 40 to avoid entrapment of air bubbles. [0115] As shown in more detail in FIG. 3 , the light diffusing tip 36 can optionally include a reflective end 42 and/or a reflective coating 44 extending along a length of one side of the light diffusing tip 36 such that the coating is substantially diametrically opposed to the target ablation site. The reflective end 42 and the reflective coating 44 interact to provide a substantially uniform distribution of light throughout the light diffusing tip 36 . The reflective end 42 and the reflective coating 44 can be formed from, for example, a mirror or gold coated surface. While FIG. 3 illustrates the coating extending along one side of the length of the diffusing tip 36 , a person having ordinary skill in the art will appreciate that the light diffusing tip 36 can be coated at different locations relative to the target ablation site. For example, the reflective coating 44 can be applied over 50% of the entire diameter of the light diffusing tip 36 to concentrate the reflected light toward a particular target tissue site; thereby forming a lesion having a relatively narrow width. [0116] In one use, the hand held ablation instrument 10 is coupled to a source of penetrating energy 50 and can be positioned within a patient's body either endocardially or epicardially to ablate cardiac tissue. When the penetrating energy is light, the source is activated to transmit light through the optical fiber 34 to the light diffusing tip 36 , wherein the light is scattered in a circular pattern along the length of the tip 36 . The tube 38 and the reflective end 42 interact to provide a substantially uniform distribution of light throughout the tip 36 . When a mirrored end cap 42 is employed, light propagating through the light diffusing tip 36 will be at least partially scattered before it reaches the mirror 42 . When the light reaches the mirror 42 , it is then reflected by the mirror 42 and returned through the tip 36 . During the second pass, the remaining radiation encounters the scattering medium 40 which provides further diffusion of the light. [0117] When a reflective coating or longitudinally disposed reflector 44 is used, as illustrated in FIG. 4 , the light 58 emitted by the diffusing tip 36 will reflected toward the target ablation site 56 to ensure that a uniform lesion 48 is created. The reflective coating or element 44 is particularly effective to focus or direct the light 58 toward the target ablation site 56 , thereby preventing the light 58 from passing through the housing 22 around the entire circumference of the housing 22 . [0118] In another embodiment as illustrated in FIG. 4A , the light emitting element can further include a longitudinally extended lens element 45 A, such that light scattered by the scattering medium 40 A is not only reflected by reflector 44 A but also confined to a narrow angle. [0119] In another aspect of the present invention, an irrigation cap 100 can be placed over the diffusing tip 36 , as illustrated in FIG. 4B . The irrigation cap 100 can be formed from a flexible material such as silicone. The irrigation cap 100 includes a pair of attached jaws 102 , 104 . As shown in cross-section in FIG. 4C , the interior of the irrigation cap 100 includes a shaped cutout portion that is configured to fit over the optical fiber 34 like an open bracket that surrounds a portion of the optical fiber 34 . The irrigation cap 100 also includes a fluid inlet 106 for the introduction of an irrigation or lubricating fluid between the light delivering element 32 and the cap 100 . When the optical fiber 36 and diffusing tip 36 are captured within the cutout portion as shown in FIGS. 4B and 4C , a fluid carrying cavity 108 is formed as part of the cutaway portion of the cap 100 . In use, fluid enters through the inlet 102 and into the cavity 108 where it cools the optical fiber 34 . The excess fluid flows around the crevices between the optical fiber 34 and the irrigation cap 100 , exiting from the cap 100 in the space between the jaws 102 , 104 . Preferably, the free ends of the jaws 102 , 104 include surface features 110 such as grooves or teeth to provide for better gripping. [0120] In yet another embodiment of the invention, illustrated in FIG. 5 , the housing that surrounds the light delivery element 40 B can include or surround a malleable element 47 B, e.g., a soft metal bar or strip such that the clinician can form the distal end of the instrument into a desired shape prior to use. Although the malleable element 47 B is shown embedded in the housing, it should be clear that it can also be incorporated into the light delivery element (e.g., as part of the longitudinally extended reflector) or be distinct from both the housing and the light emitter. [0121] In still yet another embodiment of the invention, the outer housing 122 A can comprise a plurality of linked units 120 , as shown in FIGS. 6 and 6 A, with FIG. 6B representing an exploded view of the outer housing. The linked units can be flexibly interconnected so that the housing 122 A can bend into a desired shape. The housing 122 A is associated with a control mechanism 122 that effects the movement of the units 120 . For instance, a rotatable knob 124 can be implemented for bending the distal end of the outer housing 122 A. The rotatable knob 124 can be associated with a wire or elongated filament (not shown) attached to the distal end of the housing 122 A such that, upon rotation of the knob 124 , the wire or filament is moved distally or proximally to cause longitudinal movement of the wire relative to the housing 122 A. Preferably, the wire is a shape memory wire having a preformed shape such that the outer housing 122 A can take the preshaped form. [0122] In another aspect of the invention, the ablation element, including the housing and inner lumen, can be configured with a special geometry to align the light delivering element and the outer housing. As illustrated in FIGS. 7A-7F , the outer housing 22 A′- 22 F′ and the inner lumen of the instrument 20 A′- 20 F′ can have a variety of shapes, while the light delivering element 32 A′- 32 F′ can also have a special geometry that is complementary to the shape of the inner lumen of the outer housing 22 A′- 22 F′. For instance, the light delivering element 32 A′- 32 F′ can include a shape creating element 130 A′- 130 F′ to ensure that the light delivering element 32 A′- 32 F′ is aligned with the inner lumen of the outer housing 22 A′- 22 F′. For instance, as illustrated in FIGS. 7A-7D , the light delivering element 32 A′- 32 D′ can be heat shrunk around the shape creating element 130 A′- 130 D′ to form a unique, pyramidal profile that limits the orientation and direction of the emitted ablation energy. With this profile, the light delivering element 32 A′- 32 D′ is prevented from rotating within the housing 22 A′- 22 D′ as it is sliding. The shape creating element 130 A′- 130 D′ can be, for example, a shape memory flat wire (e.g., Nitinol flat wire) as illustrated, a polymer ribbon, or any protruding device that can be adhered to or incorporated with the light delivering element 32 A′- 32 D′ to create a unique profile complementary to the inner lumen of the housing 22 A′- 22 D′. FIGS. 7E and 7F show other embodiments of light delivering elements 32 E′, 32 F′ having a shape or profile geometry that restricts rotation once inside the inner lumen of the housing 22 E′, 22 F′. As illustrated, the inner lumen of housing 22 E′, 22 F′ can form a keyhole-like shape, while the outer shape of the housing 22 E′, 22 F′ can be substantially cylindrical. [0123] The housing can be made from a variety of materials including polymeric, electrically nonconductive material, like polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoralkoxy (PFA), urethane, polyurethane, or polyvinyl chloride (PVC), which can withstand tissue coagulation temperatures without melting and provides a high degree of laser light transmission. Preferably, the housing is made of Teflon® tubes and/or coatings. The use of Teflon® improves the procedures by avoiding the problem of fusion or contact-adhesion between the ablation element and the cardiac tissue during usage. While the use of Teflon® avoids the problem of fusion or contact-adhesion, the hand held cardiac ablation instrument does not require direct contact with the tissue to effect a therapeutic or prophylactic treatment. Preferably, the housing incorporates opaque or semi-opaque materials such as expanded PTFE (ePTFE), and/or includes optically transparent windows that provide for light transmission. [0124] The housing is designed with longitudinal flexibility to ensure adequate conformance to various tissue topographies. For example, as shown in FIG. 8 , a flexible housing enables the ablation instrument to adequately contact the cardiac tissue around the pulmonary veins. In addition to longitudinal flexibility, the housing can be configured to have torsional stiffness characteristics as well to resist twisting. Resistance to twisting ensures that the ablative energy is directed toward the desired target tissue to maximize the effectiveness of the ablation and to minimize collateral damage. Because much of the housing is not visible to the surgeon during use because the left atria is located on the posterior surface of the heart, it is therefore important that the housing ensure both adequate contact and rotational alignment with the target tissue to provide effective ablation. [0125] To provide the housing with longitudinal flexibility as well as anti-twist or torsionally stiff properties, materials such as PTFE, PFA, FEP, urethane, or PVC can be used. Other similar materials can also be used which have flexural modulus properties, profile, reinforcement, or filler materials that resist twisting along the longitudinal axis. By combining various structural elements and material properties, the housing can resist twist and remain straight in two planes. In addition, by providing an element that is shaped in three dimensions inside the housing, it is possible to provide adequate positioning and flexure within difficult anatomical locations. For instance, the shaped element could include stainless steel, Nitinol or polymer round or flat wire pre-shaped to a desired shape or geometry. This shaped element could also include a malleable stainless steel or polymer structure that is manipulated by the surgeon to provide the desired positioning, as previously described in the embodiment of FIGS. 6 and 6 A. In an alternative embodiment, the housing can be provided with a series of inflatable chambers (not shown) to effect the desired shape and/or remove twist from the structure. [0126] In still a further embodiment, the housing can include a channel or lumen that, once positioned proximate to the target tissue, can be filled with a setting agent such as epoxy, UV cured adhesive, thermosetting polymer, or other material that can be inserted in liquid or gel form into the channel or lumen that, when cured, provides a rigid structure to the housing. This rigid structure then provides proper shape and position to the housing during the procedure. Alternatively, a thermoplastic metal, polymer or liquid that hardens and softens at specific temperatures can be applied to provide for a rigid structure. Following the ablation process, the filling material can be dissolved, melted, broken down, or otherwise removed to return the housing to its original flexible form for removal. [0127] Further, the housing of the present invention can include a profile that provides for longitudinal flexibility and proper orientation with respect to the target tissue to be ablated. As illustrated, FIGS. 8A-8H show a variety of profile designs for the housing 22 a , 22 b , 22 c , 22 d , as well as profile designs for the reflector 23 a , 23 b , 23 c , 23 d in accordance with the invention. FIGS. 8A, 8C , 8 E, and 8 G show that the housing 22 a , 22 b , 22 c , 22 d can be formed of an optically clear material and can be formed as an integral unit, or as discrete units linked together. The housing 22 a , 22 b , 22 c , 22 d can also include grooves to facilitate flexion. In addition, the housing 22 a , 22 b , 22 c , 22 d can be formed as a bellows to allow bending. FIGS. 8B, 8D , 8 F, and 8 H show that the reflector 23 a , 23 b , 23 c , 23 d can have a three-dimensional profile that allows the placement of the light delivering element 32 a , 32 b , 32 c , 32 d inside the housing 22 a , 22 b , 22 c , 22 d in only one direction. For example, the profiles can include “D” shapes, half moons, open “C” channels, or other similar configurations that would align with the inner lumen of the housing 22 a , 22 b , 22 c , 22 d in a specific orientation, as previously described for FIGS. 7A-7F . [0128] In another embodiment of the present invention, rather than rely on the profile geometry for alignment of the light delivering element with the housing, reflective elements can be implemented which would eliminate the need for such specific geometries. As shown in FIG. 9 , a housing 22 ″ is shown having an open “C” shape to define an inner lumen within which a light delivering element 32 ″ is slidably contained. A “C” shaped reflector 132 ″ is placed over the light delivering element 32 ″ to isolate the emission of ablative energy to the uncovered portions. This ablative energy can be transmitted through a light transmissive sheet 130 ″ placed over the housing 22 ″ and onto the target tissue. The reflector can be formed from metallic foils, polymers with highly reflective surfaces, vapor or chemical deposited surfaces, or other materials having a reflective or mirror-like surface. [0129] Although illustrated in the context of light delivering surgical instruments, the malleable structures disclosed herein are equally adaptable for use with other sources of ablative energy, such as such as RF heating, cryogenic cooling, ultrasound, microwave, ablative fluid injection and the like. RF Heating devices, for example, are described in U.S. Pat. No. 5,690,611 issued to Swartz et al. and herein incorporated by reference. Cryogenic devices are similarly described, for example, in U.S. Pat. No. 6,161,543 issued to Cox et al. and herein incorporated by reference. [0130] Epicardial ablation is typically performed during a surgical procedure, which involves opening the patient's chest cavity to access the heart. The heart can be arrested and placed on a by-pass machine, or the procedure can be performed on a beating heart. The hand held ablation instrument 10 is placed around one or more pulmonary veins, and is preferably placed around all four pulmonary veins. The connecting element 30 can then be attached to the distal end 16 of the handle 12 or the proximal, trailing end 24 of the outer housing 22 to close the open loop. The handle 12 can optionally be pulled to tighten the ablation element 20 around the pulmonary veins. The energy delivering element 32 is then moved to a first position, as shown in FIG. 10 , and the energy source 50 is activated. The first lesion is preferably about 4 cm in length, as determined by the length of the tip 36 . Since the distance around the pulmonary veins is about 10 cm, the energy delivering element 32 is moved forward about 4 cm to a second position 60 , shown in phantom in FIG. 10 , and the tissue is ablated to create a second lesion. The procedure is repeated two more times, positioning the energy delivering element 32 in a third position 62 and a fourth position 64 . The four lesions together can form a lesion 48 around the pulmonary veins, for example. Advancement in such a manner includes a certain amount of overlap between the initial position and the advanced position. Typically, for a 5 cm long ablation element 20 , the instrument 10 might be advanced 4 cm at a time to thereby create a series of local 1 cm lengths, ensuring a continuous lesion. [0131] In another aspect of the invention, the instruments of the present invention are particularly useful in forming lesions around the pulmonary veins by directing radiant energy towards the epicardial surface of the heart and the loop configuration of distal end portion of the instruments facilitates such use. It has been known for some time that pulmonary veins can be the source of errant electrical signals and various clinicians have proposed forming conduction blocks by encircling one or more of the pulmonary veins with lesions. As shown in FIGS. 11 and 12 , the instrument 10 of the present invention is well suited for such ablation procedures. Because the pulmonary veins are located at the anterior of the heart muscle, they are difficult to access, even during open chest surgery. An open loop distal end is thus provided to encircle the pulmonary veins. The open loop can then be closed (or cinched tight) by a clasp, as shown. (The clasp can also take the form of suture and the distal end of the instrument can include one or more holes to receive such sutures as shown in FIG. 2 .) The longitudinal reflector structures described above also facilitate such epicardial procedures by ensuring that the light from the light emitting element is directed towards the heart and not towards the lungs or other adjacent structures. [0132] Endocardial applications, on the other hand, are typically performed during a valve replacement procedure which involves opening the chest to expose the heart muscle. The valve is first removed, and then the hand held cardiac ablation instrument 10 according to the present invention is positioned inside the heart as shown in FIG. 12 . In another approach the instrument 10 can be inserted through an access port as shown in FIG. 13 . The ablation element 20 can be shaped to form the desired lesion, and then positioned at the atrial wall around the ostia of one or more of the pulmonary veins. Once shaped and positioned, the laser energy source 50 is activated to ablate a first portion of tissue. The light delivering element 32 can then be slidably moved, as described above with respect to the epicardial application, or alternatively, the entire device can be rotated to a second position to form a second lesion. [0133] In another aspect of the invention, the ablation element 20 can be configured to have a sufficient length to create the full encircling path without advancing the light delivering element 32 through the outer housing 22 . For instance, the ablation instrument 10 can include a long (20 cm) active length that can emit at the same energy level (W/length) as that delivered by the shorter (5 cm) instrument, or can emit at a lower level. To provide effective ablative therapy, an adequate quantity of Joules per volume of tissue should be delivered. The rate of delivery, however, can be adjusted depending upon the capabilities of the materials and components of the ablation instrument 10 . Thus, the length of the ablative element 20 and consequently, the time required to complete the ablative therapy, can be varied without affecting the integrity of the overall ablation process. [0134] Accordingly, it is possible to provide a light delivering element 32 that can emit varying amounts of ablative energy along its length. FIGS. 14A-14D illustrate such ablation elements 220 , 220 ′, each of which are configured with a length sufficient to provide a continuous encircling lesion without the need for repeated advancing of the light delivering element 232 , 232 ′ to create successive therapies along the ablative path. For example, in one particular embodiment, the optical fiber 234 can have a varying diameter along its length. As shown in FIG. 14A , a first section 234 a has a greater diameter than an adjacent second section 234 b , which has a greater diameter than an adjacent third section 234 c of the optical fiber 234 . In the embodiment shown, the light delivering element 232 comprises a plurality of segments, each segment having a different diameter than an adjacent segment to collectively form an elongate energy emitting element having variable diameters along its length. The light delivering element 232 can also be provided with a tapered profile along its length, in order to vary the amount of ablative energy emitted. [0135] In another embodiment of the ablation element 220 ′ shown in FIG. 14B , an inflatable elongate balloon 240 ′ can reside within the housing 222 ′ along with the light delivering element 232 ′. An inflation controller in communication with the balloon 240 ′ and an inflation source, e.g., an air, gas or fluid pump, can be provided to enable the selective inflation of the balloon 240 ′. Upon inflation, the balloon 240 ′ can be configured to urge against the light delivering element 232 ′, causing the angular orientation of the optical fiber 234 ′ to adjust with respect to the longitudinal axis of the housing 222 ′. Thus, by selectively inflating and deflating the balloon 240 ′, the surgeon can change the angle of the light delivering element 232 ′ and consequently the energy emitting pathway along its length. [0136] In yet another embodiment shown in FIG. 14C , the ablation element 220 ″ can be provided with a plurality of light delivering elements 232 ″ of varying lengths to deliver a fraction of the total ablation energy to different areas along the length of the ablation element 220 ″. FIG. 14C illustrates a housing 222 ″ containing six light delivering element 232 a ″- 232 e ″, e.g., optical fibers; however, it is understood that any number of fibers 232 a ″- 232 e ″ can be utilized as needed. Because the total ablation energy being delivered is fractionated, each of the fibers 232 a ″- 232 e ″ has a smaller diameter than would be required for a single optical fiber 232 a ″- 232 e ″ delivering the same total amount of energy. Therefore, the fibers 232 a ″- 232 e ″ are more flexible, resulting in an overall more flexible ablation element 220 ″. [0137] Another way to change the level of ablative energy being delivered by the ablation element is to selectively block or cover areas along the length of the light delivering element. For example, as illustrated in FIG. 14D , a reflector 150 having a window 152 or discontinuous outer surface formed from a metallic or reflective material, such as gold, can be applied over a light delivering element 153 . The reflector 150 can be configured to seat around the light delivering element 153 , and a window can be provided to allow the emission of ablative energy from the light delivering element 153 . The window 152 can be adjustably moved along the length of the light delivering element 153 to effect a change in the level of ablative energy being delivered along the length of the light delivering element 153 . Alternatively, it is also possible to provide a reflector 150 having an adjustably sized window 132 whereby the surgeon can control the amount of exposure to adjust the level of emitted ablative energy of the light delivering element 153 . [0138] Whether the ablation instrument 10 requires advancement or is completely encircling, there is a potential need to provide overlap of the ablation at either end of the outer housing 22 . A clamp or clip mechanism 154 , as shown in FIG. 15 , can be provided to fix the outer housing 22 at both ends in order to ensure that both ends of the therapeutic lesion overlap for a continuous encirclement. Of course, other configurations are also possible to connect or enable overlap of the two ends of the outer housing 22 , as previously described in connection with FIGS. 2 and 12 . It is also possible to increase the time for ablation at the overlap to better ensure a completely encircling lesion has been formed. [0139] As discussed above, correct positioning of the housing 22 with respect to the patient's anatomy is critical to the efficacy of the lesion created. Specifically, the position of the housing 22 with respect to the left atrial appendage (LAA) is important to ensure that the lesion correctly isolates the pulmonary veins. The correct position of the housing 22 in such a procedure should be posterior to the LAA or between the LAA and the pulmonary vein. Through specific surgical approaches such as thoracotomy, thorascopy, sternotomy, sub xyphoid, or other undetermined surgical or scoped approaches, delivery and positioning of the housing 22 may require additional verification of position with respect to the LAA. Accordingly, the ablation instruments 10 of the present invention can incorporate radiopaque or echogenic ultrasound visible coatings or components. In addition, the application of radiopaque markers/dyes to the blood volume with techniques such as transesophageal echocardiograms (TEE) or fluoroscopy can provide further confirmation of the position of the housing 22 . In more invasive procedures, a thorascope can be used to obtain visual confirmation from the left chest. Other less invasive methods include the use of impedance measurements between electrodes and the housing, or shaped introducing guides 156 that provide for preferential positioning of the housing, as shown in FIG. 16 . [0140] FIGS. 17B-17D illustrate another embodiment of an ablation instrument 160 of the present invention. As shown in FIGS. 17B and 17D , the ablation instrument 160 includes conduction block sensors 162 and a conduction block indicator 164 on the housing 166 for determining the effectiveness of the lesion created. These sensors can be integrated into or attached to the housing 166 . In the particular embodiment shown, the ablation instrument 170 includes a single, slidable light delivering element 168 extending into a diffuser tip 170 . The housing 166 can include a window 172 to allow ablative energy to be emitted, and a plurality of irrigation ports 174 to introduce irrigation fluid into the housing 166 to cool the instrument 160 . Similar to the previous ablation instruments 10 described for FIGS. 1 and 2 , the light delivering element 168 can be moved along the length of the housing 166 by a translatory mechanism (as previously shown). As illustrated in FIGS. 17C and 17D , indicia 176 along the window 172 provides a visual cue for the surgeon to determine how far the light delivering element 168 has moved. The ablation instrument 160 can be used with a shaped, flexible guidewire 178 as shown in FIG. 17A . [0141] FIGS. 18A-18D show a similar ablation instrument 180 but with a plurality of light delivering elements 188 of varying lengths. Similar to FIGS. 17B and 17D , the ablation instrument 180 includes conduction block sensors 182 and a conduction block indicator 184 on the housing 186 for determining the effectiveness of the lesion created, as shown in FIGS. 18B and 18D . Each of the slidable light delivering elements 188 extends into a diffuser tip 190 . The housing 186 can include a window 192 to allow ablative energy to be emitted, and a plurality of irrigation ports 194 to introduce irrigation fluid into the housing 166 to cool the instrument 160 . The light delivering elements 188 can be selectively chosen by a rotatable selection mechanism 196 which includes indicia which includes markings to indicate which of the elements 188 has been chosen. The ablation instrument 180 can be used with a shaped, flexible guidewire 198 as shown in FIG. 18A . [0142] In still yet another embodiment, the present invention provides an ablation instrument 300 that can incorporate many of the advantages and features of the previous embodiments described above. As illustrated in FIG. 19 , the ablation instrument 300 can include a handle portion 310 having a flexible sheath 330 coupled thereto. The flexible sheath 330 can connect to the handle portion 310 by way of an extension 340 . Within the sheath 330 is an ablation element 350 that can be connected to the handle portion 310 and that is moveable along an ablative path or lumen 332 inside the sheath 330 via movement of the indexing button 312 located on the handle portion 310 . The sheath 330 can extend into an atraumatic guide 370 at the tip, or opposite end, of the instrument 300 . [0143] As shown, a cable 302 extends from the ablation element 350 and handle portion 310 to an attachment device such as a cable connector 304 which is adapted to be received by an energy source such as a laser source. Also extending from the cable 302 is an irrigation line 306 which allows the instrument 300 to receive irrigation fluid. The irrigation line 306 can include an attachment device, such as a male luer lock 306 , for attachment to an irrigation fluid source. [0144] The sheath 330 of the ablation element 350 can have a variety of configurations, and the sheath 330 may be preshaped or flaccid. In an exemplary embodiment, the sheath 330 is adapted to function as a guide device to direct the ablation element 350 along the treatment path, and more preferably it can be adapted to cooperate with the ablation element to position the ablation element in a proper orientation to facilitate ablation of the targeted tissue during the advancement. Thus, once the ablation sheath 330 is stationed relative to the targeted contact surface, the ablation element 350 can be easily advanced along the ablation path to generate the desired tissue treatment. The sheath 330 can also serve as an energy shield to protect tissues not targeted for treatment. [0145] FIGS. 19A and 19B illustrate one exemplary embodiment of the sheath 330 . As shown, the sheath 330 has an inner lumen 332 extending therethrough for slidably receiving the ablation element 350 , and an optically transmissive window 336 formed along at least a portion thereof. The ablation element 350 includes a fiber having a diffuser 354 disposed therearound, and a reflective element 352 disposed on a portion thereof for reflecting emitted energy toward a target ablation site. The inner lumen 332 of the sheath 330 has a shaped profile or special geometry that is adapted to receive an ablation element 350 having a shaped profile that substantially complements the shaped profile of the lumen. While the shaped profile can vary, in the illustrated exemplary embodiment, the sheath 330 is substantially D-shaped, and the ablation element 350 includes a T-bar shaped spine element 334 formed thereon and adapted to be received within the inner lumen 332 of the sheath 330 . The T-bar shape of the spine element 334 will prevent rotation of the ablation element 350 within the lumen 330 . Thus, since the ablative instrument 300 is designed to directionally emit the ablative energy from a select area of the instrument called the energy delivery portion, the spine 334 allows the ablation element 350 and the sheath 330 to be aligned to assure that the correct directionality of emitted ablative energy toward the tissue region is emitted. [0146] The sheath 330 may be made of a variety of materials, but one exemplary material is ePTFE. The porosity, density, pore size and other physical characteristics of the material should be selected so as to improve the performance of the sheath. These characteristics should be carefully chosen to give the best combination of longitudinal flexibility, tissue conformability, torsional resistance, lubricity, atrauma and shielding. Preferably, the sheath 330 is made from a polymeric material, like polyethylene, PTFE, PTFA, FEP or polyurethane, which can withstand tissue coagulation temperatures without melting and to provide a high degree of laser light transmission. Alternative designs of the sheath may incorporate opaque or semi-opaque materials such as ePTFE that incorporate optically transparent “windows,” such as window 336 , providing for light transmission. The spine element 334 is preferably formed by extrusion in PEBAX polymer. [0147] The sheath is preferably designed with longitudinal flexibility to insure adequate contact with cardiac tissue, but it can also have torsional stiffness characteristics to resist twisting. Resistance to twisting insures that the ablative energy is directed only toward the desired tissues so as to maximize ablative effectiveness and to minimize collateral damage. Alternative designs may rely upon uniquely shaped profiles and torsional flexibility to allow conformance to the variant tissue topographies. Much of the sheath is not visible to the surgeon during use because the left atrium is located on the posterior surface of the heart and there is additionally other anatomy such as the pericardium and great vessels in close proximity. Without visualization of the sheath it is therefore important that the sheath ensure both adequate contact and rotational alignment with the target tissue. [0148] Another feature of the sheath 330 is its anti-twisting properties, which relate to the ability to correctly orientate a device that is required to be rotationally directed towards a target while traveling through a flexible linear path with a window capable of being translucent to the specific energy. The mechanism of the invention is to create loosely interlocking geometries that interact to prevent rotational displacement. These components are then utilized to fix a therapeutic device within one or both of these components such that directional orientation is assured. As shown in FIG. 19A , the T-shaped spine element 334 interacts within the larger “T” shape channel (externally “D” shaped) of the lumen 332 to properly align a reflector 352 of the therapeutic device towards the clear therapy window 336 . The sheath 330 can also include stabilizers 338 , such as Nitinol (NiTi) flat wire, polymer ribbon, or protruding devices adhered or incorporated into the profile thereof to interact with the guide sheath 330 and limit the capability of the ablation device 350 to rotate within the sheath 330 . The stabilizers 338 can also be adapted to provide a shielding effect and/or a reflective effect to direct energy toward the window 336 . Thus the shape of the stabilizers 338 can vary depending on the intended purpose. [0149] Preferred embodiments of the disclosed invention including anti-twist or torsionally stiff properties include making the sheath from PTFE, PFA, FEP, Urethane, PVC or other similar materials that by properties such as flexural modulus, profile, reinforcement, or filler materials result in a sheath that resists twist along the longitudinal axis. By combining various structural elements and material properties it is further possible to provide for a device that resist twist and remains straight in two planes or is preferentially shaped in three dimensions. By providing a three dimensionally shaped element within the sheath it is possible to provide adequate positioning within even the most variant anatomy. [0150] Yet a further embodiment of the current disclosure would include a channel or lumen within the sheath that once in position would be filled with a material such as epoxy, UV cured adhesive, thermosetting polymer or other material that can be inserted in liquid or gel form into such lumen or channel and when cured provides a rigid structure to the sheath. This rigid structure then provides proper shape and position to the sheath during the procedure. Alternately the material could be a thermoplastic metal, polymer, or liquid that hardens and softens at appropriate temperature and provides for similar structure. Following the therapy process the filling material would be dissolved, melted, broken, or otherwise affected to destroy the previous rigid structure and return the sheath to a flexible form for removal. [0151] In another exemplary embodiment, the sheath 330 can be extruded with a shielding material, such as a dye or particulate to focus the energy toward the window 336 . For example, by utilizing metallic particulates as a loading agent in the material it would be possible to adequately shield an RF or ultrasound antennae to create a directional emission of energy. FIG. 23 illustrates a sheath 330 ′ having particulate embedded therein to create a shielding effect. While a reflector 352 ′ is shown disposed on the spine 334 ′, the particulate may be effective alone to shield the energy, and thus a reflector 352 ′ may not be necessary. [0152] Anti-twist designs may further include preferable profiles of the sheath that rely upon the shape of the profile rather than torsional rigidity to provide correct alignment with the target tissue. Such preferred profiles would include “D” shapes, half moons, open “C” channels, triangular channels, or other similar and varied designs that interact to align the light delivering element with the tissue. The preferred embodiment of the current disclosure is a “D” shape whereby the flat segment of the “D” provides such accurate alignment with the tissue when coupled with a sheath material that is torsionally flaccid. The crown of the “D” further provides for visual or tactile verification of alignment. [0153] The previously described embodiments providing for anti-twist or alignment of the sheath could incorporate reflective elements that would eliminate need for the above described “special geometry” that operates to align the light emission device. By providing reflective elements on the guide sheath it would therefore be possible to eliminate the directional orientation device on the ablative device. The reflective element(s) could also be provided on the spine 334 ′, as shown in FIG. 23 , to allow the energy emitting device, e.g., the fiber 350 ′, to rotate freely within the spine 334 ′. With such a configuration, the spine 334 ′ can form a catheter or guide tube for the energy emitting device, and the spine 334 ′ interacts with the sheath 330 to position the reflective element(s) in the proper orientation. As shown in FIG. 23 , a reflective element 352 ′ is disposed within the lumen of the spine 334 ′ to direct energy toward the window 336 ′. While not shown, the spine 334 ′ can have a curved configuration or other shapes that allow the reflective element 352 ′ to direct energy toward the window 336 ′. The reflective element 352 ′ could also be disposed within the spine 334 ′ itself, rather than in the inner lumen. Diffuser 354 can also include a mirror 356 , as shown in FIG. 19B . [0154] Such reflective elements could include but are not limited to metallic foils, polymers with highly reflective surfaces, vapor or chemically deposited surfaces or other technologies that result in a reflective or mirror like surface. The advantage of this system over the prior art is that the energy emissive element is not required to be shaped to match the channel. Rather, the positioning component can be shaped appropriately and the energy emission element can then be fixed to this component, or it can be slide and/or rotate freely within this component. By attaching the reflector 352 to the positioning component, e.g., the spine 334 or the sheath 330 , rotation of the energy transmitter is irrelevant to the energy emission direction. This is beneficial in that the emitter does not require a shaped output, rather the alignment feature directs this output. [0155] The second advantage of this invention is the novel use of FEP and ePTFE to create an insulating and transmissive guide channel. This is advantageous over prior art in that the addition of FEP creates an optically clear window 336 . In an exemplary embodiment, the sheath 330 includes a semi-cylindrical portion formed from ePTFE, and a planar bottom surface formed from FEP that are bonded together using heat and pressure to form the D-shaped sheath 330 . Further, it is notable that this same technology could be utilized for endoscopic evaluation of anatomical structures whereby an endoscopic evaluation device may be passed down the length of the channel and visually inspect the tissues in contact with the guide channel. This may be of great advantage when tissues in opaque or visually impeding fluids typically surround the structure to be treated. The ability to particulate or pigment load (using multicolored extrusion lines) the alignment spine 334 in order to create either electromagnetic shielding and/or optical shielding for controlling the emissive aperture is also an additional feature of the present invention. Also, the present invention provides the ability to create an optical lens on the spine 334 to create a focused energy emission. Specifically, by bulking up or shaping the segments of the tubing, it would be possible to create a focusing or diverging lens to create the appropriate emission. [0156] Thirdly, the creation of a T-shaped shrink tube provides the ability to appropriately pass coolant throughout the length of the channel as well as providing proper orientation. In addition, the sheath 330 bears graphical markings and numberings to aid the surgeon in orienting and positioning the device on cardiac tissue. Preferably, the markings and their color are specifically designed to enhance visibility and recognition under operating room lighting conditions. For example, the markings may be blue. Further, a transmurality sensor or other lesion effectiveness/assessment sensor may also be integrated into or attached to the sheath. [0157] Turning now to another component of the ablation instrument 300 , FIGS. 20A-20C illustrate the flexible tip or guide 370 . FIG. 20A illustrates an exploded view of the atraumatic tip 370 , which also includes a window 378 for energy emission. As shown, the spine 334 enables the ablation element 350 and diffuser 354 to be slidably extended through its lumen 376 . As shown in FIGS. 20B and 20C , the guide 370 includes a blunt, atraumatic tip 372 and a flared extension 374 at an opposite end for creating an atraumatic connection with the sheath 330 . Extending longitudinally within the guide 370 is a lumen 376 for slidably passing the spine 334 and ablation element 350 . [0158] The guide component design is optimized to provide minimal trauma and resistance during surgical placement while providing maximum visibility under OR lighting and maximal grip by forceps and other surgical instruments. Its dimensions, geometry and material are specifically chosen for this purpose. Its design includes both an external flat surface for easy visual and tactile orientation during use, and an internal channel designed to provide an optimal feel to the surgeon. The guide is an injection molded component, made of a synthetic rubber (TPE). It includes an integral connector which allows it to be bonded to the distal end of the sheath with a UV adhesive. Its surgical “feel” is enhanced by its closed end, hollow cylindrical design. This internal feature is created through use of a wire placed in the mold prior to injection and removed after part molding is complete. The tip of the cylinder is closed by an RF heat forming process. Although the external cross section of the guide is essentially round, it does include a flat surface on its bottom side. This flat surface serves to improve the feel that the surgeon perceives when grasping the guide with surgical instruments. The exterior surface of the guide bears a no slip matt finish, rather than a polished finish, to improve the surgeons ability to easily grip the part with his instruments. [0159] The integral connector is designed to also function as an atraumatic means of transition from the small cross section guide to the larger cross section sheath. This feature is important since the device also dilates and separates the sometimes fragile cardiac tissues during surgical placement. [0160] The device's extension 340 is specifically designed as a flexible, rather than rigid component. This approach makes the instrument 300 both more ergonomic for the surgeon and less obtrusive in the crowded surgical field. It is formed of an extrudable polymer and contains helically wound stainless steel wire to prevent kinking when flexed. This component serves two functions. It provides room for the 7 cm movement of the therapeutic fiber 350 as it is indexed forward and backward. It also provides physical separation between the light delivering sheath 330 and the handle 310 . This separation makes the instrument 300 more easily and conveniently used in the always crowded sterile field. It allows a more ergonomic positioning of the handle relative to the surgical access site, including angular orientations. [0161] In one preferable embodiment, the extension 340 is bonded to the sheath 330 with UV cured adhesive using a molded thermoplastic connector. The extension 340 can be attached to the sheath with a sheath connector 342 , as shown in FIGS. 21A and 21B . [0162] The instrument 300 includes a handle 310 attached to the sheath 330 . An inner lumen can extend through the handle to receive the light delivering element 350 . The passing of the light delivering element is performed by incrementally advancing the ablative element 350 along a plurality of positions of the ablation path to produce a substantially continuous lesion. [0163] Ablation with a continuous encircling lesion in the current disclosure is intended to occur by advancing a short, perhaps 1-5 cm long, ablation device that is repetitively positioned, activated, and advanced to create successive therapies along the path of the guide sheath. Advancement includes a certain amount of overlap between the initial position and the advanced position. For example a 5 cm long device might be advanced 4 cm at a time thereby creating a series of local 1 cm lengths that experience double therapies. In this manner a continuous lesion set can be insured. [0164] The handle 310 is designed to allow comfortable, one handed indexing. The indexing button 312 and mechanism provide very positive tactile and audible feedback to the user when each index location is reached. Among other benefits, this design allows the surgeon to effectively index the device without looking at the handle. The surgeon is able to track the location of the ablative diffuser by the feel and sound of the handle's feedback mechanism. The surgeon is also able to visually locate and track the position of the ablative element within the sheath by observing the red glow of device's red aiming beam, which is visible through the shield side of the sheath 330 . [0165] The handle 310 has an overall triangular cross section designed to ergonomically fit the surgeons hand. It also includes multiple finger grips which aid single handed actuation of the indexing button 312 . The audible and tactile responses are created through use of a spring loaded ball detent assembly 314 contained in the indexing button 312 and corresponding slots formed in the handle at each indexing position. [0166] The handle 310 is sequentially marked by numbers 1 - 7 , one number at each index position. These numbers correspond to the ablating element indexing positions also marked on the sheath. The handle 310 also includes a dynamic o-ring seal which functions to contain the irrigation fluid inside the device while allowing easy indexing. [0167] Alternative embodiments of the device may include long (20 cm+) active lengths that are placed and left in position to create the full encircling path without advancing the device through the guide sheath. This may be enacted at the same dose level (perhaps W unit length) as that delivered by the shorter (4 cm) device or may alternatively be a significantly lower dose. It is believed that a quantity of Joules per volume of tissue must be delivered in order to provide an effective therapy. Therefore the rate of delivery of this energy can be accelerated or slowed depending upon the capabilities of the materials and components therefore allowing the use of various configurations to provide different active lengths. The variable that would be changed to control the amount of energy delivered would then be therapy time. [0168] FIG. 22 illustrates an exploded view of the handle portion 310 of the ablation instrument 300 . As shown, the extension 340 is attached to an indexing button 312 by means of an inner extension 346 . The inner extension 346 can be configured within an o-ring housing 360 between which there is an o-ring 362 for seating within the handle portion 310 . An outer fiber cover 316 and inner fiber cover 318 envelope the ablation element or fiber 350 , which extends into a flow channel 344 connected to the inner extension 346 . Seated on the exterior of the flow channel 344 is the indexing button 312 , which includes a ball detent assembly 314 as shown in FIG. 22A . By exerting a downward pressure against the indexing button 312 , the surgeon is able to effect linear movement of the flow channel 344 which then moves the ablation element 350 . FIG. 22B illustrates an alternative embodiment of the handle portion 310 in which the flow channel 344 is attached to a single o-ring 362 to form a seal near the inner extension 346 . [0169] As shown in FIG. 19 , the ablation instrument 300 of the present invention also utilizes an irrigating fluid. An irrigating fluid is disposed between the light delivery element 350 and the sheath 330 . This fluid is a physiologically compatible fluid, such as saline, and is used to cool the light emitting element and for tissue irrigation via one or more exit ports in the sheath 330 . [0170] Irrigation serves to increase the efficiency and effectiveness of the device by acting as an optical couple between the diffuser and the tissue. This in turn reduces surface temperatures and subsequent tissue charring, and reduces the chances of collateral injury. The device's irrigation design provides constant low flow when the therapy is not being applied and a higher flow rate during ablation. The continuous low flow rate irrigation is included to prevent blood, biological fluids or other fluids entering the device's irrigation holes, yet prevents the waste and inconvenience of continuous high flow irrigation. When an ablation is begun the system automatically switches to a flow rate of sufficient magnitude for irrigation. The irrigation system design includes a “loop” in the supply line to provide low flow irrigation. [0171] The device is designed so that it may be labeled as class 1 even though it is driven by 60 W of laser power. This is a great advantage for the surgical and OR staff since it relieves them of the complications of class 4 devices such as protective eyewear, warning lights on the OR door, and entry door interlocks. The class 1 labeling is achievable in part because of the diffused light delivery of the device, and also because of the product's TSS. To make the TSS workable, the E360 includes special coverings on the glass fiber. These coverings act to ensure that the laser system shuts down quickly in the case of a fiber break. The fiber is covered from the laser connector to the handle with a woven stainless steel mesh and two layers of polymer tubing. From within the handle to a point near the diffuser, the fiber is covered by two layers of polymer tubing. [0172] Preferred energy sources for use with the hand held cardiac ablation instrument 10 and the balloon catheter 150 of the present invention include laser light in the range between about 200 nanometers and 2.5 micrometers. In particular, wavelengths that correspond to, or are near, water absorption peaks are often preferred. Such wavelengths include those between about 805 nm and about 1060 nm, preferably between about 900 nm and 1000 nm, most preferably, between about 915 nm and 980 nm. In a preferred embodiment, wavelengths around 915 nm are used during epicardial procedures, and wavelengths around 980 nm are used during endocardial procedures. Suitable lasers include excimer lasers, gas lasers, solid state lasers and laser diodes. One preferred AlGaAs diode array, manufactured by Optopower, Tucson, Ariz., produces a wavelength of 980 nm. Typically the light diffusing element emits between about 2 to about 10 watts/cm of length, preferably between about 3 to about 6 watts/cm, most preferably about 4 watts/cm. [0173] The term “penetrating energy” as used herein is intended to encompass energy sources that do not rely primarily on conductive or convective heat transfer. Such sources include, but are not limited to, acoustic and electromagnetic radiation sources and, more specifically, include microwave, x-ray, gamma-ray, and radiant light sources. [0174] The term “curvilinear,” including derivatives thereof, is herein intended to mean a path or line which forms an outer border or perimeter that either partially or completely surrounds a region of tissue, or separate one region of tissue from another. Further, a “circumferential” path or element may include one or more of several shapes, and may be for example, circular, annular, oblong, ovular, elliptical, or toroidal. The term “clasp” is intended to encompass various types of fastening mechanisms including sutures and magnetic connectors as well as mechanical devices. The term “light” is intended to encompass radiant energy, whether or not visible, including ultraviolet, visible and infrared radiation. [0175] The term “lumen,” including derivatives thereof, is herein intended to mean any elongate cavity or passageway. [0176] The term “transparent” is well recognized in the art and is intended to include those materials which allow transmission of energy. Preferred transparent materials do not significantly impede (e.g., result in losses of over 20 percent of energy transmitted) the energy being transferred from an energy emitter to the tissue or cell site. Suitable transparent materials include fluoropolymers, for example, fluorinated ethylene propylene (FEP), perfluoroalkoxy resin (PFA), polytetrafluoroethylene (PTFE), and ethylene-tetrafluoroethylene (ETFE). [0177] The term “catheter” as used herein is intended to encompass any hollow instrument capable of penetrating body tissue or interstitial cavities and providing a conduit for selectively injecting a solution or gas, including without limitation, venous and arterial conduits of various sizes and shapes, bronchioscopes, endoscopes, cystoscopes, culpascopes, colonscopes, trocars, laparoscopes and the like. Catheters of the present invention can be constructed with biocompatible materials known to those skilled in the art such as those listed supra, e.g., silastic, polyethylene, Teflon, polyurethanes, etc. [0178] One skilled in the art will appreciate further features and advantages of the invention based on the above-described embodiments. Accordingly, the invention is not to be limited by what has been particularly shown and described, except as indicated by the appended claims. All publications and references cited herein are expressly incorporated herein by reference in their entirety.
Ablation instruments and methods are disclosed for ablating diseased tissue such as cardiac tissue. The method includes introducing a flexible elongate member into a predetermined tissue site with a flexible elongate member having a proximal end, a distal end and a longitudinal lumen extending therebetween. A slidable conductor is positioned through the lumen proximate to the tissue site and energy is transmitted to the distal end of the elongate member through the conductor. The flexible elongate member is both longitudinally flexible and resists twisting during bending. The target tissue is ablated, coagulated or photochemically modulated without damaging surrounding tissue.
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CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application 60/909,257, entitled, “Devices and Methods for Delivering Molecules to the Heart with Electric Fields”, filed Mar. 30, 2007, the contents of which are herein incorporated by reference. FIELD OF INVENTION This invention relates to drug delivery devices. More specifically, this invention relates electrically-mediated delivery of molecules to cells. BACKGROUND OF THE INVENTION Electroporation (“EP”) originated for in vitro transfection (Neumann et al., 1982) and over the past 25 years has become a standard laboratory method. The administration of electric fields at specific pulse conditions increases cell membrane permeability, which allows uptake of molecules through the cell membrane. The initial demonstration of in vivo electroporation was the delivery of chemotherapeutic agents to solid tumors (Okino et al. 1991). In the mid to late 1990's, the effectiveness of this approach for drug delivery was demonstrated in a variety of different tumors in animals and humans (Gotheif et al, 2003). This technique was then tested for enhanced plasmid DNA delivery (Holler et al., 1996; Nishi et al, 1996). In vivo electroporation is theoretically applicable to all tissues tested. A principal issue limiting the use of in vivo electroporation has been the accessibility of the particular tissue for the application of the electric field. The use of in vivo electroporation for plasmid DNA deliver has seen tremendous growth, including the initiation of the first clinical trials. Treatment of the tissue site by localized delivery of the therapeutic agent coupled with focused delivery of the electroporation signal facilitates selective application of the treatment to the target tissue sought to be treated. In this manner surrounding tissue is spared the adverse effects of treatment while the targeted tissue receives enhanced more optimal levels of the agent. Plasmid DNA-based gene transfer is attractive because it eliminates the need for a biological vector. Application of plasmid DNA-based gene transfer has been handicapped by the lack of efficient and/or effective delivery methods. When compared to viral delivery, the advantages of plasmid DNA-based gene transfer include reduced potential for immunogenicity, integration into the genome, and environmental spread. One method that has emerged as a means to facilitate delivery of plasmid DNA is in vivo electroporation or electropermeabilization. SUMMARY OF INVENTION The present invention provides devices and methods to deliver molecules to the cells that comprise any tissues. In certain embodiments the invention provides a catheter-based electrode and methods for its use for the delivery of molecules to cardiac tissue, blood vessels, other tissues/organs that can be accessed through a luminal tissue and luminal tissues. In additional embodiments the invention provides a non-catheter based electrode for performing the same functions. An injection and electroporation delivery device according to the invention can be fitted on the tip of a catheter to access and treat tissues that can be accessed using tissues that have a lumen. The heart provides an example of a tissue can be accessed using a catheter with this device on the tip through any number of blood vessels that lead to it. Similarly, kidney, lung, pancreas, liver, gall bladder, urinary bladder, prostate, and stomach can be accessed and treated using the device mounted on the tip of a catheter. The diameter of the device can be tailored to any size that is suitable for accessing the tissue of interest. In addition, the device can be used to treat the luminal pathway itself. One advantage of the system described herein is that it does not rely on balloon-based systems, as do many of the catheter based electrodes for treating vessels. Moreover, the device can be used in a non-expandable format. In a first aspect the present invention provides a catheter-based electroporation device. The device includes a catheter body, a guide disposed within the catheter, a retractable needle disposed within the lumen of the guide, and at least one electrode affixed to the distal tip of the catheter body. The guide has an elongate tubular body defining an inner lumen and serves to guide the needle. The needle has a distal tip with an aperture to allow the fluid to exit the tip of the needle. By exiting the tip through the aperture, the agent is delivered to the site of electroporation. Where there are a plurality of electrodes in the catheter-based electroporation device, each electrode can be independently addressable by a source of electricity. This provides an added element of control over the application of the electric field generated between the electrodes. Alternatively, the needle and each electrode of the at least one of electrode is independently addressable by a source of electricity. In certain embodiments of the electroporation device the electrode utilizes a plurality of segmented electrodes arrayed on the distal tip of the catheter body. The plurality of segmented electrodes are electrically insulated from adjacent electrodes, thus preventing interference. The plurality of segmented electrodes can be substantially equidistantly arrayed on the distal tip of the catheter body. By knowing and/or controlling the spacing, the electric field generated for a given applied voltage can be controlled. The electroporation device can employ needles composed of an electrically conductive material and can have a proximal end comprising a connector to couple the needle to a source of electricity. Further, each of the electrodes and the needle can be independently addressable by a source of electricity. The electroporation device can also employ a plurality of needles. Each of the plurality of needles can be adapted to deliver a different agent. Furthermore, each of the plurality of needles can be composed of an electrically conductive material and have proximal end comprising a connector to couple the needle to a source of electricity. Additionally, each of the at least electrodes and each of the needles can be independently addressable by a source of electricity. In a second aspect the present invention provides an electroporation device including a guide, a retractable needle disposed within the inner lumen of the guide, and at least one electrode affixed on or adjacent to the distal tip of the guide and spaced apart from needle by a predetermined space. The guide has an elongate tubular body defining an inner lumen. The needles are composed of an electrically conductive material and have a proximal end with a connector to couple the needle to a source of electricity. Each of the electrodes and the needle can be independently addressable by a source of source of electricity. In certain embodiments at least one electrode comprises a plurality of segmented electrodes substantially equidistantly arrayed on the distal tip of the guide. The needle can utilize a distal tip with an aperture to allow a fluid to exit the tip of the needle thereby delivering the agent to the site of electroporation. In further embodiments can include a catheter body where the electrodes are affixed to the tip of the catheter body and the guide is disposed with the catheter body. The device can also include a connector to connect the device to an instrument. The instrument can include a catheter, an endoscope, or a bronchoscope. Alternatively, the device can include a connector to connect the device to a handle or a probe adapted for surgical treatment. The needle can be a plurality of needles, rather than a single needle, with each needle independently addressable by a source of electricity. In a third aspect the present invention provides an electroporation device including a guide having an elongate tubular body defining an inner lumen and a plurality of segmented electrodes affixed on or adjacent to the distal tip of the guide. Each segment of the segmented electrodes can be spaced apart from adjacent electrodes by a predetermined space, with each of the electrodes independently addressable by a source of source of electricity. In certain embodiments the electroporation device has a retractable needle disposed within the inner lumen of the guide. The needle can be composed of an electrically conductive material and have a connector to couple the needle to a source of electricity. The needle can also have a distal tip with an aperture to allow a fluid to exit the tip of the needle. Rather than employing a single needle, there can be a plurality of needles, with each needle independently addressable by a source of electricity. In certain embodiments the electroporation device can include a catheter body. The electrodes can be affixed to the tip of the catheter body and the guide can be disposed within the catheter body. In further embodiments the electroporation device can include a connector to connect the device to an instrument. The instrument can be a catheter, an endoscope, or a bronchoscope. Alternatively, the device can include a connector to connect the device to a handle or probe adapted for surgical treatment. BRIEF DESCRIPTION OF THE DRAWINGS For a fuller understanding of the invention, reference should be made to the following detailed description, taken in connection with the accompanying drawings, in which: FIG. 1 is an illustration of the tip of a catheter according to an aspect of the present invention having a continuous metal end and retractable metal central needle for injecting molecules into tissues. The metal end has an independent path to a source of electricity and the needle has an independent connection to a source of electricity. FIG. 2 is an alternative illustration of the catheter tip of FIG. 1 , showing a cross-sectional view of the device. FIG. 3 is an illustration of the tip of a catheter according to another aspect of the present invention having a segmented metal end and a retractable metal central needle injecting molecules into tissues. The segments of the metal end each have an independent path to a source of electricity, and the needle also has an independent connection to a source of electricity. Alternatively, the needle may not have an independent path to a source of electricity and also may be made of a nonconductive material or insulated so that it does not influence electrical treatment. FIG. 4 is an alternative illustration of the catheter tip of FIG. 3 , showing a cross-sectional view of the device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The invention provides an injection and electroporation delivery device. In certain embodiments the device can be fitted on the tip of a catheter. The device facilitates the access and treatment of tissues that can be accessed via a lumen. In particular, the device allows a therapeutic and/or diagnostic agent or other molecule to be injected into a tissue having a cell or cells sought to be treated with the agent or molecule. The invention is described below in examples which are intended to further describe the invention without limitation to its scope. Example 1 FIG. 1 shows an exemplary embodiment of an electroporation device 10 according to the present invention. The electroporation device 10 is integral with a catheter 40 . The body of the catheter 40 can be multilayered, but should be coated with, or have peripheral layers composed of, a nonconductive material. The electroporation device 10 includes an electrode 50 that consists of a metal tip that covers the entire distal end of the catheter 40 . While described above as being metal, the electrode 50 can fabricated of any sufficiently conductive material. The metal tip electrode 50 has an independent pathway to an electrical power source. The exemplary device also includes a central metal needle 20 disposed within the lumen of the catheter 40 . As with the electrode 50 , the needle 20 is described as being metal, but can be fabricated of any conductive material. The needle 20 can be extended and retracted through a hole in the tip of the catheter 40 . The central needle 20 facilitates the injection of a molecule into a tissue and also serves as an electrode. The needle 20 has an independent pathway to an electrical power source (i.e. independent to the pathway of the electrode 50 ). The electroporation device 10 includes a guide 30 which aides in the disposition of the needle 20 including during the extension and retraction of the needle 20 . The guide 30 generally is tubular, providing an additional lumen within the lumen of the catheter 40 . Depending upon the application, the guide 30 may be conductive or nonconductive. As an alternative to having a conductive needle 20 attached to a source of electricity, the guide 30 could composed of a conductive material and connected independently to a source of electricity. With the catheter 40 in place within a lumen of the patient, the needle 20 is able to extend towards the tissue to be treated via the guide 30 . The needle 20 may be hollow or solid. Where the needle 20 is hollow, it may include an aperture at the distal end of the needle and be used to deliver the agent to the tissue. Alternatively, the agent may be delivered such as through the guide 30 . The distal end of the needle 20 may be sharp or blunt depending upon the particular application. The space 70 between the inner wall of the catheter 40 and the catheter and the outer wall of the guide 30 can comprise an insulating and/or nonconductive material. Alternatively, the space 70 may be empty or filled with air. FIG. 2 shows a cross-sectional view of the distal end of the electroporation device 10 . Electrical treatment is administered by passing electricity between the electrodes (needle 20 and metal tip electrode 50 ). The device 10 would be used by first inserting the device 10 integral with the catheter 40 into an organ that has a lumen such as a peripheral blood vessel, coronary arteries, or interior of the heart. The needle 20 would be extended so that it protrudes into a tissue, and a quantity of molecules would be injected into the tissue. The metal tip electrode 50 would be positioned so that it is near the injection site. Electrical treatment would be applied between the needle 20 and metal tip electrode 50 to deliver molecules to the interior of the cells that comprise the tissue by electroporation. Molecular delivery is just one application of the device. It can be used to manipulate molecules in any manner in or near the tissue. Example 2 Segmented Tip FIG. 3 shows an alternative embodiment of an electroporation device 10 . The embodiment shows the electroporation device 10 with a segmented tip electrode array 50 at the distal end of a catheter 40 . The metal tip electrode array 50 consists of any number of segments that each have an independent path to a source of electricity. The number of segments can range from 2 to infinity (for example, there could be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or more segmented electrodes in conjunction with the needle, which may also be independently coupled to a source of electricity). Each segment is electrically insulated 42 from adjacent segments. Each segment of the segmented tip electrode array 50 , along with the needle if the needle is attached to a source of electricity. As above, the array 50 is referred to a metal tip, but the segments of the electrode array 50 can be constructed of any electrically conductive material. Furthermore each segment of the electrode array 50 is independently addressable by the source of electricity, thus allowing a user to select which segment or segments (including the needle 20 where the needle is connected to a source of electricity) will participate in the generation of the electric field in a particular treatment. Furthermore, all segments may be simultaneously addressed depending upon the particular needs. One advantage of the independently addressable array of segments is that it gives a user better control over the applied fields, with benefit seen in subsequent expression of DNA or delivery of drugs. A central retractable needle 20 can be used to administer molecules into a target tissue as indicated above. The needle 20 , if connected to a source of electricity, can be constructed from any electrically conductive material. The central needle 20 has an independent path to an electricity source when used in electroporation. This particular embodiment can be utilized by applying an electrical potential, or current, between at least one segment of the electrode array 50 to the needle 20 . Alternatively, electricity can be applied between two or more segments of the electrode array 50 . In alternate embodiments, the central needle 50 is not used as an electrode, is not made of an electrically conductive material, is electrically insulated, or is retracted into the catheter so that it will not influence the electrical treatment occurring at the segments of the metal tip. In still further embodiments, the device includes a plurality of needles, disposed within the same guide or in separate guides, and may further be insulated from adjacent needles. Alternatively, microneedles may be employed for the delivery of the agent. Where there are a plurality of needles, each needle can be coupled independently to a source of electricity. The needles in the plurality not being used can be retracted to assure that they will not interfere with treatment. Separate needles in the plurality can then be used to deliver different agents to the tissue. The arrangement of electrodes and needles shown in FIGS. 1 through 4 can be used in further embodiments that are functionally identical with respect to the needle and electrodes. These embodiments include a device with the same relative orientation of electrodes and needles that is not attached to a catheter but are attached to a handle. These types of devices could be used for any tissue type, during open laparotomy thoracotomy, sternotomy, or during procedures using endoscopes. An additional embodiment is the general use of electric fields in cardiac muscle to deliver molecules to the cells that comprise the tissue, remove molecules from the cells that comprise cardiac tissue, or manipulate molecules in the extracellular space of cardiac tissue. The embodiments present above could be adapted for use in any type of minimally invasive technique that includes the use of catheters, endoscopes, bronchoscopes, as well as laparoscopic and thoracoscopic techniques. The embodiments presented above can be used to treat any disease in any tissue in humans or animals using minimally invasive methods, open laparotomy, thoracotomy, sternotomy, or when no surgical or other procedures are required to access the treatment site (for example, skin). Some examples of diseases that could be treated using the embodiments include, but are not limited to, re-stenosis in blood vessels including coronary vessels, cardiac ischemia, peripheral vascular disease, peripheral artery disease, lung cancer, colon cancer, prostate cancer, breast cancer, skin cancer, bladder cancer, liver cancer, brain cancer, and any cancer of the GI tract. Numerous ways of practicing the invention described in this application are possible. These include, but are not limited to, using the described devices to cause: (1) movement of molecules in the extra-cellular space; (2) movement of molecules from the extra-cellular space through the barrier surrounding a living cell, such as the cell membrane, and into the cell; (3) movement of molecules within the cell interior; (4) movement of molecules from the cell interior through the barrier surrounding a living cell and into the extracellular space; (5) a change in the properties of the barrier surrounding a living cell to make it more permeable to exogenous molecules; (6) movement of molecules into the barrier surrounding a living cell; (7) movement of molecules in a nonliving matrix; (8) movement of cells in a medium; (9) fusion of two or more cells; and (10) movement of molecules through a tissue such as but not limited to skin blood vessels, endothelial linings, cardiac muscle, smooth muscle, and skeletal muscle. For the purposes of this invention electrical treatment is defined as including the application of direct current or alternating current in any form such as, but not limited to, pulsed DC current or pulses AC current. In addition, different waveforms can be applied as pulsed DC or AC current such as but not limited to rectangular, square, triangular, sawtooth, exponentially increasing, or exponentially decreasing. It may be appreciated by one of skill in the art that biological cells exist in many forms and in many types. The devices and methods described in this document apply to all types of living cells including prokaryotes, eukaryotes, and plant cells. Therefore, the term cell is to be broadly interpreted. In addition, the term cell also includes artificial cells such as liposomes and micelles for the purposes of this document as the methods and devices described can be applied to these entities also. The term “cell” in the description above and in the claims also has additional meaning which encompasses a single cell, cells in culture, cell aggregates, and/or a cell that is part of a tissue. The term molecule has been used throughout this document and is to be defined as any type of molecular species. The devices and methods described herein are particularly applicable to therapeutic drugs, proteins, nucleic acid sequences, and plasmid DNA but can by applied for the delivery of any type of molecule and prove particularly useful for facilitating the entry of molecules into cells where the cell membrane poses a barrier to entry of the molecule under typical physiologic conditions. In addition, the devices and methods are applicable for simultaneously affecting more than one type of molecule. And furthermore, the manipulation of these molecules and cells can be for the purposes of the enhancement of therapeutic molecules for the treatment of disease or for the prevention (such as vaccine) of disease. The devices and methods described herein can be applied to any tissue type, either in vivo or in vitro. Applications will include both the treatment of humans and veterinary applications for the treatment of animals. In addition to the use of this for combating disease, the instant invention can be used for research purposes. The devices and methods described herein can be used for diagnostic and/or molecular identification purposes. For instance, a molecule comprising a marker or tag can be delivered to a targeted tissue and localization of the tagged molecule can be determined by any appropriate methodology. In the foregoing description, certain terms have been used for brevity, clarity and understanding, but no unnecessary limitations are to be implied there from beyond the requirements of the prior art, because such words are used for description purposes herein and are intended to be broadly construed. Moreover, the embodiments of the apparatus illustrated and described herein are by way of example, and the scope of the invention is not limited to the exact details of construction. The disclosure of all publications cited above are expressly incorporated herein by reference, each in its entirety, to the same extent as if each were incorporated by reference individually. It will be seen that the advantages set forth above, and those made apparent from the foregoing description, are efficiently attained and since certain changes may be made in the above construction without departing from the scope of the invention, it is intended that all matters contained in the foregoing description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween. Now that the invention has been described,
A device and related methodologies to deliver molecules to the cells that comprise any tissues. The invention includes a catheter-based electrode and methods for its use for the delivery of molecules to cardiac tissue, blood vessels, other tissues/organs that can be accessed through a luminal tissue, and luminal tissues. The invention is also a non-catheter based electrode for performing the same functions. In certain embodiments the electrode utilizes a segmented electrode array wherein each electrode is separately addressable by a source of electricity.
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CROSS REFERENCE TO RELATED APPLICATIONS [0001] Not applicable. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] Not applicable. INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISK [0003] Not applicable. BACKGROUND OF THE INVENTION [0004] 1. Field of the Invention [0005] The present invention generally relates to protective vehicle covers, more specifically, the present invention relates to a lightweight protective covering for motorcycles and motorcycle-like vehicle. [0006] 2. Background Art [0007] The deteriorating effects of direct sunlight and water are well known and much time, effort, and money has been spent protecting vehicles and other items from these effects. The detrimental effects commonly include fading, blistering, and cracking. The largest impact from these effects is often felt by the uppermost horizontal surfaces of vehicles. [0008] Vehicles such as motorcycles, bicycles, motor scooters, all terrain vehicles, personal watercraft, snowmobiles, and similarly designed vehicles are particularly susceptible to these effects since, by design, the vehicles are used in outdoor conditions and have no protective bodies or coverings inherently incorporated in their design. Due to their manner of use, such vehicles are typically exposed to atmospheric elements for extended periods of time. [0009] More specifically, vehicle owners such as motorcyclists often desire to protect their vehicles from damage that can be caused by exposure to rain and, particularly, by exposure to the sun. Commercially available covers are customarily made of material such as vinyl or canvas which is essentially non-stretchable in character. Such covers are normally relatively large and cumbersome, typically making them non-portable for a motorcyclist. [0010] Such covers are usually draped over the motorcycle and are relatively loose fitting, customarily being secured by ties or the like. In any event, such devices, being very loosely fit to the motorcycle, do not afford adequate protection from the elements. This situation is aggravated by virtue of the fact that motorcycles come in various sizes and configurations, while the conventional covers do not. [0011] In addition, motorcycle riders utilize their motorcycles for many purposes, including pleasure trips, running errands, and riding to and from work. It is therefore desirable that the seat and fuel tank be kept free of dust, dirt, and moisture which may accumulate when the motorcycle is parked, so as not to soil the rider's clothes. In hot climates, the black vinyl material of which motorcycle seats are typically composed may become very hot, causing considerable discomfort to the rider when first mounting the motorcycle. In the most extreme cases, the heat may even cause bums. Such heat further serves to seriously degrade the vinyl material. Many motorcycle riders also take pride in the overall appearance of their motorcycle, especially in the cleanliness and shininess of the fuel tank. The intense sunlight and high temperatures that characterize the motorcycle riding season, rapidly oxidizes the paint or lacquer finish of motorcycle fuel tanks, providing a degraded appearance. Some examples of motorcycle coverings and protectors that have been granted patents include the following: [0012] In U.S. Pat. No. 3,659,872, Warner discloses a foldable cover structure that completely covers a motorcycle. The cover has front and rear openings with fasteners and a top opening for the handlebars, with another covering portion that fastens over the top opening. [0013] In U.S. Pat. No. 3,884,523, Allen describes another protective cover for a motorcycle that stores within the seat of the cycle. The cover encloses the entire motorcycle, with no openings, and must be stuffed back into the seat for storage and riding of the motorcycle. [0014] In U.S. Pat. No. 4,171,145, Pearson, Sr. describes a retractable protective covering which may be unrolled from a spring loaded spool mounted in a housing attached to a motorcycle behind the motorcycle seat to cover the seat and the tank of the motorcycle. The covering has a long, rectangular top panel formed of heavy waterproof material, and two long, narrow upper side panels and two long, narrow lower side panels, with an upper and lower side panel on each side of the top panel. A pair of V-shaped bars, fastened to opposite sides of the housing, serves as guides in unfolding the upper and lower panels as the protective cover is extended. The covering is preferably fabricated from a nylon fabric. [0015] In U.S. Pat. No. 4,283,084, Gallagher discloses a protective cover for a motorcycle that is pentagonal in shape. The cover has an elastic curved edge that fits the rear seat portion, a pair of elastic bands for engaging the foot posts, and a set of Velcro strips for joining the cover about the cycle frame between the engine and the front wheel. The cover is described as fabricated from a lightweight, flexible material such as “ripstop” nylon, polyester fabric or other materials which resist the effects of weather. [0016] In U.S. Pat. No. 5,062,560, Wasden shows a flexible protective bicycle cover that fits over the seat, crossbar, handlebars and the front fork of a bicycle. The covering is a contour fitted covering of stretchable material that provides aerodynamic features with little or no protection of the bicycle it is covering. [0017] U.S. Pat. No. 5,562,139 by Cseri discloses a stretchable cover for providing a tight aerodynamic fit on the cycle to protect against the elements while the cycle is at rest or being transported. The cover is stretched over the front structure, the cycle frame and seat, attached to the front structure and seat and secured to the foot pegs to retain the cover on the cycle. Openings are provided in the cover for any side mirrors. The stretchable fabric material can be a nylon spandex fabric, known as Spandura®, which is commercially available. [0018] In U.S. Pat. No. 5,676,288, Spirk shows a portable protective cover for a bicycle adapted to be connected to the handlebars and seat of a bicycle. The protective cover is made of waterproof or water resistant materials to protect various bicycle components from the elements. The protective cover includes an elastic material design to secure the protective cover to the bicycle. The protective cover can include an integrated storage pouch to conveniently and compactly store the protective covering when not in use. [0019] In U.S. Pat. No. 5,795,009, Sack et al. describe a removable sun shade for motorcycles that includes a fabric sheet for extension over the upper part of the motorcycle, forming an air-circulating region between the motorcycle and the sheet. The sheet has a number of attachment members around its edge for securing the sheet to various parts of the motorcycle to hold the sheet in place. A storage pouch is attached to the sheet for reversible attachment to the motorcycle at various locations as most suitable for each model. The material of the fabric sheet is described as “weather resistant with breathability”. [0020] In U.S. Pat. No. 6,516,884, Henry discloses a sunscreen protector for motorcycles that covers the seat and fuel tank area to protect these components from the deteriorating effects of sunlight. The protector shade includes a rectangular sheet of tightly woven nylon/lycra elastomeric material sized to cover only the motorcycle seat and fuel tank. Four elastic strap members and a plurality of hook loop members with attached, coated J-hook members are employed for attachment to selected attachment points on the motorcycle. [0021] Thus, there is an unmet need for a protective vehicle cover that covers the seat and fuel tank regions of the vehicle and which can be employed for a large variety of vehicle designs and sizes. The cover also needs to be easily attached to and detached from the vehicle while being small enough for convenient storage. [0022] Additionally, many conventional protective covers envelope the entirety of the vehicle and are more suitable for long term storage. Everyday use of such covers requires more preparation by the user and subjects the vehicle to cross winds that may overturn the vehicle causing significant damage. Therefore, it is a purpose of this invention to provide a cover that protects the vehicle from detrimental environmental factors, while not subjecting the vehicle to destabilizing lateral forces. [0023] While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. It should be understood, however, that the intention is not necessarily to limit the invention to the particular embodiments described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention, as defined by the appended claims. BRIEF SUMMARY OF THE INVENTION [0024] It is an aspect of the present invention to provide a protective vehicle cover adapted to be releasably connected to both the handlebar region and a structure located rear of the seat of a vehicle to protect vehicle components from the elements when the vehicle is not in use. [0025] It is a further aspect of the present invention to provide a protective vehicle cover having minimal vertical surfaces thereby reducing wind resistance and lateral forces that may damage the vehicle. [0026] Yet another aspect of the present invention is to provide a protective vehicle cover with a cover sheet that lies generally in a horizontal plane and further allows air to circulate between the cover and the vehicle. [0027] A still further aspect of the present invention is to provide a protective vehicle cover that further includes an optional cover module that protects vehicle components located forward of the handle bar region of the vehicle. [0028] In accordance with one embodiment, there is provided a protective vehicle cover, comprising a flexible cover sheet for protecting a vehicle and its components disposed rearward of the handlebars, wherein the cover sheet is weather resistant, lies generally in a horizontal plane, and has minimal vertical surfaces providing for low wind resistance, two front mounting points having a releasable connection to forward structures of the vehicle, wherein the two front mounting points are fastened to a bottom surface of the cover sheet, and a rear mounting point for providing a releasable attachment to a rear structure of the vehicle. [0029] The scope of the present invention may further include a cover module for protecting vehicle components disposed forward of the handlebars wherein a rear edge of the cover module is releasably attachable to the front edge of the cover sheet and both the cover sheet and the cover module are independently functional when not releasably attached. [0030] Further, the present invention may incorporate an integrated storage pouch for retaining the vehicle cover when not in use. The integrated storage pouch may preferably be disposed at the midpoint along the rear edge of the cover sheet. [0031] The above and other aspects of the present invention will become more readily appreciated and understood from a consideration of the following detailed description of the preferred form of the present invention when taken together with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0032] FIG. 1 depicts a top view of a protective cover of the present invention. [0033] FIG. 2 depicts a bottom view of the protective cover depicted in FIG. 1 . [0034] FIG. 3 depicts a top view of the rear edge of the cover sheet of the present invention. [0035] FIG. 4 depicts a bottom view of the rear edge of the present invention. [0036] FIG. 5 depicts the protective cover of the present invention folded into a compact storage pouch. [0037] FIG. 6 depicts an attachment means between the cover sheet and the cover module of the present invention. [0038] FIG. 7 depicts a top view of protective cover of the present invention further including a motorcycle shown in phantom for illustrative purposes. [0039] FIG. 8 depicts a left side view of a protective cover of the present invention. [0040] FIG. 9 depicts a right side view of a protective cover of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0041] Referring now to the drawings, wherein the drawings are for the purpose of illustrating preferred embodiments of the invention only and not for the purpose of limiting the same, in FIGS. 1 , 2 and 7 - 9 , there is shown a protective vehicle cover 10 . [0042] The protective vehicle cover 10 is primarily intended to shield the upper portions of a vehicle from the detrimental effects of sun, heat, precipitation, and other elements. Accordingly, the vehicle cover 10 is preferably composed of a lightweight weather resistant material that may be resistant to sun, ultraviolet rays, various forms of precipitation, and/or any other known causes of weathering. The vehicle cover 10 material may further possess characteristics of breathability to permit air circulation there through. Suitable materials may include, but are not limited to, nylon, ripstop nylon, vinyl materials, polyester fabrics and other materials known within the art. In use, the vehicle sheet 10 may protect the handlebars, hand grips (HG), hand brakes, headlight (H), instrument panel (IP), fuel tank (FT), seat (S), and other central components of the vehicle. A taut fit ensures both maximal stability and protection for the vehicle. When the cover sheet 20 is extended over the vehicle and attached as described, a space will be formed between the cover sheet 20 and the upper portion of the vehicle permitting air to circulate beneath the cover sheet 20 . Further, it is important that the vehicle cover 10 material be thin and pliable so that it can be readily folded into a package corresponding in size to one's hand (as shown in FIG. 5 ). [0043] A top view and a bottom view of one embodiment of the vehicle cover are depicted in FIGS. 1 and 2 , respectively. Protective vehicle cover 10 may comprise a flexible cover sheet 20 and an optional cover module 50 that are each composed of a lightweight flexible material, as described above. Cover sheet 20 further comprises a top surface 21 and a bottom surface 22 having a reinforced peripheral edge 23 folded upon the bottom surface 22 and fixed thereto by a fixation means 24 thereby forming a finished peripheral edge (best shown in FIG. 2 ). Preferably, the fixation means 24 is embodied by stitches 24 that allow for sufficient stretching and will not break when used for their intended purpose. The stitches 24 may comprise nylon thread or any other suitable materials known within the art. Additionally, the method of stitching may include box-stitching, zig-zag stitching, or any forms of stitching known within the art that preferably adds strength and/or durability to a stitched connection. While stitching is the preferred method of reinforcing the peripheral edge 23 of the cover sheet 20 , any conventional material edge reinforcing methods (e.g. adhesives, heat seal, etc.) may be employed. [0044] The preferred overall shape of the cover sheet 20 is best described as an irregular hexagonal shape, as shown in FIGS. 1 , 2 and 7 . Cover sheet 20 may comprise a front edge 25 that is parallel but unequal in length to a rear edge 26 , a first parallel lateral edge 27 equal in length to a second parallel lateral edge 28 , and a first non-parallel lateral edge 29 equal in length to a second non-parallel lateral edge 30 . Both the first parallel lateral edge 27 and second parallel lateral edge 28 may be disposed perpendicular to both the front edge 25 and the rear edge 26 of the cover sheet 20 . [0045] The primary mounting points for attaching the cover sheet 20 to a vehicle form a three point mounting system. The mounting points may be constructed of materials including, but not limited to, a flexible nylon band, a web strap, a pocket, an elastic cord, line or strap, and any other similar materials which may further incorporate beneficial features such as snap-fastening means, hook and loop fasteners, buttons, various types of clips, clasps, belt means, buckles, and the like. Preferably, the primary mounting points are comprised of a cut-resistant material. [0046] The three point mounting system preferably comprises two front mounting points 31 and one rear mounting point 32 . The two front mounting points 31 are preferably disposed at or near the forward corners 33 of the cover sheet 20 and preferably attach to the hand grips (HG) of the vehicle. Alternatively, the two front mounting points 31 may attach to any other convenient forward components of the vehicle such as, but not limited to, the handlebars, hand levers, instrument panel (IP), mirrors (M), and mirror stem (MS). The two front mounting points 31 are preferably disposed on the bottom surface 22 of the cover sheet 20 via a stitched connection, an adhesive connection, a heat seal connection, or any conventional connection means known within the art. The configuration of the two front mounting points 31 may include, but is not limited to, loop-shaped fasteners, pockets, elastic retention straps, and the like. A pocket mounting point may be formed by sewing extra pieces of stretchable material onto the bottom surface 22 of the cover sheet 20 . Such pockets may serve to enclose the handle bars and hand levers of the vehicle. Preferably, the two front mounting points 31 are of a generally looped-shaped configuration so as not to necessitate the tying of each individual front mounting point 31 to a forward component of the vehicle, such as the hand grips HG. [0047] The rear mounting point 32 may be disposed between the rear corners 34 along the rear edge 26 of the cover sheet 20 , and may be attached to the top surface 21 , bottom surface 22 , or the peripheral edge 23 of the cover sheet 20 . The rear mounting point 32 provides the third primary point of contact with a rear structure of the vehicle such as, but not limited to, the frame, fender (F), seat (S), tire (T), tail light assembly (TA), turn signal fixtures, and the like. The rear mounting point 32 may comprise a loop-shaped configuration for attachment around an appropriate rear structure of a vehicle, such as those enumerated above. This configuration may be formed in a wide variety of embodiments including, but not limited to, a strap fixedly attached at both its ends to the rear edge 26 , a strap fixedly attached to the rear edge 26 at one of its ends and communicably connectable 35 to the rear edge 26 at its opposite end, and two respective straps each having one end fixedly attached to the rear edge 26 and each strap having a free end communicably connectable 35 to the free end of the other strap. Such communicable connections 35 are fully releasable and may include, but are not limited to, hook and loop fasteners, snap-fastening means, buttons, various types of clips, clasps, latches, belt means, buckles, hooks, hooks and D-rings, tie off strap ends, and the like. [0048] Additional secondary attachment members 36 may be used to supplement the three point mounting system. As depicted in FIGS. 1 , 2 , and 7 - 9 , secondary attachment members 36 may be fixedly secured to the cover sheet 20 along its lateral edges 27 - 30 . Preferably, the secondary attachment members 36 may be disposed at the lateral corners 37 which are located at the intersections of a parallel lateral edge 27 , 28 and the respective non-parallel lateral edge 29 , 30 . Secondary attachment members 36 may also be disposed along the front edge 25 , front corners 33 , rear edge 26 , and rear corners 34 of the cover sheet 20 if a more secured attachment to the vehicle is desired. Configurations of the secondary attachment members 36 may include, but are not limited to, loops, straps, lines or elastic cords which may further utilize hook and loop fasteners, snap-fastening means, buttons, various types of clips, clasps, latches, belt means, buckles, hooks, hooks and D-rings, and the like to provide attachment to structures of the vehicle. [0049] Referring to FIGS. 1-5 , the vehicle cover 10 may further comprise an integrated storage pouch 40 . The storage pouch 40 may be integrated along any available surface or peripheral edge 23 of the cover sheet 20 . Preferably, the attachment point for the storage pouch 40 is at the midpoint of the rear edge 26 of the cover sheet 20 . The pouch 40 may be configured in any general shape, with preferred embodiments having a rectangular or square shape. The pouch 40 may be formed by overlaying two layers of material and fixedly fastening the two layers to each other around their respective peripheries, leaving one edge unfastened forming the mouth of the pouch 40 . A portion of the mouth of the pouch 40 may be integral with or attached to cover sheet 20 , preferably along a peripheral edge 23 , so that the cover sheet 20 will remain attached to the pouch 40 in both the stored and deployed positions. As shown in FIG. 3 , each adjacent material layer at the mouth of the pouch 40 further comprises a complimentary closure means 42 a, 42 b for releasably closing the mouth of the pouch 40 when the vehicle cover 10 is deployed. During cover 10 deployment, the pouch 40 is empty and may be temporarily used to store incidental items. [0050] As depicted in FIGS. 3-5 , when storage of the vehicle cover 10 is desired the cover 10 may be compacted, rolled, or folded into a size and shape insertable within the pouch 40 via folding cover 10 over integral closure means 42 a . With cover 10 folded over closure means 42 a and into the pouch 40 , the mouth of the storage pouch 40 may be releasably fastened, as depicted in FIG. 5 , by complimentary closure means 42 b , 42 c . Complimentary closure means 42 a , 42 b , 42 c may include a wide variety of closure structures including, but not limited to, hook and loop fasteners, zippers, snaps, buttons, clasps, clips, or any other means known within the art. The storage pouch 40 is preferably composed of the same materials described in detail above regarding cover sheet 20 . Utilizing water resistant pouch material prevents liquid and other matter from penetrating the pouch 40 and moistening or soiling the flexible cover sheet 20 stored therein. As shown in FIG. 5 , protective cover sheet 20 is collapsible in a convenient and easily transportable pouch 40 when not in use. In this manner, the protective vehicle cover 10 can easily be stored in a bag, a user's pocket, or conveniently carried by the user when the cover 10 is not in use. [0051] As depicted in FIGS. 1 , 2 , and 6 - 9 , the present invention may further comprise a cover module 50 for protecting vehicle components disposed forward of the handlebars. Such a cover module 50 may overlay the instrument panel (IP), headlight (H) and other forward vehicle components, depending on the design and styling of the vehicle. Preferably, the cover module 50 may be of a substantially rectangular configuration having a front edge 51 , a rear edge 52 , and two side edges 53 , 54 . Depending on the contours of the vehicle, the cover module 50 may be relatively flat, dome-shaped, or similarly adapted to fit the specific contours of the vehicle forward of the handlebars. A cover module 50 constructed of stretchable material may fully conform to a wide variety of vehicle components and contours. Cover module 50 may be comprised of the same materials as described for the cover sheet 20 above including, but not limited to, nylon, ripstop nylon, vinyl materials, polyester fabrics and other materials known within the art. Similarly, cover module 50 may further incorporate the same manner of a reinforced peripheral edge (i.e. stitching, etc.) as described above. [0052] As depicted in FIGS. 6 and 7 , the rear edge 52 of the cover module 50 may be releasably attached 55 to the front edge 25 of the cover sheet 20 . Releasable attachment 55 comprises complimentary structures disposed on the aforementioned rear edge 52 and front edge 25 which may include a wide variety of structures including, but not limited to, hook and loop fasteners, zippers, snap-fastening means, buttons, various types of clips, clasps, latches, belt means, buckles, hooks, hooks and D-rings, and the like. Alternatively, attachment 55 may be of a fixed nature such as, but not limited to, using stitching, adhesive, or the like. Depending on the design of the vehicle, mirror stems (MS) or other protruding vehicle structures may project through the point of releasable attachment 55 . When a cover module 50 is to be used in conjunction with a cover sheet 20 , the dimensions of the integrated storage pouch 40 may be increased accordingly to accommodate the storage of both the cover module 50 and the cover sheet 20 within the pouch 40 (see FIG. 5 ). Alternatively, an integrated pouch 40 may be disposed on any available surface of cover module 50 in instances including, but not limited to, desired independent use and/or storage of cover sheet 20 and cover module 50 . [0053] In use, as depicted in FIGS. 7-9 , the protective vehicle cover 10 may be installed on a vehicle by slipping the two front mounting points 31 attached to the bottom surface 22 of cover sheet 20 over the hand grips of the vehicle. Alternatively, two front mounting points 31 can be attached to the handle bars or any other convenient forward vehicle structures. The cover sheet 20 may then be pulled or stretched rearward along the central axis of the vehicle (e.g. over the fuel tank (FT) and seat (S) of a motorcycle). Next the rear mounting point 32 may be attached about the rear taillight assembly (TA). Alternatively, the rear mounting point 32 may be attached to the vehicle by passing around, under, or through any other convenient rear structure of the vehicle including, but not limited to, the fender (F), the tire (T), the rear border of the seat (S), the frame, and the like. As described above, the rear mounting point 32 may be either a static structure or an adjustable element that allows further tightening of the rear mounting point 32 to the vehicle. Rear mounting point 32 may include a variety of embodiments, with a preferred embodiment being a strap and complimentary buckle configuration as depicted in FIGS. 7-9 . [0054] Optional secondary attachment members 36 may be employed and preferably do not distort cover sheet 20 causing significant vertical surfaces. Secondary attachment members 36 may attach to available vehicle structures including, but not limited to, the frame, seat (S), fuel tank (FT), foot pegs, cleat, or any other convenient point of attachment. Such attachment members 36 may include, but are not limited to, loops, straps, lines or elastic cords which may further utilize hook and loop fasteners, snap-fastening means, buttons, various types of clips, clasps, latches, belt means, buckles, hooks, hooks and D-rings, and the like to provide attachment to structures of the vehicle. [0055] The protective vehicle cover 10 is shown in the functional state in FIGS. 7-9 . As disclosed above, an optional cover module 50 may be utilized either in conjunction with cover sheet 20 or independent of cover sheet 20 as desired. Cover module 50 may be constructed in a variety of shapes to accommodate the wide variety of vehicle designs in the marketplace. Cover module 50 may comprise stretchable material, wherein the module 50 may thereafter stretch and conform to an unlimited number of vehicle designs. When used in conjunction with a cover sheet 20 , the rear edge 52 of the cover module 50 and the front edge 25 of the cover sheet 20 may each incorporate respective complimentary releasable attachments 55 . In this manner, the abutting edges 25 , 52 of the cover sheet 20 and module 50 , respectively, may be joined. Releasable attachments 55 may allow for the passage of vehicle structures including, but not limited to, mirrors (M) and mirror stems (MS), windshield sections, and the like (see FIGS. 8 and 9 ). Further, the cover module 50 may utilize attachment members 56 about the edges of the module 50 to provide additional points of attachment to the vehicle. Attachment members 56 may be disposed on any edge of the cover module 50 , with attachment members 56 preferably being disposed along the front edge 51 as depicted in FIGS. 7-9 . Attachment members 56 may include, but are not limited to, loops, straps, lines or elastic cords which may further utilize hook and loop fasteners, snap-fastening means, buttons, various types of clips, clasps, latches, belt means, buckles, hooks, hooks and D-rings, and the like to provide attachment to structures of the vehicle. If the cover module 50 is to be used independent of the cover sheet 20 , the rear edge 52 of the cover module 50 may incorporate attachment members 56 instead of a releasable attachment 55 . Alternatively, both releasable attachment 55 and attachment members 56 may be simultaneously disposed upon the rear edge 52 of the cover module 50 to allow for cover module 50 use both in conjunction with and independent of the cover sheet 20 . [0056] The protective vehicle cover 10 is quickly and easily installed or removed from a vehicle using the described three point attachment system. It is important to appreciate that the vehicle cover 10 is not permanently attached to the vehicle and that the cover 10 can be entirely removed and carried away from the vehicle itself. The protective cover 10 readily folds into a small size for easy storage and transport. Removal of the cover 10 from a vehicle is preferably accomplished via the release of the rear mounting point 32 followed by the release of the front mounting points 31 , respectively. With the cover 10 disengaged from the vehicle, closure means 42 a , 42 b may be spread apart to reveal the interior of the integrated pouch 40 . The user may then fold, compact or otherwise insert the cover sheet 20 and/or the cover module 50 into the integrated pouch 40 . As depicted in FIG. 5 , closure means 42 b , 42 c may then be placed in communication to fully enclose cover 10 within the integrated pouch 40 . [0057] For deployment of the cover 10 , closure means 42 b , 42 c are disengaged and the integrated storage pouch 40 is opened to allow the user access to the cover sheet 20 and/or cover module 50 therein. Once the storage pouch 40 has been opened, the protective vehicle cover 10 may be unfolded and positioned on the vehicle, as described above and depicted in FIGS. 7-9 . [0058] It will be appreciated that no attempt has been made to cover the entire vehicle. Rather, the parts which are most desirably sheltered from the elements, namely the seat (S) and fuel tank (FT) areas are protected. In this manner, a cover 10 having less material can be constructed. Additionally, the cover 10 of the invention is provided with the above-described attachment means which may be simple to use, rust proof and adapted to be securely engaged to the vehicle in such a manner that the cover 10 cannot be readily blown from the vehicle. In this manner, less bulk is required while covering the critical features of a vehicle. Also, one can readily foresee the advantage of having a cover 10 that can be compacted or folded into a size and shape roughly equivalent to the palm of one's hand. It is within the scope of the present invention to further provide an integrated storage pouch 40 for the folded cover 10 such that the entire package may be placed in one's pocket. While FIGS. 7-9 depict a cover sheet 20 in use with a cover module 50 , each of these separable components may be independently deployed without requiring the use of the complimenting component. In such a manner, vehicle structures disposed forward of the handlebars and vehicle structures disposed rearward of the handlebars may be independently or conjunctively protected. [0059] It is important to appreciate, however, that the present invention is not permanently attached to the vehicle and can be entirely removed and carried away from the vehicle itself. The present disclosure will afford significant protection for a wide variety of vehicle, as well as accomplish the other aspects of the invention set forth above. [0060] While the above description contains much specificity, this should not be construed as limitations on the scope of any embodiment, but as exemplifications of the presently preferred embodiments thereof. Many other ramifications and variations are possible within the teachings of the various embodiments. [0061] Thus the scope of the invention should be determined by the appended claims and their legal equivalents, and not by the examples given.
A removable protective vehicle cover for motorcycles and similarly designed vehicles for protecting the upper surface of the vehicle from the elements. A cover sheet component protects vehicle structures disposed rearward of the handlebars and incorporates two front mounting elements for releasably receiving forward structures of the vehicle. The cover sheet is deployed in a generally horizontal plane and provides minimal wind resistance to any such lateral forces. An optional cover module protects vehicle components disposed forward of the handlebars and may be releasably attached to the front edge of the cover sheet. A storage pouch may be integrally incorporated with the vehicle cover to allow for compact storage and portability of the vehicle cover when not in use.
1
FIELD OF THE INVENTION [0001] The present invention relates to medical syringes. More particularly it relates to a retractable syringe, and to a disposable needle unit for attachment to a syringe unit to form a syringe assembly. BACKGROUND OF THE INVENTION [0002] Syringe assemblies having a needle (“cannula”) are commonly used for the delivery of fluids, e.g. medicaments, into patients, and/or for aspirating fluids from the patients. Desirably, these syringe assemblies can be operated by a single hand, so that a doctor or nurse is able to operate them while using his or her other hand for another purpose. The force required should not be very great, or the doctor or nurse's hand will become tired if many injections are performed. Furthermore, it is often undesirable for the same needle of the syringe assembly to be used for multiple patients, and several forms of syringe assemblies are known which prevent or discourage this. [0003] A first form of syringe assembly comprises a disposable needle assembly consisting of a needle and a connector element. Using the connector element, the needle assembly is temporarily attached to a forward end of an elongate syringe unit, to form the syringe assembly. The syringe unit has a barrel, and a plunger movable forward within the barrel towards the needle assembly. A medicament fluid is located in a volume between a front face of the plunger and the needle assembly. The volume communicates with the inside of the needle, so that as the barrel is advanced the fluid is driven through the needle. When this happens, it is undesirable to have fluid leaking through the junction where the circumference of the front face of the plunger meets the walls of the barrel. In order to be compliant with the ISO 7886-1 standard, the syringe unit has to withstand a compression force resulting in an internal test pressure of 300 kPa (3 bars) without leaking. When the medicament has been dispensed, the needle assembly is removed and disposed of. [0004] Examples of such syringe assemblies are the Luer Taper and Luer Lock designs standardized under ISO 594. The Luer Taper variant uses a press fit connection between the needle assembly and syringe unit that works using friction. Unfortunately, the needle assemblies are prone to loosening and dropping off the syringe unit. The Luer Lock variant seeks to resolve the problem of loosening associated with the Luer Taper by using a thread locking system. The Luer Lock however has a complicated design involving multiply nested interlocking portions. Specifically, the syringe unit has a conical spout encircled by an internally threaded collar. The connection element of the needle assembly carries an external thread for engaging the collar, and defines a cavity for receiving the spout. The connection element is inserted into the gap between the spout and the collar. [0005] Both these syringe assemblies contain a large amount of dead space—i.e. volumes in the syringe assembly which contain medicament which cannot be expelled from the syringe assembly. There is typically dead space within the connector unit and/or the interface between the connector unit and syringe unit. This dead space is an issue of concern as the cost of medicament may be high. It is possible to reduce the size of the dead space by reducing the tolerances in the production process, but this increases the production cost of the syringe assembly. [0006] Another known form of syringe assembly is a “retractable syringe”, which comprises a syringe unit, a needle unit (which in some forms of the retractable syringe is just a needle, but in others is a needle and a “needle hub”, i.e. an encircling body of material, typically molded plastics material) located at one end of the syringe unit, a retention mechanism for maintaining the position of the needle unit with respect to the syringe unit, and a drive mechanism. Operation of syringe causes the retention mechanism to be disabled after the syringe assembly has been used to deliver a medicament, and the drive mechanism then drives the needle unit into the syringe unit, so that the needle is no longer exposed. Retractable syringes are illustrated in U.S. Pat. No. 6,994,690, WO 2005/053779, U.S. Pat. No. 6,494,863, US 2008/0033355 and U.S. Pat. No. 7,351,224. Another retractable syringe is the BD Integra Syringe marketed by Becton, Dickinson and Company of New Jersey, United States. This retractable syringe has a detachable needle, and uses a form of connection between the syringe unit and the needle reminiscent of the Luer Lock system. Experiments have found that it may take an “activation” force of about 55N in order to break the retention mechanism of a 1 ml version of the Integra syringe. This force is estimated to be over 5 times the compression force which the syringe unit has to withstand without leaking in order to achieve the ISO 7886-1 standard. [0007] Some of the earlier retractable syringes have thus reduced the amount of “activation” force required by having more dead space within the syringe and/or by staggering the activation process. In cases where staggering is used, dead space may be required to provide room for the cascaded movement of the individual elements involved in the activation process. Therefore, most designs of retractable syringe have dead spaces, resulting in wastage of the medicament. In some designs air may be trapped in the dead space, and is hard to expel this air before the syringe assembly is used. [0008] Furthermore, since the retention mechanism has to be strong enough to resist the urging force generated by the drive mechanism, the user has to apply an inconveniently large force to break the retention mechanism, and release the needle unit. [0009] Furthermore, the needle unit, syringe unit, retention mechanism and drive mechanisms of many known retractable syringes have too many parts, leading to high production cost. Since retractable syringes are expensive, some operatives are tempted to try to re-use them, and there is little to prevent this since almost all components remain intact following operation of the device. SUMMARY OF THE INVENTION [0010] A first aspect of the present invention aims to provide new and useful retractable syringe assemblies. [0011] A second aspect of the invention aims to provide a new and useful disposable needle assembly for connection to a syringe unit to form a syringe assembly. [0012] The first aspect of the invention proposes in general terms that in a retractable syringe of the kind including a needle unit, a barrel, a plunger movable within the barrel towards the needle unit, a drive mechanism for driving the needle unit into the barrel, and a retention mechanism for retaining the needle unit with respect to the barrel, the plunger has a cutting crown at its forward end, for cutting the retention mechanism as the plunger is advanced, so that the drive mechanism retracts the needle unit into the barrel. The profile of the cutting crown includes one or more cutting teeth which cut a first portion of the retention mechanism before other portions of the cutting crown cut other portions of the retention mechanism. In other words, a user does not have to apply sufficient force to the plunger simultaneously to break all portions of the retention mechanism. This reduces the required activating force. [0013] A piston may ride on the front of the plunger, such that a volume for holding a medicament is defined between the piston and the needle unit. This piston too may be cut by the cutting crown. [0014] The needle unit may consist of the needle alone, but in the preferred embodiments of the invention includes both a needle and an encircling body of material (e.g. plastics material) which functions as a needle holder. The needle holder may be formed by molding. [0015] The second aspect of the invention proposes a disposable needle assembly for attachment to a syringe unit having a plunger movable within a barrel, to form a syringe assembly. The disposable needle assembly has a needle and connector element for connecting the needle to the syringe unit. The connector element encircles the needle and has a thread on its outer surface for mating with the syringe unit. The needle assembly has a central bore of substantially constant bore extending along the whole length of the needle assembly. Thus, there is very little dead space within the needle assembly itself. [0016] Furthermore, when the needle assembly mates with the syringe unit, the central bore of the needle assembly meets a passage of the syringe unit having substantially the same bore and communicating with the barrel of the syringe unit. This substantially reduces dead space at the interface between the syringe unit and the needle assembly. [0017] Before attachment to the syringe, the needle of the needle assembly is preferably encased in a protector formed (e.g. by molding) as a one-piece unit together with the hub. The protector may be connected to the hub by a frangible portion. [0018] The two aspects of the invention are independent, but they are combinable by forming a syringe unit which mates with the needle assembly of the second aspect of the invention using an element which defines the passage, and such that when the needle assembly and element are connected together, they together play the role of the “needle unit” in the first aspect of the invention. [0019] Certain embodiments of the present invention may have the advantages of: having a design that may be simple and effective but yet resulting in almost no dead space within the assembly; having a simple design that may allow for simple tooling and production economy; having a compact design that may allows for an efficient material usage, thus resulting in a product that may be environmentally sound; having a design with a minimal part count as components may be fabricated as integrated parts, e.g. the needle protector and the needle hub may be made as a single piece; having minimized medication wastage as there is almost no dead space; allowing for the easy elimination of hazardous air bubbles as there is almost no dead space; preventing the trapping of air bubbles; allowing for easy inventory management as the needle assembly may be used with both retractable and conventional syringes; assuring the integrity of a virgin needle as the integrity is easily verified; and allowing for a tamper proof design that may prevent reuse or recycling. BRIEF DESCRIPTION OF THE FIGURES [0030] The present invention will now be described, by way of example only, with reference to the accompanying drawings, in which: [0031] FIG. 1 is an exploded view of a syringe according to a first embodiment of the present invention; [0032] FIG. 2A is a cross-sectional view of the syringe of FIG. 1 when assembled; [0033] FIG. 2B is a cross-sectional view of a piston of the syringe of FIG. 2A when the piston is proximate a retention mechanism; [0034] FIG. 2C is a cross-sectional view of the piston as in FIG. 2B when a cutting crown of the syringe is brought to bear against a weak portion of the retention mechanism; [0035] FIG. 2D is a cross-sectional view of the piston as in FIG. 2B after the cutting crown cuts the piston and the retention mechanism; [0036] FIG. 3A is a cross-sectional view of the cutting crown of FIG. 2B ; [0037] FIG. 3B is a side view of the cutting crown as in FIG. 3A ; [0038] FIG. 3C is a perspective view of the cutting crown of FIG. 2B ; [0039] FIG. 3D is a cross-sectional view of a retraction assembly of the syringe of FIG. 1 ; [0040] FIG. 3E is a cross-sectional view of the piston of FIG. 2B ; [0041] FIG. 3F is a cross-sectional view of a part of the retraction assembly of FIG. 3D when it is fitted into a front portion of a barrel; [0042] FIG. 4 is a cross-sectional view of an assembled syringe according to a second embodiment of the present invention; [0043] FIG. 5A is a drawing of a needle assembly according to a third embodiment of the present invention; [0044] FIG. 5B is a cross-sectional view of the needle assembly of FIG. 5A installed onto a syringe unit; [0045] FIG. 5C is a cross-sectional view of the needle assembly of FIG. 5B but with a needle protector removed; [0046] FIG. 6 is a cross-sectional view of fourth embodiment of the invention including a portion of the needle assembly of FIG. 5A ; [0047] FIG. 7 is a schematic drawing showing two teeth of the cutting crown of FIG. 2B with different cutting distances; [0048] FIG. 8A is a schematic side view of the cutting crown of FIG. 2B with five cutting teeth; [0049] FIG. 8B is a schematic side view of the cutting crown as shown in FIG. 8A but with two cutting teeth; [0050] FIG. 9A is a perspective view of a variation of a plunger of the syringe of FIG. 1 ; and [0051] FIG. 9B is a perspective view of a variation of a barrel of the syringe of FIG. 1 . DETAILED DESCRIPTION OF THE EMBODIMENTS A Retractable Syringe [0052] FIG. 1 is an exploded view of a syringe 100 according to a first embodiment of the present invention. FIG. 2A is a cross-sectional view of the syringe of FIG. 1 when assembled. The parts of the syringe 100 are described next with reference to FIGS. 1 and 2A . [0053] The syringe 100 comprises a hollow barrel 140 defining a chamber, a plunger 120 insertable within the chamber, a piston 130 which is inserted into the chamber before the plunger 120 , and a retraction assembly 150 to be fitted at a front portion 1420 of the barrel 140 . The barrel 140 functions as a housing providing support to the other parts of the syringe 100 , e.g. the retraction assembly 150 . In different versions of the embodiment, the size of the barrel 140 differs, so as to have varying fluid capacities. In these various versions of the embodiment, the barrel 140 has differing diameters, and the diameters of the piston 130 , plunger 120 and/or retraction assembly 150 also differ to suit the diameter of the barrel 140 . A spring 1600 surrounds the needle holder 1560 . The retraction assembly 150 includes a needle 1520 and a needle holder 1560 which encircles the needle 1520 . The needle holder 1560 is integral with a needle hub 1510 and with a seal 1540 . The junction between needle hub 1510 and the seal 1540 is an annular weak portion 1590 (shown in FIG. 3D ). As described below, the needle 1520 , needle holder 1560 and needle hub 1510 together function as a needle unit which is eventually driven into the barrel 140 , and the seal 1540 and annular weak portion 1590 function as a retention mechanism for retaining the needle unit relative to the syringe unit until the retention mechanism is disabled. Once this happens, the spring 1600 functions as a drive mechanism to drive the needle unit into the plunger 120 . [0054] The barrel 140 comprises a hollow cylinder portion 1410 , a mouth 1440 and the front portion 1420 . The front portion 1420 may be tapered. The cylinder portion 1410 forms the main body of the syringe, thus permitting a user to hold the syringe steady in place when performing an injection. Optionally, the barrel 140 comprises one or more flanges 1430 for the purpose of providing additional holding surfaces. These flanges 1430 may be as shown in FIG. 1 , situated at the mouth 1440 of the barrel away from the front portion 1420 . Alternatively, the flanges 1430 may be situated anywhere along the external surface of the cylinder portion 1410 or even the front portion 1420 . FIG. 9B is a perspective view of a variation of the barrel 140 where the flanges 1430 are disposed a suitable distance away from the mouth 1440 . The distance is chosen to allow for a separation between the flanges 1430 and the exposed end of the plunger 120 which may allow a user to have a better grip of the syringe. Further, the skilled person will also understand that the flanges 1430 may take on other forms apart from that shown in FIG. 1 , 2 A or 9 B, for example taking the form of finger loops or an annular lip. [0055] The plunger 120 comprises a stem 1290 with an end cap 1100 fitted over a top end of the plunger 120 , and a cutting crown 1200 at the bottom end of the plunger 120 . The stem 1290 is tubular. As described below, the tubular stem permits the retraction of the needle 1520 into stem 1290 and thus into the main body of the syringe 100 . The purpose of the end cap 1100 is to improve a user's grip when the user is performing the push and pull pumping action associated with performing an injection. Further, the end cap 1100 may prevent the needle holder 1560 and/or needle 1520 from dropping out of the plunger 120 after the needle 1520 is driven into the plunger. The end cap 1100 may also be suitable for a user to depress the plunger 120 within the barrel 140 with a thumb. Such an end cap 1100 may be made as a separate piece to be fitted onto the top end of the stem 1290 in which case the plunger 120 contains a retention means for holding the end cap 1100 in place. Optionally, as shown in FIG. 9A , the end cap 1100 may be made integrated with the stem 1290 . FIG. 9A is a perspective view of a variation of the plunger 120 where the end cap 1100 and the stem 1290 is formed together as a singular item. By integrating the end cap 1100 together with the stem 1290 , the part count may be lowered, thus allowing for a more efficient use of production material and an optimization of production cost. [0056] Similarly, the cutting crown 1200 may be made either integrated as part of the plunger 120 , or it may be made as a separate piece to be fitted at the bottom end of the plunger 120 . The cutting crown 1200 will be described to a greater detail below. [0057] The piston 130 is disposed over the cutting crown 1200 . The piston 130 comprises a cylindrical portion 1340 which has an outer diameter slightly less than that of the inner diameter of the cylinder portion 1410 of the barrel 140 , and further comprises one or more annular sealing lips 1310 running around the outer surface of the cylindrical portion 1340 . The cylindrical portion 1340 forms a wall around the cutting crown 1200 when the piston 130 is disposed over the cutting crown 1200 . The cylindrical portion 1340 provides support for the piston 130 , thus allowing the piston 130 to withstand the compression forces exerted on the piston 130 when the plunger 120 is depressed. The sealing lips 1310 allow the piston 130 to have a tight fit within the body of the barrel 140 and may thus permit the proper expelling or aspiration of fluids out of or into the barrel 140 . Further, the piston 130 may also be made out of a resilient material so achieve a tighter fit between the piston 130 and the barrel 140 . The tight fit may help to ensure the proper expelling or withdrawing of liquid or gas by the syringe 100 . [0058] The piston 130 will now be further described with the aid of FIG. 3E . FIG. 3E is a cross-sectional view of the piston 130 . The piston 130 comprises a central domed elevated portion 1385 , a weak portion 1380 forming a circumferential perimeter about the elevated portion 1385 , and a guiding means 1330 extending inwardly from the inner surface of the piston 130 . As described below, the piston 130 will be cut by the cutting crown 1200 , and the weak portion 1380 reduces the effort required for cutting the piston 130 . [0059] The elevated portion 1385 serves to thicken the central portion of the piston 130 . Thickening the central portion reinforces it and thus prevents an inward collapse of the piston 130 as it withstands the resistive forces exerted by the fluids contained within the barrel 140 when the plunger 120 is depressed. Further, having a domed shape for the elevated portion 1385 may serve to better diffuse the resistive forces, thus providing better reinforcement. It is noted that having such a reinforced piston 130 may also be advantageous as it serves to reduce the flexing of the piston 130 when the plunger 120 is depressed or withdrawn. [0060] Turning now to the guiding means 1330 , the guiding means 1330 may also provide support for the piston 130 so as to enable the piston 130 to withstand the compression forces exerted on the piston 130 when the plunger 120 is depressed. The elevated portion 1385 and the guiding means 1330 guide cutting teeth 1220 of the cutting crown 1200 towards the weak portion 1380 . There may be any number of cutting teeth, but there are preferably in the range 2 to 5 such teeth. The guiding means 1330 may be annular with a chamfered edge 1350 facing away from the inner surface of the piston 130 . A ledge 1230 of the cutting crown 1200 rests against the chamfered edge 1350 when the plunger 120 advances. Thus, the guiding means 1330 also plays the role of a spacer preventing the cutting teeth 1220 from prematurely cutting into the weak portion 1380 when the piston 120 is expelling fluid from the syringe 100 . The chamfered edge 1350 may also aid in the guiding of the cutting teeth 1220 towards the weak portion 1380 . Further, the guiding means 1330 may also play the role of a biasing means providing a biasing force against the cutting crown 1200 when the end of the plunger 120 approaches the seal 1540 . Such a biasing means 1330 provides a tactile feedback to a user depressing the plunger 120 in the form of a “click”. This allows the user to know when the cutting crown 1200 is about to bear against the weak portion 1380 of the piston 130 and the weak portion 1590 . In such a case, after the cutting crown 1200 breaks the weak portion 1590 , the biasing means 1330 may be deformed. [0061] The outer cylindrical portion 1340 has a catch 1370 for retaining the piston 130 over the cutting crown 1200 . This catch 1370 may take the form of an annular recess running around the inner surface of the cylindrical portion 1340 in which case the catch 1370 may also provide added rigidity to the piston 130 , thus restricting any buckling of the piston 130 when a large compression force acts upon it. With reference to FIG. 2A , the catch 1370 may be mated with a ridge 1250 running around the cylindrical sides of the cutting crown 1200 . Such a ridge 1250 and catch 1370 may permit the piston 130 to be retained over the plunger 120 when the plunger 120 is slid up or down the length of the barrel 140 . The plunger 120 and piston 130 arrangement thus enables the push and pull pumping function for injecting or aspirating a fluid. [0062] Returning to FIGS. 1 and 2A , the inner dimensions of the mouth 1440 and the cylinder portion 1410 of the barrel 140 are made suitable for receiving the piston 130 and the plunger 120 . In normal assembly, the piston 130 may be fitted to the plunger 120 before the plunger 120 is inserted into the barrel 140 . Alternatively, optionally, the piston 130 and plunger 120 may be formed as a one-piece (i.e. integral) item. After the plunger 120 and piston 130 are inserted into the barrel 140 , the plunger 120 and piston 130 are slideable within the barrel 140 . [0063] A passage 1530 runs through the needle holder 1560 , so that the volume 1470 within the barrel 140 between (i) the piston 130 , and (ii) the needle hub 1510 and seal 1540 , communicates with the inside of the needle 1520 . Otherwise, fluid cannot escape from the volume 1470 . [0064] FIGS. 3D and 3F respectively show a cross-sectional view of the retraction assembly 150 , and a cross-sectional view of part of the retraction assembly 150 of FIG. 3D when it is fitted into the front portion 1420 of the barrel 140 . The weak portion 1590 around the seal 1540 is frangible so that when it is broken, the needle holder 1560 will be released and be pushed upwardly by the spring 1600 . The weak portion 1590 allows the cutting crown 1200 of the plunger 120 to break the retention mechanism formed by the weak portion 1590 and the seal 1540 with greater ease. Further, the thinness of the weak portion 1590 allows the seal 1540 to be flexed. By flexing the seal 1540 , the retraction assembly 150 may be fitted more easily into the front portion 1420 of the barrel 140 . [0065] When the syringe 100 is assembled, the retraction assembly 150 is attached to the front portion 1420 of the barrel 140 by the outer surface 1580 of the seal 1540 . The outer circumference 1580 comes to rest against the side wall of the front portion 1420 . An annular recess 1460 may be formed into the inner wall of the front portion 1420 to function as a retaining means for holding the seal 1540 . Such an annular recess 1460 may also have the advantage of creating a more water tight seal between the seal 1540 and the front portion 1420 . An adhesive may also be applied around the outer circumference of the seal 1540 to create a tighter seal. Further, it is also envisaged that in variants of the embodiment, parts or the whole of the retraction assembly 150 may be formed integrated with the front portion 1420 . As an example, the seal 1540 may be integrated with the front portion 1420 to form a single piece. [0066] The spring 1600 is compressed within the front portion 1420 of the barrel 140 . The spring 1600 may be attached at a first end 1610 to the needle holder 1560 and at the other end 1620 attached to the front portion 1420 of the barrel 140 . The needle holder 1560 comprises one or more anchor points 1570 holding the end 1610 of the spring 1600 . The anchor point 1570 may take the form of a ledge with an outer diameter wider than that for the spring 1600 . In such a case, the end 1610 may rest upon the anchor point 1570 , the anchor point 1570 thus providing a point of resistance which permits the spring 1600 when compressed to push the needle holder 1560 upwardly. [0067] At the other end 1620 of the spring 1600 , the end 1620 of the spring 1600 bears against an annular lip 1450 of the front portion 1420 . The annular lip 1450 provides a point of support which the compressed spring 1600 pushes against. The compressed spring 1600 thus expands and pushes in opposite directions against the annular lip 1450 and the anchor point 1570 . [0068] Returning to FIGS. 1 and 2A , the syringe 100 optionally further comprises a needle protector 1700 . Such a needle protector 1700 may be fitted over the front end 1420 of the barrel 140 . The protector 1700 has a retention means for keeping the protector 1700 in place over the front end 1420 and the needle 1520 . [0069] The cutting crown 1200 will now be further described with the aid of FIGS. 3A , 3 B and 3 C. FIG. 3A is a cross-sectional view of the cutting crown 1200 . FIG. 3B is a side view of the cutting crown 1200 of FIG. 3A . FIG. 3C is a perspective view of the cutting crown 1200 of FIG. 3A . [0070] The cutting crown 1200 comprises a ledge 1230 that rubs against the chamfered edge 1350 of the piston 130 as the cutting teeth 1220 approach the seal 1540 . The cutting crown 1200 further comprises one or more cutting teeth 1220 located at the leading end of the plunger 120 . These cutting teeth 1220 are arranged circumferentially around the longitudinal axis 122 of the plunger 120 and taper inwardly towards the longitudinal axis 122 . The edge of the teeth 1220 may be chamfered to yield a sharpened cutting edge suitable for cutting into the weak portion 1380 of the piston 130 and the weak portion 1590 of the retraction assembly 150 . The teeth 1220 are thus be capable of cutting the piston 130 and the weak portion 1590 with a minimal amount of effort. Interspaced between each consecutive cutting tooth 1220 along the cutting edge are bridges 1210 . Each bridge 1210 may have an arcuate profile spanning from tooth to tooth. When the cutting crown 1200 is brought to bear against the piston 130 and/or the weak portion 1590 , such an arcuate profile may result in a better diffused distribution of resistive forces acting upon each tooth 1220 , thus resulting in teeth 1220 that are stronger and better able to cut through the piston 130 and/or the weak portion 1590 . [0071] When designing the cutting crown 1200 , a cutting distance d (as indicated in FIG. 3A ) and a puncturing force F (as indicated in FIG. 2C ) may be minimized. As is illustrated in FIGS. 3A and 3B , the cutting distance d is defined as the perpendicular distance from the apex of the teeth 1220 to the nadir of the bridge 1210 . The puncturing force F is defined as the force required for the teeth 1220 of the cutting crown 1200 to cut the piston 130 and/or the retraction assembly 150 . [0072] A short cutting distance d may be advantageous because it means a user will have to provide a sustained cutting force on the plunger 120 for a shorter sliding distance. A lesser puncturing force F may be advantageous because it means the user will have to provide less instantaneous force to pierce into the piston 130 and/or the retraction assembly 150 . [0073] There exists a trade-off between the cutting distance d and the puncturing force F. FIG. 7 shows two possible profiles for bridges 1210 and tooth 1220 , each profile having a different value of d. It can be seen that lower values of d are associated with lower sharpness of the tooth 1220 . The reduced “sharpness” of each tooth 1220 however is undesirable as it requires a greater puncturing force F. Consequently, in order to have a lower puncturing force F, the distance d may be made larger in order to increase the “sharpness” of the tooth 1220 . [0074] Holding the cutting distance d constant, the “sharpness” of each tooth 1220 may be improved by increasing the number of teeth 1220 arranged around the end of the plunger 120 . FIG. 8A shows a side view of a cutting crown 1200 with five cutting teeth 1220 (the solid lines in FIG. 8A show the port of the cutting crown which face the viewer, while the dashed portions show the part of the cutting crown facing away). FIG. 8B shows an alternative cutting crown 1200 with two cutting teeth 1220 . It can be seen that the teeth 1220 of FIG. 8A are “sharper” than the teeth 1220 of FIG. 8B . [0075] It is thus noted that there exists a further trade-off between the number of teeth 1220 and the puncturing force F. While having more cutting teeth 1220 may result in “sharper” teeth 1220 , it also results in the puncturing force F having to be greater because it is divided between a greater number of teeth 1220 . Thus in the interest of having a lesser puncturing force F, a lesser number of cutting teeth 1220 may be employed. [0076] The typical operation of the assembled syringe 100 is next described with reference to FIGS. 2A to 2D . FIG. 2A is a cross-sectional view of the assembled syringe 100 before it is used. FIG. 2B is a cross-sectional view of the piston 130 when the piston 130 is proximate the seal 1540 . FIG. 2C is a cross-sectional view of the piston 130 when the cutting crown 1200 is cutting the weak portion 1380 of the piston 130 . Finally, FIG. 2D is a partial cross-sectional view of the piston 130 after the cutting crown 1200 has cut the piston 130 and the weak portion 1590 . [0077] A user of a fresh syringe 100 first removes the needle protector 1700 . The tip 1570 of the needle may be placed in a fluid e.g. a medicament that is to be drawn into the syringe 100 . The plunger 120 is then withdrawn from the barrel 140 . This may be done by the user using a first hand to firmly grasp the outer surface of the barrel 140 while using a second hand to hold the end cap 1100 and draw back the plunger 120 . [0078] The syringe 100 has a space 1470 that is formed within the barrel 140 between an outer surface of the piston 130 facing away from the cutting crown 1200 and the top face 1565 of the needle holder 1560 . When the plunger 120 is withdrawn from the barrel 140 , the increase in the volume of the space 1470 sucks fluid into the space 1470 . The fluid is fed into the space 1470 via the passage 1530 leading through the needle holder 1560 of the retraction assembly 150 . [0079] The user then depresses plunger 120 in order to expel the fluid from the syringe 100 . This may be done by the user grasping the outer surface of the barrel 140 with the index finger and the middle finger of a hand, while using the thumb of the hand to press against the end cap 1100 . The flanges 1430 aid this action as they provide additional holding surfaces for the index and middle finger. [0080] When the plunger 120 is depressed, the piston 130 forces the fluid contained within the space 1470 out via the passage 1530 . The outer surface 1320 of the piston 130 that faces away from the cutting crown 1200 has a domed profile which matches the concave receiving surface disposed at the front portion 1420 of the barrel 140 . The receiving surface consists of the top face 1565 of the needle holder 1560 , the seal 1540 and the end wall 1461 of the cylinder portion 1410 of the barrel 140 . By having such a concave receiving surface, the syringe 100 may have the advantage of being easier to “bleed”. What this means is that air bubbles contained within the space 1470 may be removed via the passage 1530 more easily. Also, the receiving surface is smooth and there are no gaps or protruding seams at the points where the top face 1565 of the needle holder 1560 meets the seal 1540 , and where the seal 1540 meets the end wall 1461 of the barrel 140 . Such a smooth surface may further contribute to the advantage of being easier to “bleed” as there will be an absence of irregularities on the surface which may retain air bubbles. [0081] The process of “activating” the syringe 100 is described next across three “activation” states. Referring now to FIG. 2B , the plunger 120 is depressed until the cutting crown 1200 is approaches the weak portion 1380 of the piston 130 . The ledge 1230 of the cutting crown 1200 rubs against the chamfered edge 1350 of the piston 130 and the guiding means 1330 provides a tactile feedback to a user depressing the plunger 120 in the form of a “click”. When this happens, the syringe 100 is in the first “activation” state and the guiding means 1330 is also forced outwardly away from the longitudinal axis 1440 . This frees the guiding means 1330 from its role as a spacer preventing the cutting crown 1200 from prematurely cutting the weak portion 1380 . Further, the cylindrical portion 1340 may be deformed as the ridge 1250 runs down the inside of the piston 130 . As the plunger 120 is further depressed, the elevated portion 1385 and the guiding means 1330 guide the one or more cutting teeth 1220 of the cutting crown 1200 towards the weak portion 1380 . It is estimated that the force required to achieve the first “activation” state may be about 1.2 to 2 times the compression force which the syringe has to withstand without leaking in order to achieve the ISO 7886-1 standard. [0082] During this process, a radially-outer portion of the front surface 1320 of the piston 160 first meets the end wall 1461 of the cylinder portion 1410 of the barrel 140 . Gradually, more radially-inward portions of this surface 1320 contact the end wall 1461 of the portion 1410 , and then the seal 1540 and top face 1565 of the needle holder 1560 . In other words, the contact area of the plunger with the end of the chamber gradually expands radially-inwardly. When the syringe 100 is emptied, the top face 1565 fully meets the outer surface 1320 . This may assist in fully expelling the fluids contained within the space 1470 , thus preventing as fluid wastage. [0083] Turning now to FIG. 2C , the plunger 120 is depressed further until the cutting crown 1200 cuts through the weak portion 1380 of the piston 130 . The syringe 100 is now in the second “activation” state. The application of the puncturing force F on the plunger 120 forces the cutting teeth 1220 to pierce into the weak portion 1380 of the piston 130 and thereafter also cuts through the weak portion 1590 of the retraction assembly 150 . [0084] Referring now to FIG. 2D , the plunger 120 is depressed even further for a cutting distance d, at which time syringe 100 is in the “third” activation state and the sharpened cutting edge of the teeth 1220 cuts completely through the weak portion 1590 . When this happens, the retention mechanism formed by the weak portion 1590 and the seal 1540 can no longer retain the needle unit (i.e. the needle 1570 , the needle holder 1560 and the hub 1510 ). Furthermore, the elevated portion 1385 has been released from the main body of the piston 130 . This permits the needle unit to be pushed upwards by the spring 1600 and into the stem 1290 of the plunger 120 . When doing so, the spring 1600 also pushes the released elevated portion 1385 into the stem 1290 . The spring 1600 is allowed to expand to its maximum extend thus bringing the needle holder 1560 and any attached needle 1520 entirely within the stem 1290 . The needle holder 1560 and attached needle 1520 are thus retracted into the syringe 100 . The syringe 100 in this state may thus be said to have been “activated”. It is noted that the force needed to complete the cut through the weak portion 1590 in the “third” activation state may be less than the puncturing force F. [0085] It is noted that once the syringe 100 has been “activated”, the piston 130 and the retraction assembly 150 are destroyed. The syringe 100 thus may no longer be reused and this may prevent the recycling of syringes. [0086] A second embodiment of the present invention is described next with the aid of FIG. 4 . FIG. 4 is a cross-sectional view of an assembled syringe 110 according to a second embodiment of the present invention. The syringe 110 may be especially suitable for small fluid volumes (e.g. 1 ml or 10 ml), but may also be used with any other volume of fluid. The second embodiment has elements in common with the first embodiment and these like elements are designated using like reference numerals. [0087] The second embodiment differs from the first embodiment by having a wider cutting crown 1201 of a diameter that is substantially the same as that for the stem 1290 . Conspicuously, the guiding means 1330 previously present in the second embodiment is now absent and the end wall 1461 is now reduced to an annular ledge. The roles previously played by the guiding means 1330 may now be fulfilled by the outer cylindrical portion 1340 of the piston 130 . [0088] The syringe 110 may be operated the same way as the syringe 100 . When “activating” the syringe 110 , in the first “activation” state i.e. when the plunger 120 is depressed until the cutting crown 1201 approaches the weak portion of the piston 130 , the lower of the sealing lips 1310 comes to rest against the end wall 1461 . The piston 130 is thus restricted from travelling further down the barrel 140 . The cylindrical portion 1340 now performs the role of a spacer preventing the cutting crown 1201 from prematurely cutting the weak portion 1380 . [0089] A further application of downward pressure dislodges the ridge 1250 from the catch 1370 , thus permitting the cutting crown 1201 to travel downwardly free of the piston 130 . The dislodgment of the ridge 1250 from the catch 1370 may result in a tactile feedback to the user in the form of a “click”. As the cutting crown 1201 travels downwardly towards the weak portion 1380 of the piston 130 , the elevated portion 1385 and the cylindrical portion 1340 guide the one or more cutting teeth 1220 of the cutting crown 1201 towards the weak portion 1380 . Meanwhile, the ridge 1250 also deforms the cylindrical portion 1340 outwardly away from the longitudinal axis 1440 as it travels down the cylindrical portion 1340 . [0090] As in the case of the first embodiment i.e. the syringe 100 , the downward travel of the cutting crown 1201 causes the one or more cutting teeth 1220 of the cutting crown 1201 to eventually bear against the weak portion 1380 of the piston 130 . The second “activation” state is thus arrived at. In the second and third “activation” states, the further functioning of the elements of the syringe 110 are the same as that for the syringe 100 . [0091] We now turn to a third embodiment of the invention, which is a needle assembly 200 . The needle assembly 200 will be described with reference to FIGS. 5A to 5C . FIG. 5A is a needle assembly 200 in its initial state. FIG. 5B is a cross-sectional view of the needle assembly 200 of FIG. 5A when installed onto a syringe. FIG. 5C is a cross-sectional view of the needle assembly 200 of FIG. 5B but with a protector 1700 portion removed. [0092] The needle assembly 200 comprises a needle hub 1510 with threads 520 on the outer side wall, a needle (cannula) 1520 extending from a first end 522 of the hub 1510 to a distal tip 1570 , and a tubular neck 510 that is suitable for insertion into the needle holder 1560 of a syringe extending from a second end 524 of the hub. A cylindrical bore 515 runs continuously length-wise through the center of the needle 1520 from the tip 1570 , and on through the center of the hub 1510 , and further on through the center of the neck 510 before terminating as an opening 565 at an end face 560 of the neck 510 . The bore 515 functions as a conduit for the delivery of fluids from the syringe out through the tip 1570 . [0093] The needle 1520 may be made out of a metal e.g. stainless steel, or optionally other materials such as a rigid plastic. The tip 1570 of the needle 1520 may be chamfered and sharpened to assist in piercing surfaces. Optionally, the needle 1520 extends through the first end 522 of the hub 1510 and part of the way through the neck 510 . In other embodiments, the needle 1520 may extend through the entire length of the needle assembly 200 from the tip 1570 to the end face 560 . In either case, the bore 515 has a substantially constant shape (typically a circle) and size along its length, making it possible to much reduce any dead spaces. [0094] The hub 1510 is cylindrical and has one or more nested helical threads 520 running on at least part of the outer cylindrical side wall of the hub 1510 . The threads 520 of the hub 1510 mate with corresponding threads 1585 present on the inner surface of the needle holder 1560 . It is however envisaged that in a variant of the embodiment, the hub 1510 may not necessarily use a twist-locking system in order to mate the hub 1510 with the needle holder 1560 . For example, a stopper based locking system may be used. [0095] The neck 510 has a smooth outer surface. The neck 510 terminates with the end face 560 which may be beveled circumferentially so as to allow an easier fitting of the neck 510 into the needle holder 1560 . The smooth outer surface of the neck 510 may function as a guiding surface leading the corresponding threads 1585 to the threads 520 . Further, the neck 510 may result in a more secure seal, thus preventing the leaking of fluids originating from a passage 1471 of the syringe. [0096] As mentioned above, the needle assembly 200 comprises a needle protector 1700 that is disposed over the needle 1520 , thus encasing the needle 1520 . Such a needle protector 1700 may prevent the needle 1520 from becoming a sharps hazard. It is envisaged that the protector 1700 may be formed as a single piece together with the hub 1510 in which case the protector 1700 may be connected to the hub 1510 by a frangible portion 550 . Such a single piece design may confer the advantage of manufacturing ease, and a tamper proof needle assembly 200 . The integrity of a virgin needle assembly 200 with the frangible portion 550 intact may thus be assured. [0097] The frangible portion 550 is intended to break easily when a user twists the protector 1700 away relative to the hub 1510 . The protector 1700 may further comprise one or more wings 530 extending from the outer wall of the protector 1700 . The wings 530 may permit a user to better deliver rotational force to the protector 1700 about the longitudinal axis 202 of the protector 1700 when the protector 1700 is encasing the needle 1520 . The skilled person however will understand that the wings 530 may take on other forms apart from that shown in FIGS. 5A and 5B , for example taking the form of finger loops or simply just a roughened surface. [0098] The needle protector 1700 may further comprise a biasing means for holding onto the needle 1520 when the protector 1700 is encasing the needle 1520 . Such a biasing means may be disposed internally within the protector 1700 and may serve to prevent the protector 1700 falling off the needle 1520 after the frangible portion 550 is broken. [0099] The needle holder 1560 comprises a tubular recess 1575 that is suitable for receiving the needle assembly 200 . The internal surface of the recess 1575 has a threaded portion containing threads 1585 which correspond to the threads 520 of the needle assembly 200 . [0100] It is noted that the hub 1510 of the needle assembly 200 has the form of a male body with outer threads 520 , and the needle holder 1560 of the syringe has the recess 1575 which results in a female body with inner threads 1585 . This results in a needle assembly 200 and needle holder 1560 that are easier to manufacture since the interlocking portions of both the needle assembly 200 and the needle holder 1560 i.e. the hub 1510 and the recess 1575 respectively, are not multiply nested when mated. Also, the compact design of the needle assembly 200 may require less material when manufacturing, thus allowing for more efficient material usage. [0101] The needle assembly 200 may be installed into the syringe by inserting the neck 510 of the needle assembly 200 into the tubular recess 1575 first. The neck 510 is inserted past the inner threads 1585 until where the outer threads 520 of the needle assembly 200 are ready to be screwed onto the inner threads 1585 . [0102] The user may then screw the outer threads 520 of the needle assembly 200 onto the inner threads 1585 by holding onto the wings 530 of the protector 1700 and twisting. Such a mating of the outer threads 520 with the inner threads 1585 may be described as a “lock” because the interlocking threads may prevent the leakage of any fluid. Once the needle assembly 200 is fully inserted in the needle holder 1560 , the hub 1510 of the needle assembly 200 may twist no further. By further twisting the protector 1700 , the user delivers rotational force to the protector 1700 about the longitudinal axis 202 of the protector 1700 . The rotational force breaks the frangible portion 550 connecting the protector 1700 to the hub 1510 . When this happens, the protector 1700 becomes free from the rest of the needle assembly 200 and may be removed. The further twisting action that is used to break the frangible portion 550 may also assist in lodging the outer threads 520 together with the inner threads 1585 more tightly. [0103] The recess 1575 is in fluid communication with the cylindrical chamber 1470 of the barrel 140 through the passage 1471 . Thus when the needle assembly 200 is fully inserted into the recess 1575 , the opening 565 of the end face 560 coincides with the passage 1471 . The fact that the opening 565 of the end face 560 faces the passage 1471 and has substantially the same narrow diameter, prevents the existence of a dead space between the end face 560 of the needle and the passage 1471 . A substantially constant bore 515 is formed from the space 1470 in the barrel 140 of the syringe 100 , through the passage 1471 , into the opening 565 of the needle assembly 200 and out through the tip 1570 of the needle 1520 . Such a continuous bore 515 reduces dead spaces within the entire delivery channel since the diameter of each section of the continuous bore 515 may be similar. Also, the uniform diameter avoids trapping of air within the bore 515 . The continuous bore 515 may also be made to be thin so as to reduce the amount of residual fluid present in the delivery channel when the syringe 100 is fully depressed. [0104] It is noted that once the needle assembly 200 is installed onto the needle and the protector 1700 is broken free of the needle hub 1510 , there may be no practical way for unscrewing the needle assembly 200 from the syringe 100 as the protector 1700 which provides traction for a user to twist the needle assembly 200 is now free of the needle hub 1510 . This may thus also discourage the recycling of the needle assembly 200 . [0105] A fourth embodiment of the invention is shown in cross-section in FIG. 6 . The needle assembly of FIG. 6 is the third embodiment shown in FIG. 5A , but the syringe is a variant of the syringe 100 of FIG. 1 , having corresponding portions labeled by the same reference numbers. In this variant, the retraction assembly 150 of FIG. 1 is replaced by a structure which is formed by inserting the needle assembly of FIG. 5A into a needle holder 1560 . The operation of this embodiment is then the same as that of the first embodiment, except that the “needle unit” which is drawn into the syringe unit is composed of the needle 1570 , and the needle hub 1510 , and the needle holder 1560 . Note that since the needle assembly 200 is usable both in the context of a retractable syringe (as in FIG. 6 ) and a non-retractable syringe (as in FIG. 5B ) only a single type of needle assembly needs to be stocked to enable both these functions. [0106] In this specification, the terms “needle” and “cannula” have been used interchangeably to refer to the needle 1520 . Further, the term “fluid” may refer to either a “liquid” or a “gas”. [0107] Whilst example embodiments of the invention have been described in detail, many variations are possible within the scope of the invention as will be clear to a skilled reader.
A retractable syringe comprises a cutting head mounted on a plunger of the syringe. When the plunger is advanced to expel fluid from the syringe, the cutting crown cuts a retention mechanism which holds a needle unit of the syringe, allowing a drive mechanism to drive the needle unit into the syringe. The cutting crown is shaped to reduce the force which has to be applied to cut the retention mechanism. Furthermore, a disposable needle assembly for attachment to a syringe unit comprises a needle and connector element for connecting the needle to the syringe unit. The connector element encircles the needle and has a thread on its outer surface for mating with the syringe unit. When the needle assembly is mated with the syringe, a central bore of substantially constant bore extends from the tip of the needle into the interior chamber of the syringe.
0
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The invention relates to an office chair, in particular an office chair having a backrest that can be tilted into a rest position. [0003] As a rule, such an office chair is configured as an office swivel chair and has various forms of adjustment in order to permit a high degree of seating comfort. Modern office swivel chairs are provided with a “synchronous mechanism” via which a seat can be combined with the backrest in such a way that the seat is oriented in an ergonomic manner in each tilted position of the backrest. On account of the tilting capacity of the backrest, the office chair can be shifted into a rest position. In order to permit a position which is as relaxed as possible, it is advantageous if the feet can be put on a footrest. Such a footrest is configured, for example, as a separate piece of furniture or is fastened to a writing table. U.S. Pat. No. 5,727,848 discloses a chair for a computer workplace having a footrest fastened to the seat of the chair via an extendable rod. SUMMARY OF THE INVENTION [0004] It is accordingly an object of the invention to provide an office chair that overcomes the above-mentioned disadvantages of the prior art devices of this general type, having a high degree of comfort. [0005] With the foregoing and other objects in view there is provided, in accordance with the invention, an office chair. The office chair contains a backrest which can be tilted into a rest position, a support column supporting the backrest, a footrest, and a telescopically extendable connecting element connected on a first end to the support column and on a second end to the footrest. The connecting element is extendable from a basic position into an extended position. The connecting element has a restoring element exerting a restoring force on the connecting element in a direction of the basic position. [0006] The object is achieved according to the invention by the office chair, in particular by the office chair having a backrest that can be tilted into a rest position. The footrest is fastened to the office chair via the telescopically extendable connecting element that is extendable from the basic position into the extended position. In this case, the restoring element configured in particular as a spring element is provided. The restoring element exerts a restoring force on the connecting element in the direction of the basic position of the connecting element. [0007] The fastening of the footrest to the office chair, compared with a footrest configured as a separate piece of furniture, achieves the advantage that, when the feet are supported on the footrest, the office chair is not pushed away from the footrest. The distance between the footrest and the office chair therefore stays the same. Furthermore, associated with the telescopic extendability is the advantage that the footrest can be positioned at different distances from the office chair and, can be pulled up to the office chair in a space-saving manner when it is not required. The configuration of the restoring element is especially useful, since in this way the footrest is automatically retracted into the basic position when it is not required. In addition, favorable ergonomic positioning of the footrest is automatically effected without manual adjustments having to be made. In particular, an ergonomically favorable adjustment to different users is effected, or if a user changes his seating position, for example by leaning back. [0008] For a simple configuration of the connecting element, it is preferably configured as a telescopic tube. [0009] In this case, the connecting element is expediently configured in such a way that it is moved evenly from the extended position into the basic position. The automatic retraction of the connecting element, in particular, is therefore not effected suddenly, and is also effected sufficiently slowly, in order not to form any source of danger due to the footrest springing back too quickly. [0010] In this case, a valve is expediently provided on the telescopic tube, and the valve has a large outflow resistance, compared with the inflow resistance, for the air flowing out of the telescopic tube during the movement into the basic position. The outflowing air is thus choked and provides for uniform retraction into the basic position. The valve is preferably configured as a simple check valve that clears an air opening in the telescopic tube when the telescopic tube is being extended. When the telescopic tube is being retracted, the check valve at least partly covers the air opening. [0011] In an expedient development, the extension length of the connecting element is adjustable. In preferred variants, the adjustability has a displacement limit and/or a fixing device. With the displacement limit, extension of the connecting element beyond a desired extension length is prevented. It thus permits an optimum adaptation to the body size of a person using the office chair. The fixing device, in addition to the displacement limit, additionally achieves the effect that the footrest—if desired—is not automatically retracted and remains in a predefined position. [0012] In an especially advantageous embodiment variant, the connecting element is fastened so as to be pivotable about a perpendicular chair axis. This makes it possible to bring the footrest around the office chair into a rear position when it is not required in order to prevent the footrest from getting in the way in the foot region of the office chair. [0013] The connecting element is also expediently pivotable in a plane spread out by the chair axis and the connecting element in order to be able to compensate for any possible unevenness in the floor. [0014] For as simple a fastening of the connecting element as possible, the connecting element is fastened to, in particular clipped onto, a supporting column of the office chair, the supporting column holding a seat carrier. As an alternative to this, the connecting element may also be fastened directly to the seat carrier. With the fastening to the seat carrier, especially stable mechanical guidance of the connecting element is possible. [0015] For a mechanically simple and robust embodiment, a supporting element for supporting the footrest on the floor is provided on the connecting element at the foot end in the region of the footrest. The force exerted on the footrest is therefore transmitted via the supporting element to the floor and does not need to be absorbed via the fastening to the office chair. In order to ensure the mobility of the footrest, the supporting element has casters. [0016] As an alternative to this, the footrest is fastened to the office chair in a freely floating manner, that is to say without a supporting element on the floor. The seat carrier, on account of the stable mechanical guidance for the connecting element, is suitable for the freely floating fastening. [0017] In order to permit an ergonomic seating position that is as comfortable as possible, the footrest contains a pivotable foot support which, in particular by a spring, is held in an initial position and/or can be latched in a pivoted position. In addition to or as an alternative to the spring element, the pivoting capacity is kept tight on account of friction forces. [0018] Other features which are considered as characteristic for the invention are set forth in the appended claims. [0019] Although the invention is illustrated and described herein as embodied in an office chair, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims. [0020] The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0021] [0021]FIG. 1 is a diagrammatic, side-elevational view of an office chair with a footrest, which is attached thereto via a connecting element, in an extended position, according to the invention; and [0022] [0022]FIG. 2 is a side-elevational view of the office chair according to FIG. 1 with the footrest in a retracted basic position. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0023] Referring now to the figures of the drawing in detail and first, particularly, to FIG. 1 thereof, there is shown in a greatly simplified manner an office chair 2 , in particular an office swivel chair, that has a backrest 4 and a seat 6 . The seat 6 is held by a seat carrier 8 (shown by broken line). The seat carrier 8 is connected via a vertically adjustable supporting column 10 to a pedestal 14 mounted on casters 12 . The backrest 4 can be tilted into a rest position, as shown in FIG. 1. In this case, the office chair 2 has in particular a “synchronous mechanism” which connects the backrest 4 and the seat carrier 8 to one another in such a way that, when the backrest 4 is adjusted, the seat carrier 8 is at the same time adjusted in an especially ergonomic manner. [0024] A connecting element configured as a telescopic tube 16 is fastened to the supporting column 10 , in particular by being clipped on, by a fastening element 18 . In this case, the fastening element 18 preferably encloses the supporting column 10 in a loose manner, so that the connecting element can be pivoted about a perpendicular chair axis 20 running through the supporting column 10 . The fastening element 18 is connected to the telescopic tube 16 via a joint 21 . The joint 21 permits pivoting of the telescopic tube 16 in a plane spread out by the chair axis 20 and the telescopic tube 16 . The telescopic tube 16 can therefore be pivoted relative to the horizontal, so that, for example, unevenness in the floor can be compensated for. [0025] At the foot end, a footrest 22 having a foot support 24 is disposed on the telescopic tube 16 . The footrest 22 is supported on a floor (not shown in any more detail) via a supporting element 26 and a caster 28 . The foot support 24 formed in one piece with the footrest 22 is held in a pivotable manner on the supporting element 26 via a swivel joint 30 . The pivoting capacity is kept tight, for example by an adjustable friction force. In addition, the inclination of the foot support 24 can be fixed by corresponding latching in the swivel joint 30 . As an alternative to this, it is possible to provide a non-illustrated spring in the swivel joint, and this spring brings the foot support 24 in each case into a predefined initial position when not in use. [0026] Provided in the telescopic tube 16 is a spring element 32 that automatically retracts the footrest 22 from an extended position according to FIG. 1 into a retracted position according to FIG. 2. It is additionally shown in FIG. 2 that the footrest 22 is swung to the rear side of the office chair 2 in order not to get in the way in the front foot region. [0027] The spring element 32 is preferably configured in such a way that the footrest 22 is moved evenly and sufficiently slowly from the extended position into the basic position in order not to represent a risk of injury. A valve 34 , shown schematically, is provided in order to assist the even retraction. This causes the air which is to be displaced from the telescopic tube 16 during the retraction into the basic position to escape slowly and evenly, so that the footrest 22 does not spring back suddenly into the basic position. The valve 34 is configured as a simple check valve for example. [0028] Furthermore, provision is preferably made for the extension length of the telescopic tube 16 to be adjustable and in particular fixable. It is thus possible, on the one hand, to limit the distance between the footrest 22 and the seat 6 , so that the footrest is not pushed away from the office chair to an undesirable extent. On the other hand, automatic retraction into the basic position is prevented by the fixing device. [0029] The office chair 2 with the footrest directly attached thereto has the substantial advantage that the office chair 2 mounted on the casters 12 cannot be pushed away when using the footrest 22 on account of the muscle power exerted on the footrest 22 . A distance between the footrest 22 and the seat 6 is therefore kept constant. In addition, the footrest 22 is always directly accessible and can be positioned in an ergonomically favorable manner relative to the seat 6 . Operation is also especially user-friendly, since the footrest 22 can be extended in a simple manner by muscle power when required from the retracted basic position into the desired extended position. In addition, due to the pivoting capacity about the chair axis 20 , the footrest 22 can be put away in a space-saving manner. Given a suitable subdivision of the individual telescopic elements of the telescopic tube 16 , the footrest 22 can also be pulled nearer to the supporting column 10 than as shown in FIG. 2. It is thus possible to pull the footrest near to the supporting column 10 in such a way that it does not project beyond the pedestal 14 .
A footrest is fastened via a telescopically extendable connecting element to an office chair, in particular to an office chair having a backrest that can be tilted into a rest position. This results in an especially comfortable and ergonomic seating position, and in particular a situation in which the office chair is pushed away from the footrest when the footrest is not needed.
0
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a food slicer apparatus and a knife therefor and, more particularly to a knife that disturbs the airflow adjacent the perimeter thereof and precludes the buildup of food particulates on the knife surface. 2. Information Disclosure Statement In preparing for this application, a pre-examination patentability search was conducted. In performing the search, the following fields and periods covered by the search were examined. ______________________________________CLASS/SUBCLASS PERIOD COVERED______________________________________30/347 03/19/1907 to 05/28/199183/676 06/27/1839 to 01/15/1991______________________________________ The search, which reviewed several subclasses of Classes 38 and 83, uncovered the following patents: ______________________________________ ISSUEITEM NO. U.S. PAT. NO. INVENTOR DATE______________________________________1 1,120,270 A. Brussolo 12/08/19142 1,630,945 A. Jacobowitz 05/31/19273 2,531,841 F. J. Cashin 11/28/19504 2,735,468 X. B. K. Green 02/21/1956 et al.5 3,872,763 I. Kayahara 03/25/19756 4,891,885 R. R. Fischer et al. 01/09/1990______________________________________ In considering the various patents uncovered, the patent to Brussolo '270 teaches a slicer blade having the general profile of that of the common slicer blade. Brussolo '270 further teaches an edge formed by closely spaced grooves with those on the front face alternating with those on the back face with the purpose of maintaining knife sharpness. The patent to Cashin, Cashin '841, is a variant of this, in that a knife for a book block trimmer has V-shaped grooves about the perimeter. Here the purpose is the ejection of debris from the cutting site. This teaching is the antithesis of the disclosure at hand insofar as the present disclosure teaches a means of separating the knife from the food being cut. Next items 5 and 6 above, namely, Kayahara '763 and Fischer '885 are considered. The knife of Fischer '885 is of interest as detail in FIGS. 8 and 9 thereof. The Kayahara '763 patent shows a series of apertures in an annular configuration arrayed along the outer portion of the saw blade adjacent the cutting edge. In both of these patents, the teachings are for different purposes than those of the present disclosure, to wit, in the case of the scalloped edge, to maintain sharpness; and in the case of the apertured edge, to maintain thermal stability. Here again there is no application or teaching toward a food slicer of the type presented hereinbelow. In the past, food slicing machines, especially of the gravity-fed type, experience when slicing gummy or greasy foods, such as cheeses or meats, the accumulation of waste particulate matter in the area adjacent the cutting edge of the knife. This condition is often exacerbated during the back stroke of the reciprocating chute. SUMMARY In general terms, the invention disclosed hereby includes a food slicing apparatus with a gravity feed chute for reciprocally carrying food being sliced across a rotating, food-shedding knife. The food-shedding knife is characterized by indentations in an apron portion--behind the peripheral cutting edge and on the front of the knife--so that upon rotation of the knife, the indentations disturb the adjacent airflow. The apparatus includes a base; a drive motor mounted on the base, which drive motor has an output shaft; a transmission for transmitting rotatory motion from the output shaft to the knife; a knife plate or hub assembly for mounting the knife; and, a knife with a dish-shaped body. In the apparatus form of the disclosure, the food slicer operates so that, when food in the gravity feed chute is reciprocally moved across the rotating knife, the food is sliced without food particles building up on the knife surface. The disclosure further includes a food slicer knife with indentations arrayed on the apron portion. The indentations are sufficiently large, that during the rotation of the knife, the air passing along the surface of the apron portion is disturbed. It has been found that the arrangement of the knife as described in detail hereinbelow is especially useful in preventing buildup of cheese and meat particles on the knife. OBJECT AND FEATURES OF THE INVENTION It is an object of the present invention to provide a food slicer knife which provides turbulent airflow adjacent the cutting edge. It is a further object of the present invention to provide a food slicer knife which prevents the buildup of food debris thereon. It is yet another object of the present invention to provide a food slicer knife with a continuous smooth cutting edge and medial intrafacial indentations. It is still yet another object of the present invention to provide a food slicer knife wherein the indentations are air spoilers. It is a feature of the present invention that the irregular surface adjacent the cutting edge of the food slicer knife creates turbulent airflow. It is another feature of the present invention to have a food slicer knife that minimizes food buildup thereon. Other objects and features of the invention will become apparent upon review of the drawings and the detailed description which follow. BRIEF DESCRIPTION OF THE DRAWINGS In the following drawings, the same parts in the various views are afforded the same reference designators. FIG. 1 is a simplified perspective view of the food slicing apparatus of the present invention; FIG. 2 is a perspective view of the knife for the food slicing apparatus of the present invention, and is shown partially broken away to show greater detail; FIG. 3 is a cross-sectional view of the invention shown in FIG. 2, said view taken along line 3--3 thereof and showing the knife profile; FIG. 4 is a detailed perspective view of one of the intrafacial indentations of the food slicer knife showing the canted position thereof and its position relative to the knife radius and the direction of rotation; and, FIG. 5 is an operational schematic view of the invention showing food being sliced by a food slicer knife of this invention and providing arrows representing airflow patterns. DESCRIPTION OF THE PREFERRED EMBODIMENT The following description provides the details of an improvement to the art of the food slicer apparatus and to the knife therefor. In the description, the food slicer is referred to generally by the numeral 10. While context in which this improvement is described is that of the semi-automatic gravity-feed food slicer common to delicatessens and other food retail outlets, the knife is applicable to automatic feed slicers and slicers other than gravity-feed units. These food slicers are marketed under the "Globe", "Hobart", "Berkel", or "Fleetwood" trademarks with exemplary models thereof being the Globe Food Slicer Model 500L, Globe Food Equipment Co., Dayton, Ohio and Hobart Food Slicer Model 1612, Hobart, Inc., Troy, Ohio. Although these machines have evolved over the past eighty years, there has been limited industry-wide standardization and, therefore, the knives for each manufacturer differ slightly. Referring now to FIG. 1, the food slicer 10 is constructed with a base 12, in turn supported by legs 14. A single-ended drive motor 16 is mounted on the base 12 with the drive shaft thereof being connected to gear housing 18. This housing is constructed to include a drive mechanism for transmitting the rotatory motion to the slicer. To the drive mechanism, a knife plate or knife-receiving portion 20 is attached and, in turn, a knife 22 is mounted thereon. About the periphery of the knife, a knifeguard 24 is emplaced so that workers will not be unduly exposed to the rotating knife during slicing operations. The slicer 10 further is constructed to include a gravity-feed chute 26 which is mounted for reciprocal movement in a plane substantially parallel to the knife plate 20 and thereby to present food for slicing to the knife. In addition, a slice receiving tray 28 is mounted on the base and is provided to receive slices of food exiting from the rotating knife. Referring now to FIGS. 2 and 3, the structure of the knife 22 is next discussed. The knife or airflow knife 22 is constructed from food-grade stainless steel suitable for high-speed rotary blade fabrication. The knife 22 is structured with a base 30 which is a dish-shaped or disk-like body having a concave or front side 32 and a convex or back side 34. The outermost or cutting edge 36 of the knife 22 is constructed to be ground from the back and honed or deburred from the front. Thus, in the trade, the back side 34 is also referred to as the "grinding" side, and, conversely, the front side 32 of the knife, as the "trueing" side. The central interior portion of the knife 22 is constructed as a knife hub 38 for attachment to the knife plate 20. The knife hub 38 has a flat outer hub surface 40 for mating purposes. From the cutting edge 36, the cutting knife portion 42 extends radially inwardly with the upper surface 44 thereof being along a plane substantially parallel to that of hub surface 40. The upper surface 44 is also extended radially inwardly to form an apron portion or spoiler member 46 contiguous with the cutting knife portion 42 with the upper surface 48 thereof being coplanar with the face of the cutting knife portion. Medial the apron portion 46 is a plurality of indentations 50. The indentations 50 are sufficiently deep so that, during rotatory motion of the food slicer knife, the air flowing along the surface of the apron portion is disturbed. In the best mode of practicing the invention, it has been found that a row of ellipse-shaped indentations 50, described in greater detail below is efficacious. While this shape has been chosen, any shaped indentation that would disturb the airflow could be formed into the apron portion. Here the only limitations are the pragmatic aspects of: (1) machinability; (2) cleanability; and, (3) structural integrity of the knife. Referring now to FIG. 4, the indentations 50 are now described. In the disclosure at hand, the indentations 50 are shown in an array 52 of seventy two ellipsoidal wells 54. Adjacent wells 54 and 56 are shown spaced 5° apart on the apron portion 46 and on knife radii 58 and 60. The wells 54 and 56 are canted approximately 20°, that is the knife radius to the center of the well is at 20° (approx.) to the major axis 62 of the elliptical opening 64 in the surface of the apron portion. The wells 54 and 56, which, by way of example, are dimensioned with the elliptical opening 64 having a major axis 62 of 1.5 cm (approx.) and a minor axis 66 of 0.6 cm (approx.) and with a depth of 0.3 cm (approx.), have been found sufficient to disturb the air boundary about the apron portion 46. Although the airflow about the knife and the indentations is not completely understood, the structure is such that, upon the slicer chute return stroke, instead of food particles and strands agglomerating on the apron portion as occurs with a standard knife, with the airflow knife the food particles and strands are forced or maintained at a spaced distance from the apron surface. Referring now to FIG. 5, the operation is next described. A loaf of cheese 70 is placed in the gravity-feed chute 26 and is moved back and forth across the rotating knife 22. As the knife 22, configured as hereinabove described rotates, the indentations 50 act as air spoilers. The resultant turbulence, denoted by airflow arrows 72 and 74, is sufficient so that during the chute 26 return stroke--that is returning from the chute travel limit after a slice has been cut--the loaf of cheese is not pressed against the knife 22. Thus, the return stroke occurs without food particles or strands building up on the face of the knife adjacent the cutting edge. Because many varying and different embodiments may be made within the scope of the inventive concept herein taught, and because many modifications may be made in the embodiments herein detailed in accordance with the descriptive requirement of the law, it is to be understood that the details herein are to be interpreted as illustrative and not in a limiting sense.
A food slicing machine with a circular knife having a plurality of radially spaced indentations on a portion inwardly of the cutting edge to induce air flow during rotation of the knife to prevent food particles from accumulating on the knife during cutting operation.
1
FIELD OF THE INVENTION The present invention relates to water cannons and, in particular, to a pneumatic control system for a water cannon. BACKGROUND OF THE INVENTION The typical water cannon comprises a barrel assembly that has an opening or nozzle through which a body of water is driven by the application of a mechanical force. There are at least two types of barrel assemblies employed in water cannons. The first type includes a piston that is located within a barrel and used to apply a mechanical to a body of water located in the barrel. To elaborate, the operation of the piston involves: (a) positioning the piston at a location within the barrel that will allow the piston to be displaced such that water is forced through the opening; and (b) displacing the piston such that a mechanical force is applied to a body of water located between the piston and the opening so that the water is driven through the opening. An example of such a barrel assembly is illustrated in U.S. Pat. No. 6,119,955, which is incorporated herein by reference. The second type of barrel assembly utilizes a barrel with a nozzle through which a body of water is driven (i.e., the opening) and a second end that is in communication with a channel that extends towards the nozzle. Typically, the barrel, channel and communication path between the second end of the barrel and the channel have a U-shape. An example of such a barrel assembly is illustrated in U.S. Pat. No. 3,722,819, which is incorporated herein by reference. In operation, the channel is used to carry a pressurized gas (typically, air) that is used to drive a body of water held in the barrel out of the nozzle. The typical water cannon also comprises a control system that interfaces with the barrel assembly and operates: (a) to place the barrel assembly in a condition or state so a mechanical force can be applied to a body of water in the barrel of the cannon; and (b) to cause a mechanical force to be applied to the body of water that forces the body of water out of the opening of the barrel assembly. In many such control systems, electrical components are employed that are in the immediate vicinity of the water cannon and, as such, are subject to coming into contact with water. Such systems must typically employ a number of measures to prevent the electrical components of the control system from coming into contact with water and either becoming disabled or presenting a safety hazard to individuals in the vicinity of the water cannon. SUMMARY OF THE INVENTION The present invention is directed to a pneumatic control system for a water cannon that substantially avoids the need for electrical circuitry in the immediate vicinity of the cannon. Generally, the pneumatic control system is applicable to water cannons whose operation involves at least two steps, the first step being the priming of the cannon, which at least includes the loading of a body of water into the barrel of the cannon, and the second step involving the “firing” of the cannon such that the body of water is expelled from the barrel. One example of this type of water cannon is a cannon that employs a barrel assembly with a piston that is used to push a body of water out of the barrel of the cannon. With a piston-type of water cannon, the first step involves not only the loading of a body of water into the barrel of the cannon but also the positioning of the piston so that the piston can subsequently push the body of the water out of the cannon. The second step, with a piston-type of water cannon, involves moving the piston such that the body is pushed out of the barrel. Typically, the second step occurs in response to the actuation of a trigger. Another example of a water cannon whose operation involves at least two steps is the piston-less water cannon, an embodiment of which is shown in U.S. Pat. No. 3,722,819. In one embodiment, the pneumatic control system comprises a valve that interfaces with the barrel assembly and is used to apply a fluid-related force to a body of water in the barrel in response to a pneumatic “fire” signal. In the case of a pistonless water cannon, the fluid-related force is applied directly to the body of water and the fluid-related force is typically in the form of a gas (e.g., air). For a piston-type water cannon, the fluid-related force is indirectly applied to the body of water. Namely, the fluid-related force is applied to the piston and then the piston transmits the force to the body of water. In this case, the fluid-related force can take either the form of a gas (e.g., air) or a liquid (e.g., water). The control system further comprises a pneumatic trigger for producing the pneumatic “fire” signal that is applied to the valve. The pneumatic trigger is subject to a pneumatic enable/disable signal. To elaborate, when the pneumatic enable/disable signal is in the disable state, actuation of the pneumatic trigger does not cause the pneumatic “fire” signal to be produced. If, however, the enable/disable signal is in the enable state, actuation of the pneumatic trigger results in the production of the “fire” signal. The pneumatic control system further includes pneumatic logic that operates to: (a) produce a disable/enable signal in the disable state so that the pneumatic trigger cannot be fired by actuation of the pneumatic trigger when the cannon is being fired or when the cannon is being primed; (b) produce a disable/enable signal in the enable state so that the pneumatic trigger can be fired when the cannon is not already in the act of being fired and the cannon is primed to fire; and (c) cause the valve to transition from the “primed” state to the “fire” state in response to a “fire” signal from the pneumatic trigger. In one embodiment, the pneumatic logic includes at least three pneumatic devices that each have at least one input for receiving a pneumatic signal (i.e., a gas signal) and at least one output for providing a pneumatic signal. The first pneumatic device receives a pneumatic signal from a third pneumatic device that is indicative of the state of the water cannon, i.e., the cannon is either in the act of firing or in the act of being primed. The first pneumatic device provides a first “prime” signal a predetermined amount of time after receiving the signal from the third pneumatic device that indicates that the water cannon is in the act of firing. The predetermined amount of time being an amount of time for the cannon to sufficiently complete a firing. As a consequence, the first “prime” signal is an indication that priming of the water cannon can commence. The second pneumatic device receives a second “prime” signal that is produced by the third pneumatic device in response to the first “prime” signal. The second pneumatic device provides a pneumatic signal that is used to enable or disable the pneumatic trigger. The second pneumatic device operates so as to provide the pneumatic signal that shifts the trigger from a disabled state to an enabled state a predetermined amount of time after the second “prime” signal is received. Consequently, the second pneumatic device operates to produce a pneumatic signal that disables the trigger during priming of the water cannon and enables the trigger after priming of the water cannon is sufficiently complete. The third pneumatic device receives a stream of gas that is distributed throughout the pneumatic logic and provides the basis for each of the pneumatic signals produced by the pneumatic logic. Further, the third pneumatic device receives the first “prime” signal provided by the first pneumatic device and the “fire” signal provided by the pneumatic trigger. Operation of the third pneumatic device is according to exclusive-or logic, i.e., the device is only capable of responding to one of the first “prime” signal and the “fire” signal at any point in time. Stated differently, the third pneumatic device is not capable of responding to the first “prime” signal and the “fire” signal at the same time. In operation, the third pneumatic device responds to the first “prime” signal produced by the first pneumatic device by providing the second “prime” signal to the second pneumatic device. The third pneumatic device responds to the “fire” signal produced by the pneumatic trigger by providing a pneumatic signal that causes the valve to release a pressurized gas or liquid into the barrel of the cannon and thereby “fire” the cannon. This pneumatic signal is also provided to the first pneumatic device to indicate that the state of the water canon, namely, that the cannon is in the act of firing. In one embodiment, the first pneumatic device comprises a pneumatic timer that operates to produce the first “prime” signal at a predetermined amount of time after receiving a pneumatic signal indicating that the water cannon is in the act of firing. The predetermined amount of time being an amount of time for the water cannon to sufficiently complete a firing. In another embodiment, the first pneumatic device comprises a pneumatic sensor/gate assembly that operates to produce the first “prime” signal after a sufficiently complete firing of the water cannon is detected by sensing that the water in the barrel of the cannon is at or below a predetermined level. In the case of a piston-type cannon, a sufficiently complete firing is detected by either sensing that the water is at or below a predetermined level or that the piston has traveled to a predetermined location in the barrel. In any event, the pneumatic sensor/gate assembly operates such that the pneumatic signal that indicates that the water cannon is in the act of firing “sets” the gate, i.e., causes the first “prime” signal to become inactive. A pneumatic signal produced by the sensor indicating that a sufficiently complete firing has occurred is applied to the gate and causes the gate to “reset”, i.e., causes the first “prime” signal to become active. In yet a further embodiment, the second pneumatic device comprises a pneumatic timer that operates to produce the pneumatic signal that enables the trigger at a predetermined amount of time after receiving the second “prime” signal. In this case, the predetermined amount of time is an amount of time that is sufficient for the water cannon to have been primed. In another embodiment, the second pneumatic device comprises a pneumatic sensor/gate assembly that operates to produce the pneumatic signal that enables the trigger after a sufficiently complete priming of the water cannon is detected by sensing that the water in the barrel of the cannon is at or above a predetermined level. In the case of a piston-type cannon, a sufficiently complete priming is detected by sensing either that water in the barrel is at or above a predetermined level or that the piston is at a predetermined location in the barrel, i.e., a location from which the piston can be moved to cause a body of water to be ejected from the cannon. In any event, the pneumatic sensor/gate assembly operates such that the second “prime” signal “sets” the gate, i.e., causes the pneumatic signal that disables the trigger to issue. The receipt by the gate of a pneumatic signal from the sensor indicating that a sufficiently complete priming has occurred “resets” the gate, i.e., causes the pneumatic signal that enable the trigger to issue. Another embodiment of the pneumatic control system is applicable to water cannons in which a body of water is loaded before firing but that already have a pneumatic trigger and valve. In this case, the pneumatic control system comprises the pneumatic logic without the valve and pneumatic trigger, and the pneumatic logic is retrofitted to the cannon. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-section of a barrel assembly for a typical piston-type water cannon; FIG. 2 is a cross-section of a barrel assembly for a typical pistonless-type water cannon; FIG. 3 is a schematic of a pneumatic control system for a typical piston-type water cannon; and FIGS. 4A-4C respectively illustrate the states of the pneumatic control system while the piston-type water cannon is firing, after the cannon has fired and while priming of the cannon is taking place, and after priming has been complete but before the cannon is fired. DETAILED DESCRIPTION The present invention is directed to a pneumatic control system for a water cannon whose operation involves the loading of a body of water into the barrel of the cannon and the subsequent application of a force to the body of water that drives the body of water out of the barrel. Before describing the pneumatic control system, two types of water cannons to which the pneumatic control system is applicable are described. The first type is a piston-type water cannon and the second type is a pistonless-type water cannon. Characteristic of both types of cannons is that a body of water is loaded into the barrel of the cannon and a force is then applied to the body of water that drives the body of water out of the cannon. FIG. 1 is a cross-sectional view of a barrel assembly 10 of a typical piston-type water cannon. Generally, the barrel assembly 10 includes a barrel 12 and a piston 14 that resides within the barrel 12 . The piston 14 comprises a first disk 16 , a second disk 18 , and a rod 20 that connects the first disk 16 and the second disk 18 . The barrel 12 includes a first chamber 22 that holds the first disk 16 . In addition, the first chamber 22 includes a nozzle 24 , a water inlet port 26 for loading water into the first chamber 22 , and a first air port 28 that allows air to move in and out of the first chamber 22 during movement of the piston 14 and thereby facilitate movement of the piston 14 . To elaborate, the first air port 28 allows air to enter the first chamber 22 during firing of the water cannon (i.e., during movement of the piston 14 towards the nozzle 24 ) to prevent a vacuum from forming between the first disk 16 and the bottom of the first chamber 22 that would impede the movement of the piston 14 . Similarly, the first air port 28 allows air to exit the first chamber 22 during retraction of the piston 16 . The barrel 12 also includes a second chamber 30 that holds the second disk 18 of the piston 14 . In addition, the second chamber 30 includes a second air port 32 for transmitting air into the second chamber 30 to facilitate movement of the piston 14 towards the nozzle 24 and transmitting air out of the second chamber 30 when the piston 14 is being moved away from the nozzle 24 . A third air port 34 is provided for use in transmitting air that is used to move the piston 14 away from the nozzle 24 and thereby position the piston 14 for subsequently moving towards the nozzle 24 to eject water in the first chamber 22 from the nozzle 24 . A wall 36 separates the first chamber 22 and the second chamber 30 from one another. A hole 38 in the wall 34 accommodates the rod 20 of the piston 14 . Operation of the barrel assembly 10 comprises priming the barrel assembly 10 by injecting water into the first chamber 22 via the water inlet port 26 and moving the piston 14 away from the nozzle 24 by injecting a gas into the second chamber 30 via the third air port 34 . In addition, air is allowed to escape from the first chamber 22 via the first air port 28 . Likewise, gas is allowed to escape from the second chamber 30 via the second air port 32 . The “firing” of the barrel assembly 10 (i.e., the ejection of a body of water located in the first chamber 22 through the nozzle 24 ) is accomplished by injecting pressurized air into the second chamber 30 via the second air port 32 to cause the piston 14 to move towards the nozzle 24 and thereby eject the body of water previously established in the first chamber 22 . Movement of the piston 14 is facilitated by allowing air to enter the first chamber 22 via the first air port 28 and air to escape from the second chamber 30 via the third air port 34 . FIG. 2 is a cross-sectional view of a barrel assembly 42 of a typical pistonless-type water cannon. Generally, the assembly 42 includes a chamber 44 for holding a body of water. The chamber 44 is substantially defined by an inner sleeve 46 and includes a closed end 48 and a nozzle 50 . A water inlet port 52 is utilized to load a body of water into the chamber 44 . An outer sleeve 54 is separated from the inner sleeve 46 and in conjunction with the inner sleeve 46 defines a gas channel 56 . A gas inlet port 58 is used to transmit a gas to the gas channel 56 . Operation of the barrel assembly 42 comprises priming the barrel assembly 42 by injecting water into the chamber 44 via the water inlet port 52 . Once a sufficient body of water has been loaded into the chamber 44 , a gas (e.g., air) is injected into the gas channel 56 via the gas inlet port 58 . The gas travels down the gas channel and, in so doing, drives the body of water in the chamber 44 out the nozzle 50 . With reference to FIG. 3, an embodiment of a pneumatic control system 62 that is applicable to a piston-type water cannon of the type illustrated in FIG. 2 is described. A barrel assembly 64 for the piston-type water cannon is illustrated with elements that correspond to the elements of barrel assembly 10 given the same reference numbers. The control system 62 generally comprises: (a) a pneumatic valve 66 for transmitting gas (e.g., air) to and from the second chamber 30 of the barrel 12 ; (b) a pneumatic trigger 68 for generating a pneumatic “fire” signal to cause the valve 66 to inject air into the second chamber 30 of the barrel 12 to move the piston 14 and thereby eject water from the first chamber 22 via the nozzle 24 ; (c) a first pneumatic timer 70 for providing a pneumatic signal after a sufficiently completed firing of the barrel assembly 64 that is used in priming the barrel assembly 64 for another firing; (d) a second pneumatic timer 72 for providing a pneumatic signal after the barrel assembly 64 has been sufficiently primed that enables the pneumatic trigger 68 ; and (e) a pneumatic exclusive-or valve 74 that responds to the pneumatic signal output by the first pneumatic timer 70 by providing a pneumatic signal to the second pneumatic timer 72 that causes the second pneumatic timer 72 to wait a sufficient amount of time for priming activities to be completed before providing a pneumatic signal that enables the pneumatic trigger 68 and by taking action to cause the piston 14 to be positioned for a firing The pneumatic exclusive-or valve 74 also responds to the pneumatic “fire” signal output by the pneumatic trigger by providing a pneumatic signal to the first pneumatic timer 70 that indicates that the barrel assembly 64 is either in the act of being fired or primed. The control system 62 further includes a quick exhaust valve 76 that directs air to the second port 34 to cause the piston 14 to retract during priming of the barrel assembly 64 and directs air from the second chamber 30 to the exterior environment during firing of the barrel assembly 64 . The control system 62 further comprises a shot counter 78 that provides a count of the number of firings of the barrel assembly 64 , which is useful for maintenance purposes and the like. Also included in the control system 62 is a pressure indicator 80 that provides a user with an indication of when the pneumatic trigger 68 is enabled and, as a consequence, when actuation of the pneumatic trigger 68 will result in the firing of the water cannon. An air filter 82 serves to filter the air that is used by the pneumatic components in the remainder of the control system 62 . The pneumatic valve 66 is a 3-way, air actuated valve that includes an inlet port 86 for receiving air from an air supply line 88 , a bi-directional port 90 for providing air to the second chamber 30 during firing of the barrel assembly 64 and receiving air from the second chamber 30 during priming of the barrel assembly 64 , and a second outlet port 92 for venting air received by the bi-directional port 90 during priming of the barrel assembly 64 to the exterior environment. A control port 94 is used to place the valve 66 in either a “fire” state or a “primed” state. In the “fire” state, the valve 66 allows air to pass from the inlet port 86 to the bi-directional port 90 and then into the second chamber 30 of the barrel assembly 64 to move the piston 14 and thereby eject a body of water in the first chamber 22 from the nozzle 24 . In the “primed” state, the valve 66 allows air from the second chamber 30 of the barrel assembly 64 to pass from the bi-directional port 90 to the output port 92 during priming and, more specifically, during retraction of the piston 14 . The control port 94 is responsive to a pneumatic firing/priming signal that is in either a “firing” state or a “priming” state and provided by the pneumatic exclusive-or valve 74 . When the firing/priming signal is in the “firing” state, the control port 94 places the valve in the “fire” state. Conversely, when the firing/priming signal is in the “priming” state, the control port 94 places the valve in the “primed” state. The pneumatic trigger 68 is a 3-way, manually activated valve that includes an outlet port 98 for providing a pneumatic “fire” signal, a trigger 100 , and a control port 102 that is used to place the trigger 68 in either a “disabled” state or an “enabled” state. In the “disabled” state, actuation of the trigger 100 has no effect, i.e., there is no “fire” signal produced at the outlet port 98 . In effect, the trigger 68 is in a “safetyon” condition in the “enabled” state, which is effectively a “safety-off” condition, actuation of the trigger 100 results in a “fire” signal being produced at the outlet port 98 . The control port 102 is responsive to a pneumatic disable/enable signal that is either in a “disable” state or an “enable” state and provided by the second pneumatic timer 72 . When the disable/enable signal is in the “disable” state, the control port 102 places the trigger 68 in the “disabled” state. Conversely, when the disable/enable signal is in the “enable” state, the control port 102 places the trigger 68 in the “enabled” state. The first pneumatic timer 70 includes an inlet port 106 for receiving a pneumatic firing/priming signal from the exclusive-or valve 74 and an outlet port for providing a pneumatic, first “prime” signal. When the timer 70 receives a firing/priming signal that is in a “firing” state (i.e., indicative of the barrel assembly 64 being fired), the timer 70 responds by providing the first “prime” signal at a predetermined amount of time after receiving the firing/priming signal in the “firing” state. The predetermined amount of time is at least the time required for a firing of the barrel assembly 64 to be sufficiently completed. Consequently, the first “prime” signal indicates that a firing of the barrel assembly 64 is at a point that priming operations can commence for a subsequent firing. When the timer 70 receives a firing/priming signal that is in the “priming” state (i.e., indicative of the barrel assembly 64 being primed for a firing), the first “prime” signal becomes inactive. The second pneumatic timer 72 includes an inlet port 112 for receiving a second “prime” signal from the exclusive-or valve 74 and an outlet port 114 for providing the pneumatic, disable/enable signal to the trigger 68 . When the timer 72 receives the second “prime” signal (i.e., indicative of the barrel assembly 64 being primed for another firing), the timer 72 responds by providing the disable/enable signal in the enabled state at a predetermined amount of time after receiving the second “prime” signal. The predetermined amount of time is at least the time required for a the barrel assembly 64 to be primed, i.e., the barrel 12 loaded with a body of water and the piston 14 positioned to apply a mechanical force to the body of water. Consequently, the providing of the disable/enable signal in the enable state indicates that the priming of the barrel assembly 64 is sufficiently complete. As a consequence, the pneumatic trigger 68 can be actuated and the barrel assembly fired. When the second “prime” signal is inactive (i.e., indicative of the barrel assembly 64 being fired), the timer 72 provides the disable/enable signal in the disable state, which renders any actuation of the pneumatic trigger 68 ineffective. The pneumatic exclusive-or valve 74 includes a gas port 118 for receiving air from the air supply line 88 that has been processed by the air filter 82 . The air received at the gas port 118 is distributed throughout the control system 62 and used by the components of the control system 62 to generate pneumatic signals. In addition, the air received at the gas port 118 is used to retract the piston 14 during priming of the barrel assembly 64 . The valve 74 further includes a first outlet port 120 for providing the second “prime” signal to the second pneumatic timer 72 and providing gas to the second port 34 to retract the piston 14 during priming of the barrel assembly 64 . A second outlet port 122 is used to provide the firing/priming signal. A first control port 124 receives the first “prime” signal provided by the first pneumatic timer 70 . Similarly, a second control port 126 receives the “fire” signal produced by the pneumatic trigger 68 . When the first “prime” signal is received at the first control port 124 , the valve 74 responds by providing the second “prime” signal to the second pneumatic timer 72 . In addition, the valve 74 provides gas to the second port of the barrel assembly 64 to facilitate the retraction of the piston 14 . The valve 74 further responds to the first “prime” signal by providing a firing/priming signal in the “priming” state at the second outlet port 122 . In contrast, when the “fire” signal is received at the second control port 126 , the valve responds by providing the firing/priming signal in the “firing” state at the second outlet port 122 . Further, the valve 74 causes the second “prime” signal at the first port 120 to go inactive, which is indicative of the barrel assembly 64 being fired. Additionally, the valve 74 terminates the provision of any air to the barrel 12 via the second port 34 that would inhibit the firing action of the piston 14 . The shot counter 78 is incremented every time the barrel assembly is fired. In the illustrated embodiment, the counter 78 is incremented every other transition between the “firing” and “priming” states of the firing/priming signal. The pressure indicator 80 indicator provides a visual indication to an operator that the disable/enable signal provided by the second pneumatic timer 72 is in the “enable” state, meaning that the operator can actuate the trigger 100 to effect the firing of the barrel assembly 64 . A pair of lubrication ports 130 A, 130 B allow lubricants to be injected into the control system 62 during servicing that extend the life of elastomeric seals and the like that are present in many of the components of the system. Generally, operation of a pneumatic control system 62 for the piston-type water cannon involves the steps of: (a) priming the water cannon, (i.e., loading a body of water into the barrel 12 , positioning the piston 14 for subsequently applying a force to the body of water; disabling the trigger 68 , and placing the valve 66 in the “priming” state); (b) enabling the trigger 68 after the priming step is sufficiently complete; and (c) firing the cannon (i.e., placing the valve 66 in the “firing” state and thereby causing the piston 14 to apply a mechanical force to the body of water in the barrel 12 ). With reference to FIG. 4A, the operation of the pneumatic control system 62 is described beginning with the firing step. The firing step commences with a user actuating the trigger 100 after the pneumatic trigger 68 has received a disable/enable signal in the enable state from the second pneumatic timer 72 . Actuation of the trigger 100 causes the pneumatic trigger 68 to provide the pneumatic “fire” signal to the second control port 126 of the exclusive-or valve 74 . In addition, actuation of the trigger 100 causes the pressure in the line extending between the second pneumatic timer 72 and the trigger 68 to decrease and thereby place the disable/enable signal in the “disable” state. The exclusive-or valve 74 responds to the “fire” signal from the trigger 68 by blocking the outlet port 120 , which causes pressure in the line between the valve 74 and the second pneumatic timer 72 to decrease and thereby reset or render inactive the second “prime” signal. Further, the valve 74 terminates the provision of air from the outlet port 120 to the third air port 34 associated with the barrel 12 . As a consequence, air is not being forced into the second chamber 30 of the barrel 12 that would inhibit the forward movement of the piston 14 . In addition, the forward movement of the piston 14 causes air that is in the second chamber and between the second disk 18 and the wall 36 to be forced out of the third air port 34 . The air is then directed by operation of the quick exhaust valve 76 to the exterior environment. The exclusive-or valve 74 also responds to the “fire” signal by providing the firing/priming signal in the “firing” state at the second outlet port 122 . The firing/priming signal in the “firing” state is conveyed to the control port 94 of the valve 66 , the shot counter 78 , and the inlet port 106 of the first pneumatic timer 70 . In response to the firing/priming signal in the “firing” state, the control port 94 places the valve in the “firing” state, which allows pressurized air from the air supply line 88 to pass from the inlet port 86 to the outlet port 92 and into the second chamber 30 of the barrel 12 . Assuming the barrel assembly 64 has been appropriately primed, the pressurized air then forces the piston 12 towards the nozzle 24 and in so doing forces at least a portion of the body of water in the first chamber 22 of the barrel out of the nozzle 24 . The shot counter 78 responds to the transition of the firing/priming signal from the “priming” state to the “firing” state by incrementing its counter. The first pneumatic timer 70 responds to the firing/priming signal in the “firing” state by implementing a “delay” whereby the first “prime” signal will be produced at a outlet port 108 at a predetermined amount of time after the firing/priming signal in the “firing” state is received. The predetermined amount of time being a time that allows for the sufficient completion of the firing step before beginning the priming step. With reference to FIG. 4B, the priming step commences with the first pneumatic timer 70 providing the first “prime” signal at the outlet port 108 . The first “prime” signal is applied to the first control port 124 of the exclusive-or valve 74 . In response, the exclusive-or valve 74 blocks the outlet port 122 , which causes pressure in the line between the valve 74 and the first pneumatic timer 72 to decrease and thereby place the firing/priming signal in the “priming” state. The valve 74 also responds to the first “prime” signal being applied to the first control port 124 by causing air to be conveyed from the first outlet port 120 to the quick exhaust valve 76 . In turn, the quick exhaust valve directs the air to the third air port 34 . This air is then used to push the piston 14 away from the nozzle 24 and thereby position the piston 14 for a subsequent firing. The first control port 124 also responds to the first “prime” signal by causing the second “prime” signal to be provided at the first outlet port 120 . The second “prime” signal is conveyed to the inlet port 112 of the second pneumatic timer 72 . The second pneumatic timer 72 responds to the second “prime” signal by implementing a “delay” such that a disable/enable signal in the “enable” state will be produced at a outlet port 114 at a predetermined amount of time after the second “prime” signal is received. The predetermined amount of time being an amount of time that allows for the sufficient completion of the priming step before beginning the enabling step. With reference to FIG. 4C, the enabling step (which can be considered to be the end of the priming step) involves the second pneumatic timer providing the disable/enable signal in the enable state at the outlet port 114 . The disable/enable signal in the enable state is conveyed to the pressure indicator 80 and the trigger 68 . The pressure indicator 80 responds to the disable/enable signal in the enable state by providing the user of the water cannon with an indication that the cannon is primed for firing and the trigger 68 is enabled, i.e., in a safety-off condition. The trigger 68 responds to the disable/enable signal in the enable state by becoming enabled, i.e., capable of generating the “fire” signal upon actuation of the trigger 100 . With reference to FIG. 3, it should be appreciated that the control system 62 is readily modified to operate with a pistonless-type water cannon, such as the cannon shown in FIG. 2 . Namely, since there is no piston, the structure between the pneumatic exclusive-or valve 74 and the barrel assembly that is used to move the piston 14 away from the nozzle 24 is eliminated. In addition, the valve 66 is replaced with a valve that need only respond to the firing/priming signal in the “firing” state by allowing pressurized air to be transmitted from an input port that is in communication with the air supply line 88 to an outlet port that is in communication with the gas inlet port of the piston-less water cannon, e.g., the gas inlet port 58 of the barrel assembly 42 in FIG. 2 . With the exception of piston related functions, operation of the pneumatic control system for a pistonless-type water cannon is substantially identical to that for the piston-type water cannon. A number of modifications to the control system 62 are also feasible. For instance, while the operation of the control system 62 has been described with the understanding that there is a substantially continuous flow of water into the barrel of the water cannon, i.e., water is allowed to flow into the barrel regardless of the state of the barrel assembly, there are applications in which it is desirable to only allow water to flow into the barrel during priming operations. For such applications, the flow of water is controlled by a valve that is turned “on” and “off” via pneumatic signals. To elaborate, the valve is turned “on” so that water flows into the barrel using either the first “prime” signal or the “second” prime signal. Consequently, water begins flowing into the barrel at the beginning of the priming period or some predetermined time thereafter. The valve is turned “off” to terminate the flow of water the barrel at a predetermined time after the first “prime” signal or second “prime” signal becomes active and at or before the time that the trigger 68 is enabled. In one embodiment, the disable/enable in the enable state is used to terminate the flow of water to the barrel. In any event, the flow of water to the barrel is terminated sometime during the priming of the barrel assembly. Another possible modification to the control system 62 is to replace one or both of the first pneumatic timer 70 and second pneumatic timer 72 with a pneumatic sensor/gate device. The pneumatic sensor portion of the device senses the level of the water within the barrel of the water cannon. In the case of a pneumatic sensor/gate that replaces the first pneumatic timer 70 , the sensor operates to output a pneumatic signal when the level of water in the barrel is at or below a predetermined point or level, indicating that the firing of the barrel assembly is sufficiently complete for priming to commence. The pneumatic signal is applied to the gate portion. In response, the gate portion outputs the first “prime” signal. Similarly, in the case of a pneumatic sensor/gate device that replaces the second pneumatic timer 72 , the sensor operates to output a pneumatic signal when the level of water in the barrel is at or above a predetermined point or level, indicating that priming of the barrel assembly is sufficiently complete and, as such, the trigger 68 can be enabled. The pneumatic signal is applied to the gate portion, which responds to the signal by outputting the disable/enable signal in the enable state. It should be appreciated that a pneumatic sensor/gate device that replaces either the first pneumatic timer 70 or the second pneumatic timer 72 in a pneumatic control system that is used to control a piston-type water cannon can sense the position of the piston rather than sensing the level of water. Another possible modification to the pneumatic control system 62 is to invert all or some of the logic signals. For example, the firing/priming signal has been described such that when the signal is in the “firing” state the line carrying the signal has a higher pressure than when the signal is in the “priming” state. The pneumatic control system 62 is equally adaptable or capable of utilizing a firing/priming signal in which the “firing” state has a lower pressure than the “priming” state. A further possible modification involves realizing the functionality of the pneumatic exclusive-or valve 74 with two or more discrete components. Yet a further modification to the pneumatic control system 62 to employ a gas other than air. Further, the system 62 is capable of being adapted so that a liquid is the transmission medium for all or some of the signals. Consequently, the term pneumatic herein embraces fluid based signals whether in gas form or a liquid form.
A method and apparatus are provided for pneumatically controlling the operation of a water cannon such that the need for electrically power in the immediate vicinity of the water cannon is substantially avoided.
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CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation of International application No. PCT/FR2005/003,219, filed Dec. 21, 2005, which is incorporated herein by reference in its entirety; which claims the benefit of priority of French Patent Application No. 04/13,898, filed Dec. 23, 2004. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to substituted N-[(4,5-diphenyl-3-alkyl-2-thienyl)methyl]amine derivatives, to their preparation and to their therapeutic use. 2. Description of the Art Diphenylpyrazole derivatives with affinity for the cannabinoid CB 1 receptors have been described especially in patents U.S. Pat. No. 5,624,941, EP 0 576 357, EP 0 656 354, EP 1 150 961 and WO 2005/073197. 4,5-Diarylthiophene derivatives with anti-inflammatory and analgesic properties are described in international patent application WO 91/19708. Thiophene-2-carboxamide derivatives are described in international patent application WO 2005/035488. All of the references described herein are incorporated herein by reference in their entirety. SUMMARY OF THE INVENTION Novel substituted N-[(4,5-diphenyl-3-alkyl-2-thienyl)methyl]amine derivatives have now been found, which have antagonist properties towards the cannabinoid CB 1 receptors. One subject of the present invention is compounds corresponding to the formula: in which: X represents a group R 1 represents: a (C 1 -C 7 )alkyl; a (C 3 -C 12 ) non-aromatic carbocyclic radical, which is unsubstituted or substituted one or more times with a (C 1 -C 4 )alkyl; a (C 3 -C 7 )cycloalkylmethyl, which is unsubstituted or substituted one or more times on the carbocycle with a (C 1 -C 4 )alkyl; an unsubstituted phenyl or a phenyl mono-, di- or trisubstituted with substituents independently chosen from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy, a (C 1 -C 4 )alkylamino, a di(C 1 -C 4 )alkylamino, a cyano, a trifluoromethyl radical, a trifluoromethoxy radical, a group S(O) n Alk, a (C 1 -C 4 )alkylcarbonyl group; or from a phenyl, phenoxy, pyrrolyl, imidazolyl, pyridyl or pyrazolyl radical, the said radicals being unsubstituted or substituted one or more times with a (C 1 -C 4 )alkyl; an unsubstituted benzyl or a benzyl mono- or disubstituted on the phenyl with substituents independently chosen from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy or a trifluoromethyl radical, or alpha-substituted with one or two identical or different groups chosen from a (C 1 -C 4 )alkyl and a (C 3 -C 7 )cycloalkyl; an unsubstituted phenethyl or a phenethyl mono- or disubstituted on the phenyl with substituents independently chosen from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy and a trifluoromethyl radical; a benzhydryl; a benzhydrylmethyl; an aromatic heterocyclic radical chosen from a pyrrolyl, an imidazolyl, a furyl, a thienyl, a pyrazolyl or an indolyl, which is unsubstituted or substituted one or more times with substituents independently chosen from a halogen atom, a (C 1 -C 4 )alkyl and a trifluoromethyl radical; R 2 represents a hydrogen atom or a (C 1 -C 3 )alkyl; R 3 represents a (C 1 -C 5 )alkyl or a (C 3 -C 7 )cycloalkyl; R 4 represents an unsubstituted phenyl or a phenyl mono-, di- or trisubstituted with substituents chosen independently from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy, a trifluoromethyl radical and a group S(O) n Alk; R 5 represents an unsubstituted phenyl or a phenyl mono-, di-, or trisubstituted with substituents chosen independently from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy, a trifluoromethyl radical and a group S(O) n Alk; R 6 represents a hydrogen atom or a (C 1 -C 3 )alkyl; n represents 0, 1 or 2; Alk represents a (C 1 -C 4 )alkyl. The compounds of formula (I) may comprise one or more asymmetric carbon atoms. They may thus exist in the form of enantiomers or diastereoisomers. These enantiomers and diastereoisomers, and also mixtures thereof, including racemic mixtures, form part of the invention. The compounds of formula (I) may exist in the form of hydrates or solvates, i.e. in the form of associations or combinations with one or more water molecules or with a solvent. Such hydrates and solvates also form part of the invention. DETAILED DESCRIPTION OF THE INVENTION The term “halogen atom” means a bromine, chlorine, fluorine or iodine atom. The terms “(C 1 -C 3 )alkyl”, “(C 1 -C 4 )alkyl”, “(C 1 -C 5 )alkyl” and “(C 1 -C 7 )alkyl” mean, respectively, a linear or branched alkyl radical of one to three carbon atoms, of one to four carbon atoms, of one to five carbon atoms or of one to seven carbon atoms, respectively, such as a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl or heptyl radical. The term “(C 1 -C 4 )alkoxy” means a linear or branched alkoxy radical containing from one to four carbon atoms such as a methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy or tert-butoxy radical. The term “(C 3 -C 7 )cycloalkyl” means a cyclic alkyl group of 3 to 7 carbon atoms such as a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl group. The non-aromatic C 3 -C 12 carbocyclic radicals include fused, bridged or spirane monocyclic or polycyclic radicals. The monocyclic radicals include cycloalkyls, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The fused, bridged or spirane bicyclic or tricyclic radicals include, for example, norbornyl, bornyl, isobornyl, noradamantyl, adamantyl, spiro[5.5]undecyl, bicyclo[2.2.1]heptyl, bicyclo[3.2.1]octyl and bicyclo[3.1.1]heptyl radicals. Among the compounds of formula (I) that are subjects of the invention, the following are distinguished: the compounds of formula (IA) in which —X— represents a —CO— radical and the substituents R 1 to R 5 are as defined for the compounds of formula (I); the compounds of formula (IB) in which —X— represents an —SO 2 — radical and the substituents R 1 to R 5 are as defined for the compounds of formula (I); the compounds of formula (IC) in which —X— represents a radical —CON(R 6 )— and the substituents R 1 to R 6 are as defined for the compounds of formula (I); the compounds of formula (ID) in which —X— represents a —COO— radical and the substituents R 1 to R 5 are as defined for the compounds of formula (I); the compounds of formula (IE) in which —X— represents an —SO— radical and the substituents R 1 to R 5 are as defined for the compounds of formula (I). According to the present invention, the compounds of formula (I) that are preferred are those in which: X represents a group R 1 represents: a (C 1 -C 7 )alkyl; a (C 3 -C 7 )cycloalkyl which is unsubstituted or substituted one or more times with a (C 1 -C 3 )alkyl group; a (C 3 -C 7 )cycloalkylmethyl which is unsubstituted or substituted one or more times on the carbocycle with a (C 1 -C 3 )alkyl; a phenyl which is unsubstituted or mono-, di- or trisubstituted with substituents chosen independently from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy, a cyano, a trifluoromethyl radical, a trifluoromethoxy radical, a group S(O) n Alk, a (C 1 -C 4 )alkylcarbonyl group and a phenyl; a benzyl which is unsubstituted or mono- or disubstituted with substituents chosen independently from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy and a trifluoromethyl radical; an indolyl; R 2 represents a hydrogen atom or a (C 1 -C 3 )alkyl; R 3 represents a (C 1 -C 5 )alkyl or a (C 3 -C 7 )cycloalkyl; R 4 represents a phenyl which is unsubstituted or mono-, di- or trisubstituted with substituents chosen independently from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy, a trifluoromethyl radical and a group S(O) n Alk; R 5 represents a phenyl which is unsubstituted or mono-, di- or trisubstituted with substituents chosen independently from a halogen atom, a (C 1 -C 4 )alkyl, a (C 1 -C 4 )alkoxy, a trifluoromethyl radical and a group S(O) n Alk; R 6 represents a hydrogen atom or a (C 1 -C 3 )alkyl; n represents 0, 1 or 2; Alk represents a (C 1 -C 4 )alkyl, in base form and also in hydrate or solvate form. Among the compounds of formula (I) that are subjects of the invention, a first group of compounds consists of the compounds for which: X represents a —CO— group, an —SO 2 — group, an —SO— group or a —CON(CH 2 CH 3 )— group; R 1 represents: a 1-ethylpropyl; a 1-methylpentyl; a tert-butyl; an ethyl; a cycloheptyl; a 1-methylcyclopropyl; a 3-(trifluoromethyl)phenyl; a 4-(trifluoromethyl)phenyl; and/or R 2 represents a hydrogen atom; and/or R 3 represents a methyl; and/or R 4 represents a 4-bromophenyl; a 4-chlorophenyl; and/or R 5 represents a 2,4-dichlorophenyl; and also the hydrates or solvates thereof. Among the compounds of the latter group, mention may be made of the compounds of formula (I) for which: X represents a —CO— group, an —SO 2 — group; an —SO— group or a —CON(CH 2 CH 3 )— group; R 1 represents: a 1-ethylpropyl; a 1-methylpentyl; a tert-butyl; an ethyl; a cycloheptyl; a 1-methylcyclopropyl; a 3-(trifluoromethyl)phenyl; a 4-(trifluoromethyl)phenyl; R 2 represents a hydrogen atom; R 3 represents a methyl; R 4 represents a 4-bromophenyl; a 4-chlorophenyl; R 5 represents a 2,4-dichlorophenyl; and also the hydrates or solvates thereof. Among the compounds of the latter group, mention may be made of the compounds of formula (I) for which: X represents a —CO— group or an —SO 2 — group; R 1 represents: a 1-ethylpropyl; a 1-methylpentyl; a cycloheptyl; a 3-(trifluoromethyl)phenyl; R 2 represents a hydrogen atom; R 3 represents a methyl; R 4 represents a 4-bromophenyl; R 5 represents a 2,4-dichlorophenyl; and also the hydrates or solvates thereof. Among the compounds of formula (I) that are subjects of the invention, mention may be made especially of the following compounds: N-[[4-(4-bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-ethylbutanamide; N-[[4-(4-bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]cycloheptanecarboxamide; N-[[4-(4-bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-3-(trifluoromethyl)benzenesulfonamide; N-[[4-(4-bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-methylhexanamide; N-[[4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2,2-dimethylpropanamide. N-[[4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-ethylbutanamide. N-[[4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-1-methylcyclopropanecarboxamide. N-[[4-(4-bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-4-(trifluoromethyl)benzamide. N-[[4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-methylpropane-2-sulfinamide. N-[[4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-methylpropane-2-sulfonamide. 3-[[4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-1,1-diethylurea. and also the hydrates or solvates thereof. In the text hereinbelow, the term “protecting group Pg” means a group that makes it possible firstly to protect a reactive function such as a hydroxyl or an amine during a synthesis, and secondly to regenerate the intact reactive function at the end of the synthesis. Examples of protecting groups and protection and deprotection methods are given in “Protective Group in Organic Synthesis”, Green et al., 2nd Edition (John Wiley & Sons, Inc., New York), 1991. In the text hereinbelow, the term “leaving group” means a group that can be readily cleaved from a molecule by breaking a heterolytic bond, with loss of an electron pair. This group may thus be readily replaced with another group during a substitution reaction, for example. Such leaving groups are, for example, halogens or an activated hydroxyl group such as a methanesulfonate, benzenesulfonate, p-toluenesulfonate, triflate, acetate, etc. Examples of leaving groups and references for preparing them are given in “Advances in Organic Chemistry”, J. March, 3rd Edition, Wiley Interscience, 1985, p. 310-316. In accordance with the invention, the compounds of formula (I) may be prepared according to a process that is characterized in that: a compound of formula:  in which R 2 , R 3 , R 4 and R 5 are as defined for a compound of formula (I), is treated: either with an acid or a functional derivative of this acid of formula: HOOC—R 1   (III) in which R 1 is as defined for a compound of formula (I), when a compound of formula (I) is to be prepared in which —X— represents a —CO— group; or with a sulfonyl halide of formula: Hal-SO 2 —R 1   (IV) in which R 1 is as defined for a compound of formula (I) and Hal represents a halogen atom, preferentially chlorine, when a compound of formula (I) is to be prepared in which —X— represents an —SO 2 — group; or with a haloformate of formula: HalCOOAr  (V) in which Hal represents a halogen atom and Ar represents a phenyl or a 4-nitrophenyl, to give an intermediate compound of formula: in which R 2 , R 3 , R 4 and R 5 are as defined for a compound of formula (I), which is then reacted with an amine of formula: HN(R 6 )R 1   (VII) in which R 1 and R 6 are as defined for a compound of formula (I), when a compound of formula (I) is to be prepared in which —X— represents a group —CON(R 6 )—; or with a haloformate of formula: HalCOO—R 1   (XXIV) in which Hal represents a halogen atom and R 1 is as defined for a compound of formula (I), when a compound of formula (I) is to be prepared in which —X— represents a —COO— group, or with a sulfinyl halide of formula: Hal-SO—R 1   (XXV) in which R 1 is as defined for a compound of formula (I) and Hal represents a halogen atom, when a compound of formula (I) is to be prepared in which —X— represents an —SO— group. When a compound of formula (II) is treated with the acid of formula (III) itself, the process is performed in the presence of a coupling agent used in peptide chemistry, such as 1,3-dicyclohexylcarbodiimide or benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate or benzotriazol-1-yloxy-tris(pyrrolidino)phosphonium hexafluorophosphate or 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate, in the presence of a base such as triethylamine, N,N-diisopropylethylamine or 1a 4-dimethylaminopyridine, in a solvent such as dichloromethane, dichloroethane, N-N-dimethylformamide or tetrahydrofuran, at a temperature of between −10° C. and the reflux temperature of the solvent. A functional derivative of the acid (III) that may be used is the acid chloride, the anhydride, a mixed anhydride, a C 1 -C 4 alkyl ester in which the alkyl is straight or branched, or an activated ester, for example the p-nitrophenyl ester. Thus, in the process according to the invention, the acid chloride obtained by reacting thionyl chloride or oxalyl chloride with the acid of formula (III) may also be reacted with the compound of formula (II), in a solvent such as a chlorinated solvent (for example dichloromethane, dichloroethane or chloroform), an ether (for example tetrahydrofuran or dioxane) or an amide (for example N,N-dimethylformamide), under an inert atmosphere, at a temperature of between 0° C. and room temperature, in the presence of a tertiary amine such as triethylamine, N-methylmorpholine or pyridine. One variant consists in preparing the mixed anhydride of the acid of formula (III) by reacting ethyl chloroformate with the acid of formula (III), in the presence of a base such as triethylamine, and in reacting it with the compound of formula (II), in a solvent such as dichloromethane, under an inert atmosphere, at room temperature, in the presence of a base such as triethylamine. When the compound of formula (II) is treated with a sulfonyl halide of formula (IV), the process is performed in the presence of a base such as triethylamine or diisopropylethylamine, in a solvent such as dichloromethane or tetrahydrofuran and at a temperature of between room temperature and the reflux temperature of the solvent. According to one variant of the process, the compounds of formula (I) in which —X— represents an —SO 2 — group may be prepared by reacting a compound of formula (I) in which —X— represents an —SO— group with an oxidizing agent. An oxidizing agent that may be used is 3-chloroperbenzoic acid, in a solvent such as dichloromethane and at a temperature of between 0° C. and room temperature. When a compound of formula (II) is treated with a haloformate of formula (V), the process is performed in the presence of a base such as triethylamine, in a solvent such as dichloromethane and at a temperature of between 0° C. and room temperature. The intermediate compound of formula (VI) thus obtained is then reacted with an amine of formula (VII), in a solvent such as dichloromethane, in the presence of a base such as triethylamine and at a temperature of between 0° C. and the reflux temperature of the solvent. According to one variant of the process, the compounds of formula (I) in which —X— represents a group —CON(R 6 )— in which R 6 =H may be prepared by reacting a compound of formula (II) with an isocyanate of formula R 1 —N═C═O (VIII), in the presence of a base such as triethylamine, in a solvent such as dichloromethane and at a temperature of between room temperature and the reflux temperature of the solvent. According to another variant of the process, the compounds of formula (I) in which —X— represents a group —CON(R 6 )— may be prepared by reacting a compound of formula (II) with a compound of formula ClCON(R 6 )R 1 (IX) in the presence of a base such as triethylamine or 4-dimethylaminopyridine, in a solvent such as dichloromethane and at a temperature of between 0° C. and the reflux temperature of the solvent. When a compound of formula (II) is treated with a haloformate of formula (XXIV), the process is performed in the presence of a base such as triethylamine, in a solvent such as dichloromethane and at a temperature of between 0° C. and the reflux temperature of the solvent. When a compound of formula (II) is treated with a sulfinyl halide of formula (XXV), the process is performed in the presence of a base such as triethylamine, in a solvent such as dichloromethane and at a temperature of between room temperature and the reflux temperature of the solvent. According to another variant of the process, a compound of formula (I) in which R 2 represents a (C 1 -C 3 )alkyl may be prepared by reacting a compound of formula (I) in which R 2 =H with a (C 1 -C 3 )alkyl halide, in the presence of a base such as sodium hydride, in a solvent such as N,N-dimethylformamide and at a temperature of between room temperature and the reflux temperature of the solvent. The compounds of formula (I) thus obtained may be subsequently separated from the reaction medium and purified according to standard methods, for example by crystallization or chromatography. The compounds of formula (II) are prepared by reacting a compound of formula: in which R 3 , R 4 and R 5 are as defined for a compound of formula (I) and Y represents a leaving group as defined above, preferably a halogen atom or an activated hydroxyl group such as a methanesulfonate, benzenesulfonate, p-toluenesulfonate or triflate group, with a compound of formula: H 2 N—R 2   (XI) in which R 2 is as defined for a compound of formula (I). The reaction is performed in a solvent such as N,N-dimethylformamide, acetonitrile, dichloromethane, toluene or 2-propanol, and in the presence or absence of a base. When a base is used, it is chosen from organic bases such as triethylamine, N,N-diisopropylethylamine or N-methylmorpholine. The reaction is performed at a temperature of between 0° C. and the reflux temperature of the solvent. According to one variant, a compound of formula (II) in which R 2 =H may also be prepared by reacting a compound of formula (X) in which Y=Cl with 1,3,5,7-tetraazatricyclo[3.3.1 3,7 ]decane (or hexamethylenetetramine), followed by hydrolysis with a strong acid such as hydrochloric acid. According to another variant, a compound of formula (II) in which R 2 =H may also be prepared by reducing a compound of formula: in which R 3 , R 4 and R 5 are as defined for a compound of formula (I). The reaction is performed using a reducing agent such as borane in a solvent such as tetrahydrofuran, at a temperature of between room temperature and the reflux temperature of the solvent, followed by an acid hydrolysis. The compounds of formula (III) are known. The compounds of formula (IV) are commercially available or described in the literature, or may be prepared according to methods described therein such as in J. Org. Chem. USSR, 1970, 6, 2454-2458; J. Am. Chem. Soc., 1952, 74, 2008; J. Med. Chem., 1977, 20(10), 1235-1239; EP 0 469 984; WO 95/18105. For example, the compounds of formula (IV) may be prepared by halogenation of the corresponding sulfonic acids or salts thereof, for example the sodium or potassium salts thereof. The reaction is preformed in the presence of a halogenating agent such as phosphorus oxychloride, thionyl chloride, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride, without solvent or in a solvent such as a halogenated hydrocarbon or N,N-dimethylformamide and at a temperature of between −10° C. and 200° C. The compounds of formulae (V), (VII), (VIII) and (IX) are known or are prepared according to known methods. The compounds of formula (X) are prepared from compounds of formula: in which R 3 , R 4 and R 5 are as defined for a compound of formula (I), according to the standard methods mentioned above. Thus, for example, when, in a compound of formula (X), Y represents a halogen atom, a compound of formula (XIII) is treated with a halogenating agent such as PCl 5 , PBr 3 , HBr or BBr 3 , in a solvent such as dichloromethane and at a temperature of between 0° C. and room temperature. When, in a compound of formula (X), Y represents a methanesulfonate, a benzenesulfonate, a p-toluenesulfonate or a trifluoromethanesulfonate, a compound of formula (XIII) is reacted with a sulfonyl chloride of formula W—SO 2 —Cl in which W represents a methyl, a phenyl, a p-tolyl or a trifluoromethyl. The reaction is performed in the presence of a base such as triethylamine, pyridine or N,N-diisopropylethylamine, in a solvent such as dichloromethane or toluene and at a temperature of between −20° C. and the reflux temperature of the solvent. The compounds of formula (XI) are known. The compounds of formula (XII) are prepared by reacting an acid or a functional derivative of this acid of formula: in which R 3 , R 4 and R 5 are as defined for a compound of formula (I), with aqueous ammonia according to the methods described above for the reaction of a compound (II) with a compound (III). The compounds of formula (XIII) are prepared via a reduction reaction of the compounds of formula: in which R 3 , R 4 and R 5 are as defined for a compound of formula (I) and Z represents a hydroxyl or a (C 1 -C 2 )alkoxy. The reaction is performed in the presence of a reducing agent such as sodium borohydride or lithium aluminum hydride, in a solvent such as tetrahydrofuran, and at a temperature of between −20° C. and room temperature. When a compound of formula (XV) in which Z=OH is reduced, the acid may be preactivated by reaction with ethyl chloroformate in the presence of triethylamine. The compounds of formula (XIV) or the compounds of formula (XV) in which Z=OH are prepared via standard hydrolysis of a compound of formula (XV) in which Z=(C 1 -C 2 )alkoxy. The reaction is performed via hydrolysis in alkaline medium using, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in a solvent such as water, methanol, 1,2-dimethoxyethane, 1,4-dioxane or a mixture of these solvents and at a temperature of between 0° C. and the reflux temperature of the solvent. The compounds of formula (XV) in which Z=(C 1 -C 2 )alkoxy are prepared according to Scheme I below in which Hal represents a halogen atom, preferably bromine. In step a1 of Scheme I, the reaction of a compound of formula (XVI) with a compound of formula (XVII) is performed in the presence of an alkali metal salt of hexamethyldisilazane, for example such as the sodium salt, in a solvent such as tetrahydrofuran and at a temperature of between −70° C. and 0° C. In step b1, the compound of formula (XVIII) thus obtained is reacted with an N,N-dimethylformamide/phosphorus oxychloride mixture, in a solvent such as 1,2-dichloroethane and at a temperature of between −10° C. and the reflux temperature of the solvent. The compound of formula (XIX) thus obtained is reacted in step c1 with a (C 1 -C 3 )alkylmagnesium halide or a (C 3 -C 7 )cycloalkylmagnesium halide, in a solvent such as tetrahydrofuran and at a temperature of between −20° C. and room temperature. The compound of formula (XXI) thus obtained is oxidized in step d1 in the presence of an oxidizing agent such as pyridinium dichromate and molecular sieves, in a solvent such as dichloromethane and at room temperature. The compound (XXII) thus obtained is reacted in step c1 with compound (XXIII), in the presence of a base such as 1,8-diazabicyclo[5.4.0]undec-7-ene, in a solvent such as acetonitrile and at a temperature of between room temperature and the reflux temperature of the solvent. The compounds of formulae (XVI), (XVII), (XX), (XXIII), (XXIV) and (XXV) are known or prepared according to known methods. The EXAMPLES below describe the preparation of certain compounds in accordance with the invention. These are non-limiting examples and serve merely to illustrate the present invention. The numbers of the compounds given as examples refer to those given in TABLE I below, which illustrates the chemical structures and the physical properties of a number of compounds according to the invention. In the Preparations and in the Examples, the following abbreviations are used: ether: diethyl ether iso ether: diisopropyl ether DMSO: dimethyl sulfoxide DMF: N,N-dimethylformamide THF: tetrahydrofuran TBTU: 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate DCM: dichloromethane EtOAc: ethyl acetate DIPEA: diisopropylethylamine DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene TFA: trifluoroacetic acid 2N hydrochloric ether: 2N solution of hydrogen chloride in diethyl ether m.p.: melting point RT: room temperature b.p.: boiling point HPLC: high performance liquid chromatography Silica H: 60 H silica gel sold by Merck (Darmstadt) pH 2 buffer solution: solution of 16.66 g of KHSO 4 and 32.32 g of K 2 SO 4 in 1 liter of water. The proton nuclear magnetic resonance ( 1 H NMR) spectra are recorded at 200 MHz in DMSO-d 6 . The chemical shifts δ are expressed in parts per million (ppm). For the interpretation of the spectra, the following abbreviations are used: s: singlet, d: doublet, t: triplet, q: quartet, m: unresolved complex, mt: multiplet, bs: broad singlet, dd: doubled doublet. The compounds according to the invention are analyzed by LC/UV/MS coupling (liquid chromatography/UV detection/mass spectrometry). The molecular peak (MH + ) and the retention time (rt) in minutes are measured. Method 1: A Symmetry C18 2.1×50 mm, 3.5 μm column is used, at 30° C., flow rate 0.4 ml/minute. The eluent is composed as follows: solvent A: 0.005% trifluoroacetic acid (TFA) in water at pH 3.15; solvent B: 0.005% TFA in acetonitrile. Gradient: Time (minutes) % A % B 0 100 0 10 10 90 15 10 90 16 100 0 20 100 0 The UV detection is performed at λ=210 nm and the mass detection is performed in positive ESI chemical ionization mode. Method 2: An XTerra MS C18 2.1×50 mm, 3.5 μm column is used, at 30° C., flow rate 0.4 ml/minute. The eluent is composed as follows: solvent A: 10 mM ammonium acetate (NH 4 AcO) in water at pH 7; solvent B: acetonitrile. Gradient: Time (minutes) % A % B 0 100 0 10 10 90 15 10 90 16 100 0 20 100 0 The UV detection is performed at λ=220 nm and the mass detection is performed in positive ESI chemical ionization mode. PREPARATIONS 1. Preparation of the Compounds of Formula (XVIII): Preparation 1.1 2-(4-Bromophenyl)-1-(2,4-dichlorophenyl)ethanone 436 ml of a 2M solution of the sodium salt of hexamethyldisilazane in THF are cooled to −60° C., under a nitrogen atmosphere, 400 ml of THF are added, followed by dropwise addition of a solution of 75 g of 4-bromophenylacetic acid in 100 ml of THF, and the mixture is stirred for 1 hour 30 minutes at −70° C. 67.9 g of methyl 2,4-dichlorobenzoate are then added dropwise and the mixture is stirred for 30 minutes and then allowed to warm to 5° C. The reaction mixture is poured into a mixture of ice/1 liter of 2N HCl and extracted with ether, the organic phase is washed with saturated NaHCO 3 solution and with water, and dried over Na 2 SO 4 , the solvent is evaporated off under vacuum to a volume of 200 ml, pentane is added and the crystalline product formed is filtered off by suction. 80 g of the expected compound are obtained. Preparation 1.2 2-(4-Chlorophenyl)l-1(2,4-dichlorophenyl)ethanone 417 ml of a 2M solution of the sodium salt of hexamethyldisilazane in THF are cooled to −60° C., under a nitrogen atmosphere, 350 ml of THF are added, followed by dropwise addition of a solution of 57 g of 4-chlorophenylacetic acid in 70 ml of THF and the mixture is stirred for 2 hours while allowing the temperature to rise to −40° C. The reaction mixture is cooled to −60° C., 65.3 g of methyl 2,4-dichlorobenzoate are added dropwise and the mixture is stirred while allowing the temperature to rise to 0° C. The reaction mixture is poured into a mixture of ice/1 liter of 2N HCl and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is concentrated under vacuum to a volume of 150 ml. The remaining solution is poured into 300 ml of pentane and the crystalline product formed is filtered off by suction. 60 g of the expected compound are obtained. 2. Preparation of the Compounds of Formula (XIX): Preparation 2.1 2-(4-Bromophenyl)-3-chloro-3-(2,4-dichlorophenyl)acrylaldehyde A solution of 33.7 ml of DMF in 75 ml of 1,2-dichloroethane is cooled to −50° C., 40.6 ml of POCl 3 are added dropwise and the mixture is then stirred while allowing the temperature to return to RT. A solution of 40 g of the compound obtained in Preparation 1.1 in 300 ml or 1,2-dichloroethane is then added and the mixture is refluxed for 48 hours. After cooling, the reaction mixture is poured into 1.5 liters of ice/water, the pH is brought to 7 by addition of NaHCO 3 , the resulting mixture is extracted with DCM, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with a gradient of a heptane/DCM mixture of from (90/10; v/v) to (50/50; v/v). 39 g of the expected compound are obtained. Preparation 2.2 3-Chloro-2-(4-chlorophenyl)-3-(2,4-dichlorophenyl)acrylaldehyde A solution of 54.5 ml of DMF in 80 ml of 1,2-dichloroethane is cooled to 0° C., 60.7 ml of POCl 3 are added dropwise and the mixture is then stirred while allowing the temperature to return to RT. A solution of 30 g of the compound of Preparation 1.2 in 300 ml of 1,2-dichloroethane is then added and the mixture is heated at 80° C. for 4 hours. After cooling, the reaction mixture is poured onto ice, the pH is brought to 7 by adding sodium acetate, the resulting mixture is extracted with DCM, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with DCM. 35 g of the expected compound are obtained. 3. Preparation of the Compounds of Formula (XXI): Preparation 3.1 3-(4-Bromophenyl)-4-chloro-4-(2,4-dichlorophenyl)but-3-en-2-ol A solution of 10 g of the compound obtained in Preparation 2.1 in 100 ml of THF is cooled to −20° C. and 25 ml of a 1.4M solution of methylmagnesium bromide in THF are added dropwise. The reaction mixture is poured into saturated NH 4 Cl solution and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. 11 g of the expected compound are obtained. Preparation 3.2 4-Chloro-3-(4-chlorophenyl)-4-(2,4-dichlorophenyl)but-3-en-2-ol A solution of 35 g of the compound obtained in Preparation 2.2 in 200 ml of THF is cooled to −20° C. and 54.2 ml of a 1.4M solution of methylmagnesium bromide in THF are added dropwise. The reaction mixture is poured into saturated NH 4 Cl solution and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with heptane and then with a heptane/EtOAc mixture up to (80/20; v/v). 16 g of the expected compound are obtained. 4. Preparation of the Compounds of Formula (XXII): Preparation 4.1 3-(4-Bromophenyl)-4-chloro-4-(2,4-dichlorophenyl)but-3-en-2-one A mixture of 7 g of the compound obtained in Preparation 3.1, 12.8 g of pyridinium dichromate and 15 g of 4 Å molecular sieves in 200 ml of DCM is stirred for 24 hours at RT. The reaction mixture is filtered through Celite and the filtrate is concentrated under vacuum. The residue is chromatographed on silica gel, eluting with heptane and then with a heptane/EtOAc mixture (96/4; v/v). 7 g of the expected compound are obtained. Preparation 4.2 4-Chloro-3-(4-chlorophenyl)-4-(2,4-dichlorophenyl)but-3-en-2-one A mixture of 16 g of the compound obtained in Preparation 3.2, 41.6 g of pyridinium dichromate and 40 g of 4 Å molecular sieves in 200 ml of DCM is stirred overnight at room temperature. The reaction mixture is filtered through Celite and the filtrate is concentrated under vacuum. The residue is chromatographed on silica gel, eluting with a heptane/EtOAc mixture (90/10; v/v). 15 g of the expected compound are obtained. 5. Preparation of the Compounds of Formula (XV): Preparation 5.1 Methyl 4-(4-bromophenyl)-5-(2,4-dichlorophenyl)-3-methylthiophene-2-carboxylate To a solution of 2.7 g of the compound obtained in Preparation 4.1 in 25 ml of acetonitrile are added 1.49 ml of methyl mercaptoacetate and then 2.4 ml of DBU, and the mixture is stirred overnight at RT. The reaction mixture is poured into 12.5 ml of 1N HCl and extracted with EtOAc, the organic phase is washed with water and dried over Na 2 SO 4 , and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with a heptane/EtOAc mixture (95/5; v/v). 1.21 g of the expected compound are obtained. Preparation 5.2 Methyl 4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-3-methylthiophene-2-carboxylate A mixture of 7.5 g of the compound obtained in Preparation 4.2 and 4.4 g of methyl mercaptoacetate is heated to 80° C., 3 ml of DBU are added dropwise and the mixture is stirred overnight at 60° C. The reaction mixture is concentrated under vacuum, the residue is taken up in 1N HCl solution and extracted with an ether/EtOAc mixture, the organic phase is dried over Na 2 SO 4 and the solvents are evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with heptane and then with a heptane/EtOAc mixture up to (90/10; v/v). 3.5 g of the expected compound are obtained after crystallization from MeOH. 6. Preparation of the Compounds of Formula (XIV): Preparation 6.1 4-(4-Bromophenyl)-5-(2,4-dichlorophenyl)-3-methylthiophene-2-carboxylic acid To a solution of 1.21 g of the compound obtained in Preparation 5.1 in 6 ml of 1,2-dimethoxyethane are added 3 ml of MeOH and then 1.73 ml of 30% NaOH solution, and the mixture is stirred for 24 hours at 50° C. The reaction mixture is concentrated under vacuum, the residue is taken up in water, the aqueous phase is washed with ether, acidified to pH 2 by adding concentrated HCl solution and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. 0.75 g of the expected compound is obtained after crystallization from a pentane/iso ether mixture (75/25; v/v). Preparation 6.2 4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methylthiophene-2-carboxylic acid To a solution of 3.5 g of the compound obtained in Preparation 5.2 in 15 ml of 1,2-dimethoxyethane are added 15 ml of MeOH and then 0.68 g of NaOH pellets, and the mixture is stirred overnight at room temperature and then heated at 60° C. for 3 hours. The reaction mixture is concentrated under vacuum, the residue is taken up in water, washed with ether, acidified to pH 2 by adding concentrated HCl solution and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. 3 g of the expected compound are obtained after crystallization from a DCM/iso ether mixture. 7. Preparation of the Compounds of Formula (XII): Preparation 7.1 4-(4-Bromophenyl)-5-(2,4-dichlorophenyl)-3-methylthiophene-2-carboxamide A mixture of 3 g of the compound obtained in Preparation 6.1 and 1.98 ml of thionyl chloride in 60 ml of 1,2-dichloroethane is heated at 70° C. for 4 hours. The reaction mixture is concentrated under vacuum, the residue is taken up in 1,2-dichloroethane and the solvent is evaporated off under vacuum to give 3 g of the acid chloride. A solution of 6.51 ml of 2M aqueous ammonia in MeOH and 1.37 ml of triethylamine in 10 ml of DCM is cooled to 50° C., a solution of 3 g of the acid chloride in 5 ml of DCM is added dropwise and the mixture is stirred overnight while allowing the temperature to return to RT. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with EtOAc, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. 2.5 g of the expected compound are obtained after crystallization from an ether/iso ether mixture. Preparation 7.2 4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methylthiophene-2-carboxamide A mixture of 3 g of the compound obtained in Preparation 6.2 and 2.2 ml of thionyl chloride in 60 ml of 1,2-dichloroethane is refluxed for 2 hours 30 minutes. The reaction mixture is concentrated under vacuum, the residue is taken up in 1,2-dichloroethane and the solvent is evaporated off under vacuum to give 3 g of the acid chloride. A solution of 7.21 ml of 2M aqueous ammonia in MeOH and 1.52 ml of triethylamine in 20 ml of DCM is cooled to 0° C., a solution of 3 g of the acid chloride in 20 ml of DCM is added dropwise and the mixture is stirred overnight while allowing the temperature to return to room temperature. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with DCM and then with a DCM/2-propanol mixture up to (95/5; v/v). 2 g of the expected compound are obtained after crystallization from iso ether. 8. Preparation of the Compounds of Formula (II): Preparation 8.1 1-[4-(4-Bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methanamine hydrochloride To a solution of 2.5 g of the compound obtained in Preparation 7.1 in 50 ml of THF are added 22.67 ml of a 1M solution of borane in THF, and the mixture is then refluxed for 15 hours. MeOH is then added until the evolution of gas has ceased, and 10 ml of a 2N solution of HCl in ether are added. The reaction mixture is concentrated under vacuum to a volume of 10 ml and then added dropwise, at RT, to 150 ml of iso ether and stirred overnight at RT, and the precipitate formed is filtered off by suction. 1.9 g of the expected compound are obtained. Preparation 8.2 1-[4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methanamine hydrochloride To a solution of 2 g of the compound obtained in Preparation 7.2 in 20 ml of THF are added 20.2 ml of a 1M solution of borane in THF, and the mixture is then refluxed for 5 hours. MeOH is then added until the evolution of gas has ceased, and 10 ml of a 2N solution of HCl in ether are added and the mixture is stirred for 30 minutes. The reaction mixture is concentrated under vacuum to a volume of 10 ml, which is added dropwise at room temperature to 150 ml of an ether/iso ether mixture (50/50; v/v) and stirred overnight at room temperature, and the precipitate formed is filtered off by suction. 1.5 g of the expected compound are obtained. EXAMPLE 1 Compound 1 N-[[4-(4-Bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-ethylbutanamide A mixture of 0.35 g of the compound obtained in Preparation 8.1, 0.32 ml of triethylamine and 0.1 g of 2-ethylbutyryl chloride in 20 ml of DCM is stirred for 1 hour at RT. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with EtOAc, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is dissolved in DCM, iso ether is added and the crystalline product formed is filtered off by suction. 0.28 g of the expected compound is obtained. MH + =524; rt=11.86 (method 2) 1 H NMR: DMSO-d 6 : δ (ppm): 0.8: t: 6H; 1.4: mt: 4H; 1.85-2.15: m: 4H; 4.45: d: 2H; 6.9-7.7: m: 7H; 8.5: t: 1H. EXAMPLE 2 Compound 2 N-[[4-(4-Bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]cycloheptanecarboxamide A mixture of 0.35 g of the compound obtained in Preparation 8.1, 0.11 g of cycloheptanecarboxylic acid, 0.32 mg of triethylamine and 0.27 g of TBTU in 20 ml of DCM is stirred overnight at RT. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with EtOAc, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is dissolved in DCM, iso ether is added and the crystalline product formed is filtered off by suction. 0.27 g of the expected compound is obtained. MH + =550; rt=12.4 (method 2) 1 H NMR: DMSO-d 6 : δ (ppm): 1.2-1.9: m: 12H; 2.02: s: 3H; 2.3: mt: 1H; 4.4: d: 2H; 6.9-7.7: m: 7H; 8.4: t: 1H. EXAMPLE 3 Compound 3 N-[[4-(4-Bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-3-(trifluoromethyl)benzenesulfonamide A mixture of 0.35 g of the compound obtained in Preparation 8.1, 0.2 g of 3-(trifluoromethyl)benzenesulfonyl chloride and 0.32 ml of triethylamine in 20 ml of DCM is stirred overnight at RT. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with EtOAc, the organic phase is washed with water and dried over Na 2 SO 4 , and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with a DCM/EtOAc mixture (90/10; v/v). 0.25 g of the expected compound is obtained. MH + =632; rt=12.28 (method 2) 1 H NMR: DMSO-d 6 : δ (ppm): 1.9: s: 3H; 4.3: s: 2H; 6.7-8.2: m: 11H; 8.65: bs: 1H. EXAMPLE 4 Compound 4 N-[[4-(4-Bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-methylhexanamide A mixture of 0.35 g of the compound obtained in Preparation 8.1, 0.35 ml of triethylamine, 0.11 g of 2-methylhexanoic acid and 0.29 g of TBTU in 20 ml of DCM is stirred for 48 hours at RT. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with EtOAc, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. 0.3 g of the expected compound, which crystallizes, is obtained. MH + =538; rt=12.71 (method 1) 1 H NMR: DMSO-d 6 : δ (ppm): 0.8: t: 3H; 1.0: d: 3H; 1.05-1.65: m: 6H; 2.05: s: 3H; 2.25: mt: 1H; 4.45: mt: 2H; 6.9-7.7: m: 7H; 8.55: t: 1H. EXAMPLE 5 Compound 5 N-[[4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2,2-dimethylpropanamide A mixture of 0.35 g of the compound obtained in Preparation 8.2, 0.35 ml of triethylamine and 0.11 ml of 2,2-dimethylpropanoyl chloride in 20 ml of DCM is stirred for 2 hours at room temperature. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. 0.3 g of the expected compound is obtained after crystallization from an ether/iso ether mixture. 1 H NMR: DMSO-d 6 : δ (ppm): 1.12: s: 9H; 2.03: s: 3H; 4.43: d: 2H; 7.07: d: 2H; 7.24-7.40: m: 4H; 7.58: bs: 1H; 8.19: t: 1H. EXAMPLE 6 Compound 6 N-[[4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-ethylbutanamide A mixture of 0.35 g of the compound obtained in Preparation 8.2, 0.35 ml of triethylamine and 0.12 g of 2-ethylbutyryl chloride in 20 ml of DCM is stirred for 2 hours at room temperature. The reaction mixture is concentrated under vacuum, the residue is taken up in 0.5 N HCl solution and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. 0.3 g of the expected compound is obtained after crystallization from iso ether. 1 H NMR: DMSO-d 6 : δ (ppm): 0.81: t: 6H; 1.42: mt: 4H; 1.91-2.15: m: 4H; 4.47: d: 2H; 7.07: d: 2H; 7.22-7.44: m: 4H; 7.61: d: 1H; 8.50: t: 1H. EXAMPLE 7 Compound 7 N-[[4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-1-methylcyclopropanecarboxamide A mixture of 0.35 g of the compound obtained in Preparation 8.2, 0.35 ml of triethylamine, 0.09 g of 1-methylcyclopropanecarboxylic acid and 0.3 g of TBTU in 30 ml of DCM is stirred for 12 hours at room temperature. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. 0.2 g of the expected compound is obtained after crystallization from iso ether. 1 H NMR: DMSO-d 6 : δ (ppm): 0.53: q: 2H; 0.97: q: 2H; 1.27: s: 3H; 2.05: s: 3H; 4.43: d: 2H; 7.07: d: 2H; 7.25-7.43: m: 4H; 7.59: d: 1H; 8.25: t: 1H. EXAMPLE 8 Compound 8 N-[[4-(4-Bromophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-4-(trifluoromethyl)benzamide A mixture of 0.35 g of the compound obtained in Preparation 8.1, 0.17 g of 4-(trifluoromethyl)benzoyl chloride and 0.32 ml of triethylamine in 20 ml of DCM is stirred overnight at room temperature. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with heptane and then with a heptane/EtOAc mixture to (90/10; v/v). 0.3 g of the expected compound is obtained. 1 H NMR: DMSO-d 6 : δ (ppm): 2.12: s: 3H; 4.68: d: 2H; 7.02: d: 2H; 7.25-7.41: m: 2H; 7.49: d: 2H; 7.59: d: 1H; 7.87: d: 2H; 8.09: d: 2H; 9.44: t: 1H. EXAMPLE 9 Compound 9 N-[[4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-methylpropane-2-sulfinamide A mixture of 0.3 g of the compound obtained in Preparation 8.2, 0.12 g of 2-methylpropane-2-sulfinyl chloride and 0.3 ml of triethylamine in 20 ml of DCM is stirred for 2 hours at room temperature. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with DCM and then with a DCM/EtOAc mixture to (90/10; v/v). 0.2 g of the expected compound is obtained. 1 H NMR: DMSO-d 6 : δ (ppm): 1.16: s: 9H; 2.03: s: 3H; 4.36: mt: 2H; 6.03: t: 1H; 7.07: d: 2H; 7.22-7.47: m: 4H; 7.60: d: 1H. EXAMPLE 10 Compound 10 N-[[4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-2-methylpropane-2-sulfonamide A mixture of 0.35 g of Compound 9 and 0.3 g of 3-chloroperbenzoic acid in 20 ml of DCM is stirred for 1 hour at room temperature. 10% NaHCO 3 solution is then added, the mixture is extracted with DCM, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with DCM. 0.18 g of the expected compound is obtained after crystallization from iso ether. 1 H NMR: DMSO-d 6 : δ (ppm): 1.30: s: 9H; 2.03: s: 3H; 4.42: d: 2H; 7.08: d: 2H; 7.27-7.44: m: 4H; 7.62: d: 1H; 7.66: t: 1H. EXAMPLE 11 Compound 11 3-[[4-(4-Chlorophenyl)-5-(2,4-dichlorophenyl)-3-methyl-2-thienyl]methyl]-1,1-diethylurea A mixture of 0.35 g of the compound obtained in Preparation 8.2, 0.165 ml of diethylcarbamic chloride, 0.1 g of 4-dimethylaminopyridine and 0.11 g of K 2 CO 3 in 30 ml of DCM is heated at 45° C. for 48 hours. The reaction mixture is concentrated under vacuum, the residue is taken up in water and extracted with ether, the organic phase is dried over Na 2 SO 4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica gel, eluting with DCM and then with a DCM/MeOH mixture to (97.5/2.5; v/v). 0.25 g of the expected compound is obtained. 1 H NMR: DMSO-d 6 : δ (ppm): 1.03: t: 6H; 2.05: s: 3H; 3.22: q: 4H; 4.41: d: 2H; 6.95: t: 1H; 7.07: d: 2H; 7.24-7.44: m: 4H; 7.59: d: 1H. The table that follows illustrates the chemical structures of a number of examples of compounds according to the invention. TABLE I (I) Compounds —X— R 1 R 2 R 3 R 4 R 5 1 —CO— —CH(CH 2 CH 3 ) 2 H —CH 3 2 —CO— H —CH 3 3 —SO 2 — H —CH 3 4 —CO— H —CH 3 5 —CO— —C(CH 3 ) 3 H —CH 3 6 —CO— —CH(CH 2 CH 3 ) 2 H —CH 3 7 —CO— H —CH 3 8 —CO— H —CH 3 9 —SO— —C(CH 3 ) 3 H —CH 3 10 —SO 2 — —C(CH 3 ) 3 H —CH 3 11 —CH 2 CH 3 H —CH 3 The compounds of formula (I) show very good in vitro affinity (IC 50 ≦5×10 −7 M) for the CB 1 cannabinoid receptors, under the experimental conditions described by M. Rinaldi-Carmona et al. (FEBS Letters, 1994, 350, 240-244). The antagonist nature of the compounds of formula (I) was determined by means of the results obtained in models of inhibition of adenylate cyclase as described in M. Bouaboula et al., J. Biol. Chem., 1995, 270, 13 973-13 980, M. Rinaldi-Carmona et al., J. Pharmacol. Exp. Ther., 1996, 278, 871-878 and M. Bouaboula et al., J. Biol. Chem., 1997, 272, 22 330-22 339. The toxicity of the compounds of formula (I) is compatible with their use as medicaments. Thus, according to another of its aspects, a subject of the invention is medicaments comprising a compound of formula (I) or an addition salt thereof with a pharmaceutically acceptable acid, or alternatively a solvate or a hydrate of the compound of formula (I). Thus, the compounds according to the invention may be used in man or animals in the treatment or prevention of diseases involving the CB 1 cannabinoid receptors. For example, and in a non-limiting manner, the compounds of formula (I) are useful as psychotropic medicaments, especially for treating psychiatric disorders including anxiety, depression, mood disorders, insomnia, delirium disorders, obsessive disorders, psychoses in general, schizophrenia, attention and hyperactivity disorders (AHD) in hyperkinetic children (MBD), and also for the treatment of disorders associated with the use of psychotropic substances, especially in the case of a substance abuse and/or dependency on a substance, including alcohol dependency and nicotine dependency. The compounds of formula (I) according to the invention may be used as medicaments for treating migraine, stress, diseases of psychosomatic origin, panic attacks, epilepsy, motor disorders, in particular dyskinesia or Parkinson's disease, trembling and dystonia. The compounds of formula (I) according to the invention may also be used as medicaments in the treatment of memory disorders, cognitive disorders, in particular in the treatment of senile dementia and Alzheimer's disease, and also in the treatment of attention or consciousness disorders. Furthermore, the compounds of formula (I) may be useful as neuroprotective agents, in the treatment of ischemia, cranial trauma and the treatment of neurodegenerative diseases: including chorea, Huntington's chorea and Tourrette's syndrome. The compounds of formula (I) according to the invention may be used as medicaments in the treatment of pain, neuropathic pain, acute peripheral pain, chronic pain of inflammatory origin. The compounds of formula (I) according to the invention may be used as medicaments in the treatment of appetite disorders, appetence disorders (for sugars, carbohydrates, drugs, alcohol or any appetizing substance) and/or eating behavioral disorders, especially for the treatment of obesity or bulimia and also for the treatment of type II diabetes or non-insulin-dependent diabetes and for the treatment of dyslipidemia and metabolic syndrome. Thus, the compounds of formula (I) according to the invention are useful in the treatment of obesity and the risks associated with obesity, especially the cardiovascular risks. Furthermore, the compounds of formula (I) according to the invention may be used as medicaments in the treatment of gastrointestinal disorders, diarrhea disorders, ulcers, vomiting, bladder and urinary disorders, disorders of endocrine origin, cardiovascular disorders, hypotension, hemorrhagic shock, septic shock, chronic cirrhosis of the liver, hepatic steatosis, steatohepatitis, asthma, Raynaud's syndrome, glaucoma, fertility disorders, premature interruption of pregnancy, inflammatory phenomena, immune system diseases, in particular autoimmune diseases and neuroinflammatory diseases such as rheumatoid arthritis, reactional arthritis, diseases resulting in demyelinization, multiple sclerosis, infectious and viral diseases such as encephalitis, strokes, and also as medicaments for anticancer chemotherapy, for the treatment of Guillain-Barré syndrome and for the treatment of osteoporosis. According to the present invention, the compounds of formula (I) are most particularly useful for treating psychotic disorders, in particular schizophrenia, attention and hyperactivity disorders (AHD) in hyperkinetic children (MBD); for treating appetite and obesity disorders; for treating memory and cognitive deficits; for treating alcohol dependency and nicotine dependency, i.e. for weaning from alcohol and for weaning from tobacco. According to one of its aspects, the present invention relates to the use of a compound of formula (I), pharmaceutically acceptable salts thereof and solvates or hydrates thereof for treating the disorders and diseases indicated above. According to another of its aspects, the present invention relates to pharmaceutical compositions comprising, as active principle, a compound according to the invention. These pharmaceutical compositions contain an effective dose of at least one compound according to the invention, or a pharmaceutically acceptable salt, a solvate or a hydrate of the said compound, and also at least one pharmaceutically acceptable excipient. The said excipients are chosen according to the pharmaceutical form and the desired mode of administration, from the usual excipients known to those skilled in the art. In the pharmaceutical compositions of the present invention for oral, sublingual subcutaneous, intramuscular, intravenous, topical, local, intratracheal, intranasal, transdermal or rectal administration, the active principle of formula (I) above, or the possible salt, solvate or hydrate thereof, may be administered in a unit form of administration, as a mixture with standard pharmaceutical excipients, to man and animals for the prophylaxis or treatment of the above disorders or diseases. The appropriate unit forms of administration include oral-route forms such as tablets, soft or hard gel capsules, powders, granules and oral solutions or suspensions, sublingual, buccal, intratracheal, intraocular and intranasal administration forms, forms for administration by inhalation, topical, transdermal, subcutaneous, intramuscular or intravenous administration forms, rectal administration forms and implants. For topical application, the compounds according to the invention may be used in creams, gels, pomades or lotions. By way of example, a unit form of administration of a compound according to the invention in tablet form may comprise the following components: Compound according to the invention 50.0 mg Mannitol 223.75 mg Sodium croscarmellose 6.0 mg Corn starch 15.0 mg Hydroxypropylmethylcellulose 2.25 mg Magnesium stearate 3.0 mg Via the oral route, the dose of active principle administered per day may be from 0.01 to 100 mg/kg in one or more dosage intakes, preferentially 0.02 to 50 mg/kg. There may be particular cases in which higher or lower dosages are appropriate; such dosages do not depart from the context of the invention. According to the usual practice, the dosage that is appropriate to each patient is determined by the doctor according to the mode of administration and the weight and response of the said patient. According to another of its aspects, the present invention also relates to a method for treating the pathologies indicated above, which comprises the administration to a patient of an effective dose of a compound according to the invention, or a pharmaceutically acceptable salt or hydrate or solvate thereof.
The invention concerns compounds of formula (I), wherein X, R 1 , R 2 , R 3 , R 4 and R 5 are as defined herein. The invention also concerns a method for preparing said compounds and their use as cannabinoid CB1 receptor antagonists.
2
CROSS-REFERENCE TO RELATED APPLICATION [0001] The present U.S. Non-Provisional patent application claims the benefit as a continuation of U.S. application Ser. No. 12/220,456, filed on Jul. 23, 2008, currently pending, which in turn cross-references and claims priority and benefit as a continuation of U.S. Design patent application Ser. No. 29/254,444, filed Feb. 23, 2006, entitled “Non-Threaded Fastener Pulling Tool with Saw Wrench, Nail Pick, and Bottle Opener Combination,” issued as U.S. Patent D579,292 on Feb. 23, 2006, which is hereby incorporated by reference in its entirety. TECHNICAL FIELD [0002] The present disclosure relates generally to hand tools, and, more particularly, to construction tools, such as a pulling tool, or the like. BACKGROUND OF THE INVENTION [0003] Construction work typically requires the use of a plurality of tools, including hand tools and electric tools. Necessary hand tools usually include tools designed for joining particular materials together, as well as tools designed to assist in breaking apart construction materials, such as when improper installation or measurement error is detected. Electric tools, such as saws, drills, and the like, further frequently necessitate the utilization of additional tools, such as chucks, for adjustment, adaptation, and exchange of component parts during a project. Thus, each construction worker is often faced with a myriad of tools to transport. [0004] Transport of such a collection of tools to a jobsite is a dubious task in and of itself, but maintaining mobility of such a number of tools and exchanging between tools while working is disadvantageously time and energy consuming. Further disadvantages can be realized directly by the workforce. That is, in addition to time and material costs, worker performance can be compromised by premature exhaustion as a result of repeatedly expending energy exchanging between a plurality of heavy tools, and necessarily transporting those tools about a work site. [0005] Thus, it is clear that there is an unmet need for a construction tool that advantageously provides a plurality of on-board tools to assist in user accomplishment of a variety of tasks at a given job site, coincidentally maximizing workforce energy and efficiency. BRIEF SUMMARY OF THE INVENTION [0006] Briefly described, in an exemplary embodiment, the pulling tool of the present disclosure overcomes the above-mentioned disadvantages and meets the recognized need for such a tool by providing a non-threaded fastener pulling tool having a saw wrench, nail pick, and bottle opener. [0007] More specifically, the exemplary pulling tool of the present disclosure includes a generally elongated handle portion with a lever pulling head at a first end of the handle portion, and a nail pick at a second end of the handle portion. The handle portion preferably includes generally broad, flat side-wall surfaces for stability and strength, wherein at least one of which is adapted to receive a plurality of on-board tools. The handle portion may further include generally narrow edge surfaces, at least one of which may be adapted with grip-enhancing features. Thus, the handle portion is generally formed as a sturdy bar, grippable for ease of use in a plurality of positions relative to the workpiece. The handle portion may also include a comfortable grip operable therewith to provide a comfortable gripping surface by which a user may grasp the tool, while maintaining strength of hold, wherein such a comfort grip may be provided in addition to or in lieu of the on-board grip-enhancing features. [0008] The nail pick portion is generally a slightly angular extension of the handle and has a preferably broad front and rearward surface, corresponding to the broad, flat side-wall surfaces of the handle, to facilitate effective delivery of prying forces, such as to withdraw nails from a workpiece. The lever pulling head, or non-threaded fastener puller, similarly has a broad front and rearward surface, however, the broadened tine or claw of the pulling surfaces preferably extends dimensionally and angularly from the heel, which corresponds to the narrow edge surfaces of the handle. This facilitates effective delivery of lever action, such as to pull nails firmly embedded in a workpiece. For example, while removal of an improperly positioned nail may require a simple nail pick, some instances of fully seated nails may necessitate the use of a pulling lever claw for beneficial fulcrum action. [0009] The generally broad, flat side-wall surface of the handle portion proximate the heel of the lever pulling head may preferably include additional useful tools, such as a saw wrench, a bottle opener, and an open wrench. The optional saw wrench is preferably disposed as a functional feature extending from the handle side-wall surface, with an outer edge angularly disposed relative to the plane of the handle side-wall. Such an orientation facilitates access to the recess wrench feature while also enabling a user to retain grippable positioning of the tool relative to the workpiece. That is, the configuration is preferred for use with a circular saw, wherein a blade fastener may be engaged by the saw wrench, with the handle of the tool extending away from the saw blade surface due to the angular outer edge of the saw wrench such that the user may grip the handle for application of force to loosen and remove the fastener without fear of inadvertent engagement with the saw blade. For example, the saw wrench may extend to an angle approximately equal to 60 degrees and preferably greater than 45 degrees. [0010] The optional bottle opener may preferably be disposed proximate the saw wrench, on the handle side-wall, in order to facilitate insertion of a capped bottle according to the traditional functional configuration of a bottle opener, wherein pulling forces applied to the handle of the tool can easily and effectively remove a bottle cap. Preferably abutting the bottle opener, the optional open wrench may extend outwardly from the handle side-wall, preferably with a length of extension greater than that of the bottle opener or saw wrench relative to the side-wall. The wrench is preferably open such that a narrow article could be inserted therewithin via the open side. The outer edge of the open wrench is preferably generally flat, with the elongated nature of the preferred wrench socket facilitating loosening of even deep set bolts with application of the handle leverage. [0011] Accordingly, one feature and advantage of the tool of the present disclosure is its ability to provide a strong handle portion having surfaces adapted to grip comfort and easy application of force during a plurality of tool uses. [0012] Another feature and advantage of the tool of the present invention is its ability to provide grip-enhancing recesses that facilitate grasping of the edges of the device. [0013] Another feature and advantage of the tool of the present disclosure is its ability to provide a durable pulling tool capable of delivering leveraged forces while providing a beneficial weight distribution and balance for ease of use. [0014] Yet another feature and advantage of the tool of the present disclosure is its ability to provide a plurality of on-board tools to efficiently assist in the accomplishment of a plurality of construction-related tasks. [0015] Still another feature and advantage of the tool of the present disclosure is its ability to perform as a balanced lever for transfer of forces. [0016] Yet still another feature and advantage of the tool of the present disclosure is its ability to provide a bottle opener for opening bottles. [0017] Still yet another feature and advantage of the tool of the present disclosure is its ability to eliminate the need for the transport of a plurality of specialized tools to a work site. [0018] Another feature and advantage of the tool of the present disclosure is its ability to provide for user performance of a variety of different work efforts, according to the nature of the job component needs. [0019] Still another feature and advantage of the tool of the present disclosure is its ability to provide a nail picking region to offer assistance with nail removal. [0020] And yet still another feature and advantage of the tool of the present disclosure is its ability to provide a non-threaded fastener puller that can leverage forces for maximum work. [0021] Another feature and advantage of the tool of the present disclosure is its ability to provide a saw wrench that can facilitate the quick removal and secure replacement of circular saw blades. [0022] Still another feature and advantage of the tool of the present disclosure is its ability to provide am open wrench that can facilitate the loosening and/or tightening of even deeply recessed bolts. [0023] These and other features and advantages of the tool of the present disclosure will become more apparent to those ordinarily skilled in the art after reading the following Detailed Description of the Invention and Claims in light of the accompanying drawing Figures. BRIEF DESCRIPTION OF THE DRAWINGS [0024] Accordingly, the present disclosure will be understood best through consideration of, and with reference to, the following drawings, viewed in conjunction with the Detailed Description of the Invention referring thereto, in which like reference numbers throughout the various drawings designate like structure, and in which: [0025] FIG. 1 is a perspective view of the pulling tool of the present disclosure, according to a preferred embodiment; [0026] FIG. 2 is a top view of the pulling tool of FIG. 1 ; and [0027] FIG. 3 is a side view of the pulling tool of FIG. 1 . [0028] It is to be noted that the drawings presented are intended solely for the purpose of illustration and that they are, therefore, neither desired nor intended to limit the scope of the disclosure to any or all of the exact details of construction shown, except insofar as they may be deemed essential to the claimed invention. DETAILED DESCRIPTION OF THE INVENTION [0029] In describing exemplary embodiments of the hammer of the present disclosure illustrated in the drawings, specific terminology is employed for the sake of clarity. The claimed invention, however, is not intended to be limited to the specific terminology so selected, and it is to be understood that each specific element includes all technical equivalents that operate in a similar manner to accomplish a similar purpose. [0030] In that form of the pulling tool of the present disclosure chosen for purposes of illustration, FIGS. 1-3 show tool 100 including handle 101 and grip features 103 . Handle 101 is preferably formed from a suitable metal, composite, or synthetic material, or the like, defining nail pick tool 130 and levered pulling head 150 , and may include a comfort grip member (not shown) installed thereon. The comfort grip member may be formed from natural or synthetic rubber, plastic, composite, form, combinations, or the like, and may be resilient and/or sculptured or contoured to provide a comfortable and secure grasping surface. [0031] Handle 101 is preferably configured to provide durability and/or strength while reducing a total mass thereof and while providing a beneficial balance or distribution of mass, preferably defining a bar shape, with broad sidewall surfaces 105 a , 105 b and narrow edge surfaces 107 a , 107 b . Preferably, grip features 103 are defined in narrow edge surface 107 a , disposed in a balanced arrangement, and recessed relative to narrow edge surface 107 a . The preferred shape for grip features 103 is that of an elongate hexagonal shape, wherein the length of each recess facilitates reception of one or more fingertips of a user therein for grip enhancement. As noted, handle 101 may also include a comfortable grip operable therewith to provide a comfortable and secure gripping surface by which a user may grasp the tool. [0032] Nail pick tool 130 is preferably included at a distal end 109 of handle 101 , and is preferably wedge-shaped, as best seen in FIG. 2 , to facilitate effective delivery of prying forces. Pick surface 132 a is preferably angularly related to sidewall surface 105 a , and pick surface 132 b is preferably coplanar with sidewall surface 105 b . This configuration facilitates the pulling action of nail pick tool 130 . [0033] The non-threaded fastener puller, or lever pulling head, 150 preferably has broad front and rearward surfaces 152 a , 152 b . The broadened tine or claw 154 of pulling surfaces 152 a , 152 b preferably extends dimensionally and angularly from heel 156 , which may extend from narrow edge surface 107 a of handle 101 . This facilitates effective delivery of lever action, such as to pull nails firmly embedded in a workpiece. Non-threaded fastener puller 150 may be thus adapted to pry articles, such as nails, via application of force to handle 101 . [0034] Tool zone 170 of broad side-wall surface 105 a of handle 101 is preferably provided proximate heel 156 of lever pulling head 150 and may include a variety of additional useful tools. In one preferred embodiment, tool zone 170 may include saw wrench 190 , bottle opener 210 , and open wrench 230 . Saw wrench 190 is preferably disposed as a functional feature extending from side-wall surface 105 a , with outer edge 192 angularly disposed relative to the plane of side-wall 105 a . Once again, this preferred angular outer edge 192 facilitates positioning of puller 100 in a default extension position, wherein second end 109 of handle 101 is outwardly and angularly extended relative to the saw work surface upon which saw wrench 190 is being utilized. In such manner, a user may be able to retain a safe grip at a distance removed from the blade edge during circular saw blade removal and installation. The preferred angular disposition is about 60 degrees, and preferably greater than 45 degrees. [0035] Optional bottle opener 210 may be positioned proximate saw wrench 190 , on handle side-wall 105 a . The preferred traditional configuration of bottle opener 210 includes cap lip 212 , wherein outer edge 192 of saw wrench 190 performs as a fulcrum for bottle opener leverage. Preferably abutting bottle opener 210 , and opposingly positioned to saw wrench 190 , optional open wrench 230 may also extend outwardly from handle side-wall 105 a , preferably with a length of extension greater than that of bottle opener 210 or saw wrench 190 relative to side-wall 105 a . Preferably, opening 232 is defined in open wrench 230 in order that a nut may be selectively slidably inserted therethrough, rather than from outer end 234 . The open wrench is preferably approximately octagonal in shape wherein three sides of the octagon are missing, thereby providing two parallel sides of the octagon proximate the opening for gripping of bolts and the like. The extended socket of the open wrench may be generally narrowed in the top portion to provide a sharp edge along the top rim of the wrench. [0036] Having thus described exemplary embodiments of the present invention, it should be noted by those skilled in the art that the within disclosures are exemplary only and that various other alternatives, adaptations, and modifications may be made within the scope and spirit of the present invention. Accordingly, the present invention is not limited to the specific embodiments as illustrated herein, but is only limited by the following claims.
A multi-function tool having a handle portion and a plurality of structures operable therewith for the performance of a plurality of functions. The multi-function tool allows fast and convenient transition between any of the plurality of functions in order to enable completion of jobs or tasks requiring such functions without acquisition, storage, and/or maintenance of a plurality of specialized tools.
1
BACKGROUND OF THE INVENTION 1. Field of Invention This invention relates to wrought nickel-base superalloys with improved creep and stress rupture resistance and, in particular, to Ni--Cr--Co alloys solid solution strengthened by Mo and/or W, and precipitation hardened by the intermetallic compound gamma prime (γ') which has a formula of Ni 3 Al,Ti (and sometimes Nb and Ta). 2. Description of the Prior Art Steady advances over the years in the performance of the gas turbine engine have been paced by improvements in the elevated temperature mechanical property capabilities of nickel-base superalloys. Such alloys are the materials of choice for the largest share of the hottest components of the gas turbine engine. Components such as disks, blades, fasteners, cases, shafts, etc. are all fabricated from nickel-base superalloys and are required to sustain high stresses at very high temperatures for extended periods of time. As engine performance requirements are increased, components are required to endure higher temperatures and/or stresses or longer service lifetimes. In many cases, this is accomplished by redesigning parts to be fabricated from new or different alloys which have higher properties at higher temperatures (e.g., tensile strength, creep rupture life, low cycle fatigue, etc.). However, introduction of a new alloy, particularly into a critical rotating component of a jet engine, is a long and extremely costly process (many years and multiple millions of dollars today). Material property improvements can sometimes be achieved by means other than changing the basic alloy composition, as for example heat treatment, thermomechanical processing, microalloying, etc. These types of changes are considered less risky and can be made for substantially lower cost and much more quickly. In the area of microalloying, the positive effect of Boron (hereinafter referred to as B) in nickel-base superalloys has been known since the late 1950's, R. F. Decker et al. in Transactions of the AIME, Vol. 218, (1961), page 277 and F. N. Damana et al. in Journal of the Iron & Steel Institute, Vol. 191, (1959), page 266 demonstrated significant improvements in rupture life for nickel-base alloys from small B additions of 0.0015% to 0.0090% by weight. Phosphorus (hereinafter referred to as P), on the other hand, is an almost unavoidable element which is present in many metallic raw materials commonly used in the manufacturing of nickel-base alloys. There is relatively little published information on the effect of P in nickel-base alloys, and what is available is somewhat contradictory. For the most part, P has been considered to be a harmful, or at best, relatively innocuous element and is controlled to relatively low maximum limits (e.g., 0.015% P and B max. in specification AMS 5706H). Recent work, however, has shown that in certain superalloy compositions, P can, in fact, be beneficial to creep and stress rupture properties. See Wei-Di Cao and Richard L. Kennedy, "The Effect of Phosphorous on Mechanical Properties of Alloy 718", Superalloys 718, 625, 706 and Various Derivatives, 1994, edited by E. A. Loria, TMS, pages 463-477. P is extremely difficult to remove in most pyrometallurgical practices and, in fact, is not changed at all in normal, commercial vacuum melting practices used to produce the alloys of this invention. Therefore, the only means of control of P is to limit the amount in the starting raw materials. With the normal variations in raw material lots, this typically leads to analyzed contents in a commercial nickel-base alloy such as described in AMS 5706H (trade name WASPALOY®, registered trademark of Pratt & Whitney Aircraft) of 0.003% to 0.008%, well within specification limits. To achieve ultra-low P contents, as required in this invention, mandates the use of special, high purity raw materials which are available, but at substantially higher costs or perhaps very specialized melting practices. Prior to this invention, there has been no recognition of the benefits of producing nickel-base superalloys with such ultra-low P contents (<0.0030% P, or more preferably <0.001% P), and since commercial specifications of <0.015% P have been comfortably met with normal commercial raw materials, there has been a disincentive to produce alloys with very low P. However, it has been discovered that ultra-low P contents (<0.003%, or more preferably <0.001%) when employed in conjunction with higher than normal B levels (0.004% to 0.025%, or more preferably 0.008% to 0.016%) result in significantly improved creep and stress rupture life. SUMMARY OF THE INVENTION This invention relates to wrought nickel-base superalloys and articles made therefrom with improved creep and stress rupture resistance containing 0.005 to 0.15% C, 0.10 to 11% Mo, 0.10 to 4.25% W, 12-31% Cr, 0.25 to 21% Co, up to 5% Fe, 0.10 to 3.75% Nb, 0.10 to 1.25% Ta, 0.01 to 0.10% Zr, 0.10 to 0.50% Mn, 0.10 to 1% V, 1.8-4.75% Ti, 0.5 to 5.25% Al, less than 0.003% P, and 0.004-0.025% B. In all cases, the base element is Ni and incidental impurities. Advantageously, the superalloy composition may contain 0.005 to 0.15% C, 3-11% Mo, 0.10 to 4.25% W, 12-21% Cr, 7-18% Co, up to 5% Fe, 0.10 to 3.75% Nb, 0.01 to 0.10% Zr, up to 0.3% Mn, 2-4.75% Ti, 1.2-4.25% Al, <0.01 P, 0.008-0.020% B, balance Ni and incidental impurities. In one preferred embodiment, this invention relates to a wrought superalloy containing 0.02-0.10% C, 3.50-5.0% Mo, 18-21% Cr, 12-15% Co, up to 1.0% Fe, 0.4-0.10% Zr, up to 0.15% Mn, 2.75-3.25% Ti, 1.2-1.6% Al, <0.001% P, 0.008-0.016% B, balance Ni and incidental impurities. The superalloy compositions of this invention have ultra-low P contents in combination with higher than normal B contents. One means by which such low P limits can be obtained is by the selection of expensive, high purity raw materials. The critical combination of these two elements result in significant increases in creep and stress rupture resistance over the level which can be achieved by either element acting independently. Accordingly, it is the objective of this invention to provide wrought nickel-base superalloys suitable for use in gas turbine engines and articles made therefrom with substantially improved creep and stress rupture resistance. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 compares the stress rupture life of one preferred embodiment of this invention to commercial WASPALOY® and several variations thereof. FIG. 2 compares the stress rupture life of a nominal WASPALOY® base composition with variations of both P and B. FIG. 3 is a three-dimensional graph showing the strong inter-relationship of P and B on the stress rupture life of a nominal WASPALOY®-base composition. FIG. 4 compares the most preferred P and B compositional ranges of this invention to current commercial practice and specification limits of WASPALOY®. DESCRIPTION OF THE PREFERRED EMBODIMENTS It has been the general belief and understanding from the earliest days of superalloy production that P plays an insignificant role in the properties of nickel-base alloys if it is held anywhere below some nominal maximum value, e.g., 0.015% in AMS 5706H. Manufacturers and users of superalloys consider P to be a trace element which is commonly found in many raw materials, and numerous specifications and alloy patents specify and teach only that P content should not exceed some nominal maximum limit (as above). Applicants have discovered, however, that P can play a very large role in the creep and stress rupture life of nickel-base superalloys if it is controlled precisely to very critical limits within the nominal maximums that industry or previous inventors have specified. Applicants have further discovered that the effect of P is alloy specific. That is, in some alloys, e.g., the Ni--Cr--Co-base γ' precipitation hardened alloys of this invention that extremely low levels of P are critical, e.g., <0.003%, or more preferably <0.001%. Such levels are substantially lower than normal commercial practice of about 0.003-0.008%, and can only be achieved with special raw materials or manufacturing practices. However, in other alloys such as the Ni--Cr--Fe γ" precipitation hardened alloy 718, e.g., Applicants have demonstrated that a benefit to creep and stress rupture properties can be obtained by the purposeful addition of P in amounts substantially above that present in normal commercial practice (this discovery is the subject of a currently pending patent application). One preferred composition, for example, contains 0.022% which can only be obtained by the selection of special raw materials with purposefully high P contents or by the highly unusual practice of purposefully adding P in elemental or alloy form. A further critical part of these two inventions is the previously unrecognized interaction of P with B to achieve optimum creep and stress rupture resistance. Lowering P by itself to ultra low levels does not result in a significant change in stress rupture life for the Ni--Cr--Co γ' hardened alloys. Rather, the most significant and unexpected change in rupture life occurs when B is raised to higher than normal levels in combination with P at ultra low levels. This is clearly shown from FIGS. 1 and 2. It has further been discovered that the known beneficial effect of B on creep and stress rupture properties can be extended to much larger amounts of B if P is reduced to ultra low levels. This effect is also clearly shown in FIG. 2. The benefits of ultra low P in combination with higher than normal B can be explained from an understanding of the nature of creep deformation and the behavior of P and B in nickel-base alloys. At the test conditions employed in this work, creep deformation occurs mainly by grain boundary sliding and microvoid formation. Thus, specimen failures are almost completely intergranular. P and B both segregate to grain boundaries, resulting in changes in grain boundary cohesion and modification of boundary precipitates. Many studies have shown that P and B compete for grain boundary sites, and they produce different effects. P has a stronger tendency to segregate to boundaries but has a weaker grain boundary strengthening effect than B. Therefore, if sufficient P is present, it will preferentially segregate to the grain boundaries and exclude B, resulting in a weaker alloy. Conversely, if P is held to lower than normal levels, more B can segregate to the boundaries, strengthening them and thereby raising creep resistance. This explanation is consistent with our observations that B additions at levels higher than normally employed can substantially improve creep rupture resistance, but only if P levels are held to much lower than normal levels. These results are clearly shown in Table 1 and in FIGS. 2 and 3. TABLE 1__________________________________________________________________________CHEMICAL COMPOSITION OF WASPALOY TEST ALLOYSHeat Chemical Composition (wt %)No. C S Mo Cr Fe Co Ti Al Si B P__________________________________________________________________________Commercial AlloysG752-20.036 0.0006 4.21 19.72 0.07 13.46 2.96 1.30 0.01 0.006 0.004G753-10.038 0.0005 4.21 19.82 0.07 13.44 2.97 1.30 0.01 0.005 0.006WB74 0.036 0.0006 4.27 19.81 0.06 13.40 3.01 1.31 0.01 0.005 0.006P-B Modified AlloysG757-10.037 0.0006 4.23 19.75 0.07 13.48 2.96 1.30 0.01 <0.001 0.001G752-10.037 0.0006 4.19 19.74 0.07 13.50 2.92 1.29 0.01 0.006 0.001G757-20.036 0.0006 4.23 19.73 0.07 13.49 2.95 1.29 0.01 0.008 0.001WB71 0.032 0.0003 4.28 19.77 0.07 13.47 2.97 1.31 0.01 0.009 0.001G947-10.037 0.0005 4.27 19.85 0.08 13.44 3.00 1.30 0.01 0.012 0.001G949-10.039 0.0005 4.32 19.72 0.08 13.43 3.00 1.30 0.01 0.014 0.001WA52-10.036 0.0005 4.26 19.78 0.10 13.47 2.99 1.31 0.01 0.017 0.001WA52-20.037 0.0004 4.25 19.80 0.10 13.45 2.97 1.31 0.01 0.021 0.001WA53-10.036 0.0005 4.26 19.76 0.09 13.48 2.99 1.31 0.01 0.014 0.003G761-10.028 0.0005 4.26 19.74 0.07 13.45 3.01 1.31 0.01 <0.001 0.006G761-20.028 0.0005 4.28 19.76 0.09 13.42 3.07 1.31 0.01 0.009 0.006WA53-20.037 0.0006 4.26 19.75 0.09 13.50 2.97 1.31 0.01 0.014 0.005G753-20.037 0.0005 4.22 19.83 0.07 13.47 2.98 1.31 0.01 0.005 0.008G763-10.036 0.0005 4.23 19.72 0.07 13.47 2.95 1.33 0.01 <0.001 0.012G754-10.036 0.0006 4.22 19.72 0.08 13.42 2.93 1.35 0.01 0.005 0.012G754-20.037 0.0006 4.28 19.72 0.07 13.44 2.93 1.30 0.01 0.005 0.016G766-10.035 0.0005 4.28 19.74 0.08 13.46 3.03 1.29 0.01 <0.001 0.022G755-10.038 0.0006 4.22 19.76 0.07 13.42 2.95 1.28 0.01 0.005 0.022G766-20.037 0.0005 4.27 19.74 0.09 13.47 2.98 1.30 0.01 0.011 0.022__________________________________________________________________________ Having described the basic aspects of the invention, the following examples are given to illustrate specific embodiments thereof. EXAMPLE 1 In order to determine the effect of P and B content on mechanical properties, a large number of 50 pound heats were prepared by vacuum induction melting. Alloys were further processed by vacuum are remelting followed by homogenization, forging and rolling to nominal 5/8" diameter bar stock. Test samples were then cut from the bar, heat treated to the standard Aeronautical Materials Specification or commercial specification requirements and tested in accordance with appropriate ASTM standards. In all cases, the only purposeful variable was the P and/or B content. The remainder of the chemistry of the alloys was kept as constant as possible, as were all of the thermomechanical processing conditions. Chemical analysis results of a series of heats using the commercial Ni superalloy WASPALOY® as a base are presented in Table 1. Stress rupture results of these alloys are shown in Table 2. Because the stress rupture properties of WASPALOY® are so sensitive to grain size and since it is extremely difficult to reproduce exactly a constant grain size from bar to bar, even with constant process parameters, sufficient samples were prepared to determine the grain size dependence on stress rupture life. Although the grain size variation was very small (6 to 12 microns), this figure was then used to normalize the stress rupture values for different heats to the same grain size for comparison purposes. Both values (as tested and normalized) are presented in Table 2. The effects of P and B on stress rupture properties are best seen from FIGS. 1-3. From FIG. 1, it is observed that the stress rupture life for a "commercial" composition WASPALOY® (0.006% P and 0.006% B) is about 27 hours. Lowering the P to <0.001% by itself, a level far below normal commercial levels, or raising the B to 0.014% by itself, a level much above normal levels and above commercial specification limits, does not significantly change the stress rupture life for the alloy. However, if the P level is reduced to 0.001% and the B is simultaneously raised to 0.014%, the rupture life increases to 71 hours, an increase of 2.8× (280%). TABLE 2______________________________________STRESS RUPTURE PROPERTIES OF MODIFIEDWASPALOYALL SAMPLES HEAT TREATED:1865° F. × 4 HRS., WQ + 1550° F. × 4 HRS.,AC + 1400° F. × 16 HRS., AC S/R Properties at 1400° F./ S/R Life 64 Ksi CorrectedHeat Chemistry (wt %) Grain Size Life EL toNo. B P D, (μm) (HRS.) (%) D = 10.5 μm______________________________________Commercial AlloysG752-2 0.006 0.004 7.2 15.8 36.0 27.0G753-1 0.005 0.006 6.0 12.6 39.0WB74 0.005 0.006 12.0 33.6 40.0P-B Modified AlloysG757-1 <0.001 0.001 8.9 1.1 39.2 4.6G752-1 0.006 0.001 6.5 15.8 49.0 27.8G767-2 0.008 0.001 7.3 28.6 42.0 38.1WB71 0.009 0.001 11.2 51.3 40.5 49.2G947-1 0.012 0.001 10.5 54.7 39.5 54.7G949-1 0.014 0.001 10.3 70.6 41.0 71.2WA52-1 0.017 0.001 6.5 26.1 40.1 38.1WA52-2 0.021 0.001 7.2 16.6 46.8 26.4WA53-1 0.014 0.002 7.5 43.2 49.4 52.2G761-1 <0.001 0.006 9.0 1.4 42.0 5.9G761-2 0.009 0.006 8.5 16.7 39.5 22.7WA53-2 0.014 0.005 8.5 19.9 50.5 25.9G753-2 0.005 0.008 7.5 18.8 44.0 27.8G763-1 <0.001 0.012 8.5 3.6 11.5 9.6G754-1 0.005 0.012 7.0 15.6 37.5 26.1G754-2 0.005 0.016 9.5 19.4 43.6 22.4G766-1 <0.001 0.022 8.0 4.3 19.5 11.8G755-1 0.005 0.022 7.6 12.4 39.0 21.4G766-2 0.011 0.022 10.3 16.3 43.0 16.9______________________________________ The interdependence of the stress rupture life of WASPALOY® on P and B content is more clearly illustrated in FIG. 2 based on normalized data. Here, it can be seen that if the P content of the alloy is at 0.006% (normal commercial levels) or higher (0.022%), stress rupture life never exceeds about 30 hours, regardless of B content. Further, at these P levels, it appears that the beneficial effect of B saturates or reaches its maximum value at about 0.005% B which is approximately the normal commercial level for WASPALOY®. Beyond this level, further additions of B do not raise stress rupture life. In contrast, with an exceptionally low P level of 0.001%, stress rupture life of WASPALOY® increases continuously with B additions at least up to 0.014%. The critical inter-relationship of P and B with stress rupture life of WASPALOY® is shown even more clearly in FIG. 3. Over the full range of P and B contents investigated, exceptional rupture lives are displayed only at extremely low P levels <0.003% and more preferably <0.001%, and at higher than normal B levels 0.008% to 0.016% and more, preferably 0.012% to 0.016%. FIG. 4 shows the preferred ranges for P and B in an alloy of this invention for substantially improved stress rupture life compared to the level typically practiced in commercial WASPALOY® and the ranges allowed by typical commercial specifications. EXAMPLE 2 A series of test heats of a commercial Ni--Co--Cr precipitation hardened superalloy designated GTD-222 were prepared using exactly the same manufacturing practices as described in Example 1. The resulting bar was solution treated and aged in accordance with commercial specification requirements prior to testing. The only purposeful changes in composition again were P and B. The aim composition for the remaining elements was held constant. The slight variations observed in Table 3 are typical of those encountered in manufacturing and chemical analysis of these materials. TABLE 3__________________________________________________________________________CHEMICAL COMPOSITION OF GTD-222 TEST ALLOYSHeat Chemical Composition (wt %)No. C S W Cr Co Nb Ta Al Ti B P__________________________________________________________________________Commercial AlloysWC24 0.082 0.0006 2.11 22.35 19.24 0.77 0.99 1.19 2.35 0.0038 0.007P-B Modified AlloysWC21 0.085 0.0007 2.10 22.25 19.07 0.76 0.98 1.16 2.38 <0.001 0.003WC22 0.082 0.0006 2.14 22.73 19.33 0.81 0.98 1.34 2.36 0.0042 0.003WC23 0.080 0.0005 2.16 22.37 19.28 0.77 0.99 1.26 2.37 0.0108 0.003WC27 0.080 0.0007 2.15 22.39 19.32 0.77 1.01 1.17 2.37 <0.001 0.017WC26 0.078 0.0006 2.13 22.21 19.23 0.77 0.99 1.20 2.36 0.0046 0.020WC25 0.081 0.0006 2.15 22.36 19.21 0.76 0.98 1.17 2.39 0.0086 0.020__________________________________________________________________________ Table 4 presents the stress rupture results for this series of alloys. These data clearly show that changes in P or B content by themselves do not allow achieving optimum stress rupture life. Although the lowest P level achieved in this series of experiments was 0.003%, when combined with the highest level of B at 0.0106% B, a maximum stress rupture life of 76.2 hours (average) and the best elongation were achieved in the 1400° F.-67 ksi test. Maximum results were obtained at 1600° F.-30 ksi test conditions with peak rupture life and ductility at 0.003% P and 0.0042% B. TABLE 4______________________________________Stress Rupture Properties of Modified AlloyGTD-222ALL SAMPLES HEAT TREATED:2100° F. × 1 HR., WQ + 1475° F. × 8 HRS., WQHeat Chemistry S/R, 1400° F./67 ksi S/R, 1600° F./30 ksiNo. P B Life (hrs) EL (%) Life (hrs) EL (%)______________________________________WC-21 0.003 <0.001 3.8 2.0 17.0 10.0 2.2 0 13.1 9.0 av. 3.0 av. 1.0 av. 15.1 av. 9.5WC-22 0.003 0.0042 48.6 6.0 54.6 21.0 67.7 9.0 44.7 23.0 av. 58.3 av. 7.5 av. 49.7 av. 22.0WC-23 0.003 0.0106 70.0 12.0 48.6 19.0 82.4 10.0 43.0 20.0 av. 76.2 av. 11.0 av. 45.8 av. 19.5WC-24 0.007 0.0038 36.6 6.0 41.2 18.0 39.0 7.0 37.2 20.0 av. 37.8 av. 6.5 av. 39.2 av. 19.0WC-27 0.017 <0.001 4.6 2.0 11.5 2.5 5.4 0.5 12.7 4.0 av. 5.0 av. 1.3 av. 12.1 av. 3.3WC-26 0.020 0.0046 34.1 4.0 38.1 14.0 33.4 3.5 41.3 13.0 av. 33.8 Av. 3.8 Av. 39.7 Av. 13.5WC-25 0.020 0.0086 54.9 6.0 38.9 12.0 56.4 6.0 33.1 10.0 av. 55.7 av 6.0 av. 36.0 av. 11.0______________________________________ It is understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of this invention.
Nickel-base alloys with improved elevated temperature creep and stress rupture lives are disclosed which are particularly useful for components in gas turbine engines exposed to high temperatures and stresses for long periods of time. The alloys are nickel-based consisting essentially of 0.005 to 0.15% C, 0.10 to 11% Mo, 0.10 to 4.25% W, from 12 to 31% Cr, 0.25 to 21% Co, up to 5% Fe, 0.10 to 3.75% Nb, 0.10 to 1.25% Ta, 0.01 to 0.10% Zr, 0.10 to 0.50% Mn, 0.10 to 1% V, l.8-4.75% Ti, 0.5 to 5.25% Al, less than 0.003% P, and 0.004 to 0.025% B. Key to the improvement of creep and stress rupture lives is the extremely low P content in conjunction with high B contents.
2
This application is a divisional of 08/760,396, filed Dec. 4, 1999, now U.S. Pat. No. 5,830,121, which is a continuation of 08/330,258, filed Oct. 27, 1994, now abandoned. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an endoscopic apparatus which includes an endoscope and peripheral device to which the endoscope can be detachably attached. 2. Description of the Related Art The light source for an endoscope is required to supply light to a light guide and is essential to the endoscope. Further, in the case where the endoscope is a so called electronic endoscope, in which the image is transmitted via electric signals through a solid state image sensor, a video processor for accessing video signals from the solid state image sensor is also essential to the endoscope. Such support devices such as the light source and video processors described above are themselves expensive and large in size, so an endoscope is detachably attached to such a support (peripheral) device so that various types of endoscopes may be used with a single support device. Not only is an endoscope susceptible to wear, but it is also inserted into the human body and it is therefore necessary to check the endoscope every 100 hours or once every 50 to 100 uses in order to keep it in perfect working order. However, since various types of endoscopes are applied to a single light source, a single video processor or the like by replacing one endoscope with another as stated above, it is impossible to calculate the amount of time or the number of times that every endoscope is used with a single light source or a video processor. Therefore, it is unknown how many hours or how many times each endoscope is used after its initial use or after it is inspected or maintenanced, which sometimes leads to a worn or faulty endoscope being used. SUMMARY OF THE INVENTION The primary object of the present invention is to provide an endoscopic device in which the total usage hours and/or number of times used by each endoscope are recorded. To achieve the object mentioned above, according to the present invention, there is provided an endoscopic apparatus in which an endoscope is detachably attached to a peripheral device essential to the endoscope, the endoscopic apparatus comprising, means for detecting a total duration for the endoscope being in operation, and, storage means for storing the total duration detected by the detecting means. Preferably the detecting means further comprises means for sensing whether or not the endoscope is in operation, and means for measuring the current duration every time the sensing means senses that the endoscope is in operation. There is further provided an embodiment which has detecting means further comprising means for sensing whether or not the endoscope is in operation, and means for counting a number of times that the endoscope is in operation. The present disclosure relates to subject matter contained in the Japanese patent application Nos. 05-268472 (filed on Oct. 27, 1993), 05-276313 (filed on Nov. 5, 1993), 06-167755 and 06-167756 (both filed on Jul. 20, 1994) which are expressly incorporated herein by reference in its entirety. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described below in detail with reference to the accompanying drawings, in which; FIG. 1 shows a schematic view of the overall endoscope device according to an embodiment of the present invention; FIG. 2 shows a block diagram of a control circuit according to the embodiment; FIG. 3 shows a flow chart of a main program of the control process according to the embodiment; FIG. 4 shows a part of a flow chart of a program of an endoscope-related process according to the first embodiment; FIG. 5 shows a part of the flow chart of the program of the endoscope-related process according to the first embodiment; FIG. 6 shows a flow chart of a program of an interruption process according to the first embodiment; FIG. 7 shows a flow chart of a part of the endoscope-related process program according to the first embodiment; FIG. 8 shows is a schematic view of the picture of a monitor according to the first embodiment; FIG. 9 shows a flow chart of a keyboard processing program according to the first embodiment; FIG. 10 shows a schematic view of a RAM according to the second embodiment; FIG. 11 shows a part of a flow chart of the endoscope related process program according to the second embodiment; FIG. 12 shows a part of the flow chart of the endoscope-related process program according to the second embodiment; FIG. 13 shows a part of the flow chart of the endoscope-related process program according to the second embodiment; FIG. 14 shows a part of the flow chart of the endoscope-related process program according to the second embodiment; FIG. 15 shows a schematic view of the storage area of a RAM according to the third embodiment; FIG. 16 shows a part of a flow chart of an endoscope-related process program according to the third embodiment; FIG. 17 shows a part of the flow chart of the endoscope-related process program according to the third embodiment; FIG. 18 shows a part of the flow chart of the endoscope-related process program according to the third embodiment; FIG. 19 shows a flow chart of a keyboard processing program according to the third embodiment; FIG. 20 shows a flow chart of the endoscope-related processing program according to the fourth embodiment; FIG. 21 shows a flow chart of an interruption processing program according to the fourth embodiment; and, FIG. 22 shows a schematic view of the storage area of a RAM according to the fourth embodiment. DESCRIPTION OF THE PREFERRED EMBODIMENT An endoscopic system according to an embodiment of the present invention will be explained with reference to the drawings. FIG. 1 is a schematic view of the overall configuration of the endoscope system. Reference numeral 10 is an endoscope. An operating portion 14 with operating devices is connected to the base of a flexible insertion portion 11 with a built-in objective optical system 12, and a solid-state image sensor 13 and the like at the tip 11a thereof. Further, a connector 16 at the tip of a flexible connecting tube 15 is removably connected to a video processor and light source device 20. In the connection tube 15, a light guide fiber bundle (not shown) for transmitting light for lighting the subject and a signal cable 17 for transmitting video signals from the solid-state image sensor 13 are inserted and connected to the connector 16. A storage cell 19 comprising an electrically erasable programmable read only memory (EEPROM), for example, is built into the connector 16. In the video processor and light source device 20, a light source 22 for supplying light to the light guide fiber bundle, a video signal processor 21 for processing video signals transmitted from the solid-state image sensor 13, and controller 30 with a microcomputer for various controls (hereinafter merely referred to as "microcomputer") are accommodated. As a result, in order to use the endoscope 10, the connector 16 is always connected to the video processor and light source device 20, and since it is required to clean and disinfect the endoscope 10 in a disinfectant after use, the connector 16 is always disconnected from the video processor and light source device 20 after each use of every endoscope. Numeral 50 shows a monitor for reproducing visible images from the image signals which are transmitted from the solid state image sensor 13. The endoscope system is further provided with an air tube, a water tube, and a suction tube (not shown). FIG. 2 is the microcomputer 30 in the video processor and light source device 20 and peripheral device therefor for controlling the brightness of the light source bulb 22a, images displayed on the monitor 50, and superimposition of date on the display. A system bus 32 is connected to a central processing unit (CPU) 31. A read only memory (ROM) 33 in which programs and the like are installed, a random access memory (RAM) 34 and a real time clock (RTC) 35 are connected to the system bus 32. Character data for display installed in a video random access memory (video RAM) 36 and the image data outputted from the video signal processor 21 are synthesized by the CRT controller (CRTC) 37 connected to the system bus 32 and outputted to the monitor 50. A panel switch 23 of the video processor and light source device 20, a lamp control circuit 22b for controlling the light source lamp 22a, and a keyboard 24 are connected to each other through input/output ports 40, 38 and 39 respectively. Numeral 41 is a programmable interruption controller (PIC) and numeral 42 shows a programmable interval timer (PIT). To the input/output port 43, to which the connector 16 of the endoscope 10 is connected, is further connected the storage cell 19 in the endoscope 10 via the connector 16 to serially transmit and receive data. A switch 45 connected to the input/output port 43 is depressed by connecting the connector 16 to the video processor and light source device 20; the corresponding terminal turns to low level, which causes the connection of the endoscope 10 to be detected. Numeral 46 shows an alarm buzzer. Data indicating the type of endoscope in operation is installed in the storage cell 19 which is built into the connector 16 of the endoscope 10 in advance. Further, the connector 16 is connected to the video processor and light source device 20, and the total usage operating time while the light source lamp 22a is switched on, that is, the time that the endoscope 10 is in service is stored. Then, the total usage operating time is displayed on the monitor 50. When the total usage operating time of the endoscope 10 reaches a standard time between maintenance value, the alarm 46 is actuated. The above operation and control method will be explained below. FIGS. 3-5 are flow charts showing the content of the main program installed in the ROM 33 of the microcomputer 30. In the flow chart, "S" indicates the step processed. Reference symbols u1 and u3 are variables (flags) for classifying programs. The variable "u1" shows whether or not the connector 16 of the endoscope 10 is connected to the video processor and light source device 20 ("u1=1" means connected and "u1=0" disconnected). The variable "u3" is use to shows whether or not to indicate a total operating time of the endoscope 10 exceeds a standard value ("u3=1" is displayed and "u3=0" not displayed). After the initial setting such as "u1=0" at step S1, an endoscope-related process is executed at step S2. The content of the process will be explained in detail with reference to FIG. 4 and following figures. After the endoscope-related process at step S2, lamp-control-circuit-related processing is executed at step S3 and the process set by the panel switch 23 is executed at step S4. After the panel-switch processing at step S4, input processing from the keyboard 24 at step S5, the date-and time display processing at step S6 and other processing at step S7 are executed, and the sequence returns to the endoscope-related processing at step S2 to repeat the above process. FIGS. 4 and 5 are flow charts showing the content of the endoscope-related process at step S2. At first, the condition of the input/output port 43 to which the connector 16 of the endoscope 10 is connected is inputted at step S11. Then, whether or not the variable u1 is zero is judged at step S12. If u1=0 at step S12, which means the connector 16 was not connected to the video processor and light source device 20 immediately after the initial setting or at the last checking, whether the connector 16 is connected to or disconnected from the video processor and light source device 20 is judged based on whether the connector input terminal of the input port 43 is at a high level or at a low level at step S13. Subsequently, if the connector 16 is disconnected, "0" is set to u1 and interruption is prohibited to finish the endoscope-related processing at S2; then the sequence advances to the lamp-related processing at step S3. If the connector 16 is judged to be connected at step S13, the variable u1 is set to 1 at step S14, the counter of the programmable interval timer (PIT) 42 is set at step S15, and the interruption flag of the programmable interruption controller (PIC) 41 is reset to allow the interruption at step S16. The interruption process is executed every seven-and-half minutes, for instance, by the PIC 41 and PIT 42 based on the program described by the flow chart in FIG. 6. In this process, for caution's sake as at step S13, whether or not the connector 16 of the endoscope 10 is connected to the video processor and light source device 20 is judged at step S31. This step S31 is executed as a precaution and is therefore negligible. Subsequently, the connector 16 is disconnected and the interruption is finished without execution. To the contrary, if the connector 16 of the endoscope 10 is connected to the video processor and light source device 20, whether or not the light source lamp 22a is turned on is checked at step S32, and the interruption is completed unless the lamp 22a is turned on. At step S32, if the light source lamp 22a is turned on, the endoscope 10 is in service; therefore number of n units of time data is read from the storage cell 19 of the endoscope 10 at step S33 and "1" is added to number of n at step S34; the result is written in the storage cell 19 of the endoscope 10 at step S35. As described above, the total number of n units of time for the endoscope 10 is stored in the storege cell 19 after each 7.5 min. period that the endoscope has been used the number is incremented by "+1 (1 is added)". Referring to FIGS. 4 and 5 again, immediately after the interruption is permitted at step S16, the type of endoscope 10 in operation and the operating time of the endoscope 10 are read from the storage cell 19 of the endoscope 10 at step S17. Then, the standard time between maintenance value and the variable u3 are set in accordance with the type of endoscope 10 at steps S18 to S24. The setting of the variable u3 is executed based on the program shown in the flow chart in FIG. 7. At first, whether or not the total usage operating time exceeds the standard time between maintenance value is checked at step S41. The standard value varies with the type of endoscope used, i.e. for the upper alimentary canal, colon, or other special purpose. The result of the judgment of type of endoscope at steps S18 to S20 gives different standard operating time at steps S18, S21, S19, S22a, S20 and S23a. Unless the total usage operating time reaches the standard time between maintenance value, the variable u3 set to zero at step S42. To the contrary, if the total usage operating time reaches the standard time between maintenance value, u3 is set to "1" at step S43. After the variable u3 is set, referring to FIGS. 3 and 4 again, whether or not the variable u3=1 is judged at step S25. If the variable u3 is not "1", the sequence advances to the lamp-related process at step S3. If the variable u3 is "1", as illustrated in FIG. 8, overuse of the endoscope is displayed on the monitor 50 at step S26 and the alarm buzzer 46 is simultaneously actuated for five seconds for example, then the sequence advances to the lamp-related process at step S3. As described above, the integrated operating time of the endoscope 10 is compared with the standard value based on the type of endoscope. When exceeding the standard operating time, the result is displayed on the monitor 50 and the alarm buzzer 46 is actuated at step S27. If the variable u1 is not "0" at step S12, which means it is not just after the initial setting and the connector 16 was connected to the video processor and light source device 20 at the last checking, whether or not the connector 16 is disconnected from the video processor and light source device 20 is checked at step S28 as at step S13. Then, if the connector 16 is judged to be connected also, the sequence immediately advances to the lamp-related process at step S3. To the contrary, if the connector 16 is disconnected, the variable u1 is set to zero at step S29 and the interruption is prohibited at step S30, then the sequence advances to the lamp related process at step S3. In this embodiment, the total usage operating time of the endoscope 10 can be displayed on the monitor 50. However, whether the result is to be displayed on the monitor 50 or not is choosable through the eighth key F8 of function keys on the keyboard not shown. FIG. 9 is a flow chart showing the content of the program for switching the display of the integrated operating time as one of the processes of keyboard at step S5. In this step, whether or not any key of the keyboard 24 is depressed is checked first, and if no key is depressed, the processing of key board at step S5 is finished and the sequence advances to the date and time related process at step S6. If any key of the keyboard is depressed, whether or not the depressed key is the eighth key F8 is checked at step S52. Unless the key is F8 key, the processing corresponding to the depressed key is executed at step S53 and the sequence advances to the date and time related process at step S6. If the F8 key is switched on, whether or not the integrated operating time is already displayed on the monitor 50 is judged at step S54, and if so, the indication is erased at step S58 and the sequence advances to the date and time related process at step S6. If the total usage operating time is not displayed on the monitor 50, the total usage operating time is read from the storage cell 19 of the endoscope 10 at step S55, and the data is converted into the amount of time at step S56 to display it on the monitor 50 at step S57, and then the sequence advances to the date and time related process at step S6. In the conversion at step S56, the interruption for adding "1" to the data on the service of the endoscope is executed once per seven-and-half minutes (eight times an hour), so the data on the operating time is set to "n" represents the number of interruption loop cycles, the total usage operating time that the endoscope is in service equals n/8 hours or 7.5×n minutes. Next, the endoscope-related process at step S2 according to the second embodiment of the present invention will be explained. In this embodiment, the serial number of the endoscope 10 is installed in the storage cell 19 of the endoscope 10 in advance. The total usage operating time of the endoscope 10 measured with the timer (RTC) 35, and the count (one hour) is also stored in the storage cell 19. As illustrated in FIG. 10, the RAM 34 of the video processor and light source device 20 is provided with a storage area where the serial number of the connected endoscope 10 and the operating time for its single usage are written as a data set, and the stored data is sustained using a cell or the like. The data may be written to a recording media such as a magnetic recording media including a hard disk. In this embodiment, no interruption is executed to calculate the total usage operating time of the endoscope, so the PIC 41 and PIT 42 are unnecessary. Valuables u1 and u5 are used for classifying programs, and the variable u1 is similar to that used in the first embodiment. The variable u5 is set to "1" when the connector 16 is connected to the video processor and light source device 20 and the light source lamp is turned on, and the variable u5 is set to zero in other cases. FIGS. 11 to 14 are flow charts showing programs for the endoscope related process at step S2 in the second embodiment. The content of programs other than main program is the same as those of the first embodiment. The same processes as at steps S11 to S13 of the first embodiment are executed at steps S61 to S63. Then, if the connector 16 is judged to be disconnected from the video processor and light source device 20 at step S63, the sequence immediately advances to the lamp-related process at step S3. To the contrary, if the connector 16 is judged to be connected to the video processor and light source device 20 at step S63, the variable u1 is set to "1" at step S64, and the serial number of the endoscope in the storage area of the RAM 34 is searched for at step S65, and then the serial number of the endoscope 10 connected at that time is read from the storage cell 19 for comparison at step S66. Then, if the serial number of the endoscope 10 in operation is stored in the storage area of the RAM 34, the amount of time that the endoscope has been used (operating time at last single usage) which is stored in the RAM 34 is added to the total usage operating time in the storage cell 19 of the endoscope 10, and the operating time stored in the RAM 34 is reset to zero at step S67. Further, when the number of the endoscope 10 in service is not stored in the storage area of the RAM 34, the number of the endoscope is written in a vacant area of the RAM 34 at step S68. Subsequently, whether the light source lamp 22a is turned on or not is checked at step S69. If the lamp 22a is turned off, the variable u5 is set to zero at step S72, and the sequence advances to the lamp-related process at step S3. To the contrary, the light source lamp 22a is turned on, the variable u5 is set to "1" at step S 70; the present time is read from the RTC 35 and is stored at step S71; and the sequence advances to the lamp-related process at step S3. If it is judged at step S62 that the variable u1 is not zero, which means the connector 16 is connected to the video processor and light source device 20 at the last checking but immediately after initial setting, as at step S28, whether or not the connector 16 is disconnected from the video processor and light source device 20 is checked at step S73. Subsequently, if the connector 16 is disconnected, the operating time at that time is calculated by RTC 35 at step S74, and the operating time is written in an address of the RAM 34 corresponding to the number the endoscope in service at step S75. Then, both variables u1 and u5 are set to zero and the sequence advances to the lamp-related process at step S3. The present operating time is obtained at step S74 by calculating the interval between the time starting the lighting stored in steps S71 or S80 and the present time. If the connector 16 is judged to be connected at step S73 also, whether or not the variable u5 is zero is checked at step S77. If the variable u5 is zero and the light source lamp 22a is turned off at step S78, the sequence immediately advances to the lamp-related process at step S3. To the contrary, if the light source lamp 22a is turned on, the variable u1 is set to "1" at step S79; and the time is stored at step S80; and the sequence advances to the lamp-related process at step S3. If the variable u5 is not zero at step S77, and unless the light source lamp 22a is turned on at step S81, the sequence soon advances to the lamp-related process at step S3. To the contrary, if the lamp 22a is turned on, the variable u5 is set to "1" at step S79; the present operating time is calculated at step S82; the data is written in the RAM 34 as at steps S74 and S75; and the sequence advances to the lamp-related process at step S3. The present invention is not limited to the above embodiments and a part or all of integration means for calculating the total usage operating time may be mounted on the endoscope side for example. Further, the total usage operating time storage means for storing total usage operating time may be mounted on the side of the support device such as the video processor or light source device. With the construction described above, the operating time for each endoscope for a variety of types of endoscopes are read at once from the total usage operating time storage means without having to connect each endoscope to the support device one by one, and the data is displayed in a table on the monitor or the like, which permits the total usage operating time for each endoscope to be confirmed at a glance. For the above purposes, the storage area of the RAM 34 in the microcomputer 30 should be enlarged, for example as illustrated in FIG. 15, and the area where the total usage operating time as well as the operating time for that specific event is stored and prepared in accordance with the serial number of each endoscope. Then, at the processing step S67 indicated in FIG. 12, the operating time data for that specific event which is stored in the RAM 34 is added to the total usage operating time data in the RAM 34. With the construction of the endoscope device according to the present invention, since the total usage operating time for each endoscope is stored in the storage cell, the total usage operating time for that endoscope can be displayed, and when it reaches the standard time between maintenance value, the result is displayed and an alarm is actuated, which prevents the overuse of the endoscope in advance. As a result, the failure of the endoscope system or the accidents caused by the system is avoidable through inspection, maintenance and exchange of worn parts. As a result of employing this apparatus manufacturers of endoscopes will be able to easily gather data on the relationship between total usage time number of operations and types of failure this will contribute greatly to improvements and quality. In the case where the total usage operating time storage means is mounted on the endoscope side, the total usage operating time of the endoscope can be checked regardless of the support device to which the endoscope is connected. On the other hand, if the total usage operating time storage means is attached to the support device side, the total usage operating time of several endoscopes can be confirmed at a glance with a table without having to connect each endoscope one by one. In the embodiment described above, total usage operating time of the endoscope is calculated. Next, an endoscope apparatus according to another embodiment of the present invention will be explained. In this embodiment, the number of times that the endoscope is connected to the video processor and light source device is counted. The construction of the endoscope apparatus in this embodiment is the same as the apparatus shown in FIGS. 1 and 2, and a main flow chart of this embodiment is the same as that shown in FIG. 3, therefore the indication thereof will be omitted. FIGS. 16 and 17 are flow charts showing the third embodiment of the endoscope-related processing at step S2. In this embodiment, the programmable interrupting controller(PIC) 41 and the programmable interval timer (PIT) 42 are unnecessary to the microcomputer 30, resulting in simple construction. In this embodiment, firstly, the condition of the input/output ports 43 to which the connector 16 of the endoscope 10 is connected is inputted at step S111. Then, whether or not the variable u1 is zero is judged at step S112. If the variable u1 is zero at step S112, which means that the connector 16 was disconnected from the video processor and light source device 20, whether or not the connector 16 is connected to the video processor and light source device 20 is judged based on whether the input terminal of the input port 43 is in high level or in low level at step S113. If the connector 16 is disconnected, the endoscope-related processing at step S2 is finished soon, then the sequence advances to the lamp-related process at step S3. To the contrary, if the connector 16 is connected, a variable u7 is set to "1" at step S114 , and the type and the number of connections for that endoscope 10 in service is read from the storage cell 19 of the endoscope 10 at step S115. Subsequently, "1" is added to the number of times that the endoscope 10 is connected at step S116 to write the result in the storage cell 19 of endoscope 10 at step S117. Subsequently, the variable u7 is set in accordance with the type of endoscope 10 at steps S118 to S124. The variable u7 is set based on the program shown in a flow chart of FIG. 18. Whether or not the number of times that the endoscope 10 is connected is more than the standard maintenance value is checked at step S141. The standard maintenance value varies with the type of endoscope used, which is judged at steps S118 to S120, i.e. for the upper alimentary canal, colon, bronchus or other special purpose. The result of the judgment of type of endoscope at steps S18 to S20 gives different standard maintenance values. Unless the number of connections reaches the standard maintenance value, the variable u7 set to zero at step S142. To the contrary, if the number of connections reaches the standard maintenance value, u7 is set to "1" at step S143. After the variable u7 is set at steps S121 to S124, referring to FIGS. 16 and 17 again, whether or not the variable u7=1 is judged at step S125. If the variable u7 is not "1", the sequence advances to the lamp related process at step S3. To the contrary, if the variable u7 is "1", as illustrated in FIG. 8, overuse of the endoscope 10 is displayed on the monitor 50 at step S126 and the alarm buzzer 46 is simultaneously actuated for five seconds for example, then the sequence advances to the lamp-related process at step S3. As described above, the number of connections of the endoscope 10 is compared with the standard maintenance value based on the type of endoscope. When exceeding the standard maintenance value, the result is displayed on the monitor 50 and the alarm buzzer 46 is actuated at step S127. If the variable u1 is not "1" at step S112, which means it is not just after the initial setting and the connector 16 was connected to the video processor and light source device 20 at the last checking, whether or not the connector 16 is disconnected from the video processor and light source device 20 is checked at step S128 as at step S113. Then, if the connector 16 is judged to be connected also, the sequence immediately advances to the lamp-related process at step S3. To the contrary, if the connector 16 is disconnected, the variable u1 is set to zero at step S129 and the sequence advances to the lamp-related process at step S3. In this embodiment, the number of connections of the endoscope 10 can be displayed on the monitor 50. However, whether the result is to be displayed on the monitor or not is changeable through the ninth key F9 (not shown) of function keys on the keyboard 24. FIG. 19 is a flow chart showing the content of the program for switching the display of the number of connections as one of the processes of keyboard at step S5. In this step, whether or not any key of the keyboard 24 is depressed is checked first at step S151, and if no key is depressed, the processing of key board at step S5 is finished and the sequence advances to the date-and-time-related process at step S6. If any key of the keyboard 24 is depressed, whether or not the depressed key is the ninth key F9 is checked at step S152. Unless the key is F9 key, the processing corresponding to the depressed key is executed at step S153 and the sequence advances to the date-and-time-related process at step S6. If the F9 key is switched on, whether or not the number of connections is already displayed on the monitor 50 is judged at step S154, and if so, the indication is erased at step S157 and the sequence advances to the date-and-time-related process at step S6. If the number of connections is not displayed on the monitor 50, the number of connections is read from the storage cell 19 of the endoscope 10 at step S155, and the data is displayed on the monitor 50 at step S156, and then the sequence advances to date and time related process at step S6. Next, the fourth embodiment of the endoscope-related processing at step S2 will be explained. In this embodiment, a connecting operation carried out within four minutes of the last use is not counted as one this will exclude connecting or disconnecting operations of the connector 16 not for the purpose of using the endoscope from the connection count processing. FIG. 20 is a flow chart used in this embodiment. Firstly, the condition of the input/output ports 43 to which the connector 16 of the endoscope 10 is connected is inputted at step S161. Then, whether or not the variable u1 is zero is judged at step S162. If the variable u1 is zero at step S162, which means that the connector 16 was disconnected from the video processor and light source device 20, whether or not the connector 16 is connected to the video processor and light source device 20 is judged based on whether the input terminal of the input port 43 is at a high level or at a low level at step S163. If the connector 16 is disconnected, the endoscope-related processing at step S2 is finished soon, then the sequence advances to the lamp-related process at step S3. To the contrary, if the connector 16 is judged to be connected at step S163, the variable u1 is set to "1" at step S164, and the counter of the programmable interval timer (PIT) 42 is set such that the interruption is executed after four minutes at step S165 and the interruption mask of the programmable interruption controller (PIC) 41 is reset to prepare for the interruption at step S166. The interruption is executed based on the program shown in a flow chart of FIG. 21. For caution's sake as at step S113, whether or not the connector 16 of the endoscope 10 is connected to the video processor and light source device 20 is judged at step S171. This step is executed as a precaution and is therefore negligible. Subsequently, if the connector 16 is disconnected, the interruption is finished without execution. To the contrary, if the connector 16 of the endoscope 10 is connected to the video processor and light source device 20, the number of connections of the endoscope 10 is read from the storage cell 19 of the endoscope 10 at step S172, and "1" is added to the data at step S173 to write the result in the storage cell 19 of the endoscope 10 at step 174. Finally, for caution's sake, the programmable interruption controller (PIC) 41 is brought to the state that interruption can not be executed at step S 175. Referring to FIG. 20 again, if the variable u1 is not "1" at step S162, which means it is not just after the initial setting and the connector 16 was connected to the video processor and light source device 20 at the last checking, whether or not the connector 16 is disconnected from the video processor and light source device 20 is checked at step S167 as at step S163. Then, if the connector 16 is judged to be connected also, the sequence immediately advances to the lamp-related process at step S3. To the contrary, if the connector 16 is disconnected, the variable u1 is set to zero at step S168 and the interruption is prohibited at step S169, then the sequence advances to the lamp related process at step S3. The present invention is not limited to the above embodiment and a part or all of integration means for number of connections may be mounted on the endoscope side for example. Further, the storage means for storing number of connections may be mounted on the side of essential device such as the video processor and light source device. With the construction described above, the number of connections of each endoscope in a various types of endoscopes is read at once from the total usage operating time storage means without connecting each endoscope to the essential device one by one, and the data is displayed in a table on the monitor or the like, which permits the number of connections of each endoscope to be confirmed at a glance. The indication on the monitor may be carried out by depressing the F9 key of the keyboard 24. For the above purposes, the storage area of the RAM 34 in the microcomputer 30 should be extended, for example as illustrated in FIG. 22, and area where the number of connections is prepared in accordance with the number of every endoscope. The number of connections of the endoscope 10 is written in the storage area of the RAM 34 at the processing at step S117 in FIG. 16. In the present invention, the video processor and light source device includes a single light source, a single video processor, or other devices essential to the endoscope. Further, the device essential to the endoscope includes not only a unit such as a light source device and a video processor but also an element or a part composing such unit device. The present invention is applicable to an endoscope in which image is transmitted through image guide fiber bundle. With the construction of the endoscopic apparatus according to the present invention, since the number of connections of each endoscope is stored in the storage cell, the number of connections of the endoscope can be displayed, and when the number of connections reaches the standard maintenance value the result is displayed and alarm is actuated, which prevents the overuse of the endoscope in advance. As a result, the failure of the endoscope system or the accidents caused by the system are avoidable through inspection, maintenance and exchange worn parts. As a result of employing this apparatus the manufacturer of endoscopes will be able to easily gather data on the relationship between the total usage time, the number of operations and types of failures, this will contribute greatly to improvements and quality through the feedback of this data to designers. In the case where the storage means is mounted on the endoscope side, the number of connections of the endoscope can be checked regardless of the support device to which the endoscope is connected. On the other hand, the storage means is attached on the support device side, the number of connections of many endoscopes is confirmed at a glance with a table without connecting each endoscope one by one. Although the total usage operating time of the endoscope is calculated or the number of connections thereof is counted in the embodiments illustrated in the drawings, both of them may be carried out at the same time by combining those functions of the apparatus.
An endoscope apparatus includes at least one endoscope, a peripheral device having a light source, and a detachable connecting device to connect the endoscope to the peripheral device. The emission time or illumination duration of the light source is measured and stored in the peripheral device. An indicating device is used to display the stored emission time or illumination duration independent of the connection between the endoscope and the peripheral device.
0
DESCRIPTION The invention relates to a ready-to-use support, which has a self-adhesive coating on one side, for stabilizing and guiding the patella in its natural slide bearing. The functional bandaging technique called taping is a treatment method for the prophylaxis and therapy of injuries, disorders and changes in the locomotor system. The aim of taping is specifically to simulate the capsule/ligament structures and thus achieve selective support and stabilization. The actual taping bandage is for this purpose applied stripwise from preferably inelastic self-adhesive tapes, called straps, or in conjunction with self-adhesive tapes with short-stretch elasticity. It protects, supports and relieves portions of a functional unit which are at risk, damaged or impaired. It permits functional loading in the pain-free movement range but prevents extreme or painful movements. However, the application of such bandages requires expert skill and experience and therefore, as a rule, cannot be carried out by laypeople without taping experience. An additional difficulty specifically in the region of the knee joint is that the hollow of the knee is in most cases covered with bandaging material, and thus flexion of the knee is not sufficiently possible. So-called ready-to-use supports of elastic fabric or neoprenes have the disadvantage that they are not adequately fixed to the skin and thus may act only globally on a large area, not selectively. Specific stabilization and guidance is impossible in most cases. It was therefore an object of the invention to provide a ready-to-use support which, by reason of its design, its material and its properties, is suitable for prophylactic support and selective guidance of the patella and which can be applied in a simple manner even by the user. This object is achieved by a ready-to-use support according to claim 1. It has proved particularly advantageous to have a circular cutout which is located in the middle of the strip and which has a diameter of about 4 cm suited to the size of the patella. This makes it possible to employ the ready-to-use support according to the invention universally for guiding the patella to prevent lateralization, that is to say displacement sideways of the patella, or medialization, that is to say displacement of the patella parallel to the vertical axis of the body. The strips of the ready-to-use support have a length of about 1 m, preferably about 80 cm, with the unslit part of the strip being about 8 cm long and 10 cm wide, and the two strips produced by the slit each being about 68 cm long and 5 cm wide. Thus, with the cutout, which has a length of about 4 cm, the resulting total length of the ready-to-use support is about 80 cm. The ready-to-use support preferably consists of a longitudinally elastic woven or knitted fabric which may, where appropriate, also have a slight transverse elasticity, in particular based on cotton. The longitudinal elasticity preferably corresponds to that of so-called short-stretch bandages, that is to say bandages with an extensibility of about 60-90%. In order to relieve the leg muscles, the ready-to-use support should be applied with the knee slightly flexed. For this reason, the unslit narrow side of the strip preferably has a concave curvature which reproduces the curve of the knee and thus facilitates application of the ready-to-use support to the knee joint. It is advantageous, in order to make it easy to pull the ready-to-use support off the knee joint, for the ends of the two strips which are separated by the slit to have a convex curvature. The ready-to-use support is coated on the side which is placed on the skin with one of the known self-adhesive compositions which are based on rubber or synthetic polymers and which adhere well. The compositions advantageously have other properties such as good compatibility with skin or permeability to air and water vapour. Until the support is used, the adhesive layer is covered with a sheet material with an abherent finish, such as, for example, siliconized paper or plastic film. In this connection, it has proved to be particularly user-friendly to divide the covering into several individual parts, preferably three parts. One part covers the unslit part, and in each case one other strip-shaped part covers the narrow strips of the ready-to-use support. In order further to facilitate application, these individual covering parts can also be appropriately visually distinguished. FIG. 1 shows the ready-to-use support in its preferred embodiment. The ready-to-use support is composed of the unslit part (1) and of the strips (2) and (3) produced by the slit, called the straps. The unslit part (1) has a concave curvature (5), and the two strips (2) and (3) have a convex one. FIG. 2 depicts the preferred embodiment of the ready-to-use support as applied to the knee joint to immobilize the patella against lateralization. In the first step, the covering paper is pulled off the unslit part (1) of the ready-to-use support. The unslit part (1) of the ready-to-use support is subsequently applied laterally to the knee joint which is flexed in a small angle of, preferably, 20°-30° in such a way that the circular cutout (4) in the ready-to-use support firmly encloses the patella, and the two straps (2) and (3) point in the medial direction. After removal of the covering paper on the strap (2) which is in proximal/ventral contact with the patella, the strap is guided distally with a slightly spiral movement around the leg. The strap (2) is moreover guided dorsally in such a way that the hollow of the knee remains substantially uncovered. The end of the strap (2) on the lower leg is located on the ventral side. The strap (3) which is in distal/ventral contact with the patella is applied analogously after the covering paper has previously been pulled off. The strap (3) is applied proximally, with a spiral movement, to the leg. The two straps (2) and (3) cross over on the medial part of the patella in order thus to provide the patella with the required support. The second strap (3) is also placed in such a way that, on the one hand, the dorsal portion of the hollow of the knee is left substantially uncovered and, on the other hand, the end thereof is located on the ventral side on the thigh. The described mode of application of the ready-to-use support results in stabilization of the patella and, at the same time, lateralization of the latter is counteracted. The strap (2) provides distal and lateral support for the patella, and strap (3) provides proximal and lateral support. Hence unwanted lateral movement of the patella is substantially precluded. Alternatively, the ready-to-use strap can, however, also restrict medialization of the patella, in that the unslit part (1) of the ready-to-use support is firmly applied distally or proximally to the patella, and the straps (2) and (3) are subsequently stuck on in analogy to that described above.
Ready-to-use support with a self-adhesive coating on one side for stabilizing and guiding the patella, characterized in that the ready-to-use support consists of an elongate strip which has, approximately over the entire length, a slit in the longitudinal direction on one side, and in that a cutout is located at the inner end of the slit and serves to receive the patella when the ready-to-use support is applied to the knee.
0
This application is a continuation-in-part of PCT/EP 98/01678, filed Mar. 23, 1998. BACKGROUND OF THE INVENTION The present invention concerns nonpneumatic wheels, notably, those capable of being used in substitution for tires on vehicles. It has been tried for a long time to design such nonpneumatic wheels, that is, operating without compressed air, in order to overcome every problem raised by flats or reduction of inflation pressure of tires. Among very numerous proposals, the one described in U.S. Pat. No. 3,234,988 can be cited. That patent describes a nonpneumatic deformable wheel containing a disk, an internal element fastened to the disk, an annular external element, flexible and appreciably inextensible, intended to come in contact with the road, and a plurality of spokes arranged between the internal and external elements. The external element has a length such that it stresses the spokes under radial compression. In other words, they are prestressed (that is, preloaded). Beyond a certain stress threshold, since the spokes are stressed on end, the radially oriented reaction force that each of those spokes can develop remains constant. The wheel also contains means of stabilization of the relative positions of the external and internal elements. The spokes bend in a meridian plane and the means of stabilization limit the relative axial displacements of the internal and external elements. This deformable wheel uses as connection between the internal and external elements spokes prestressed beyond their buckling load. Thus, in case of increase of the load supported by the wheel, that increase is compensated only by an increase in number of spokes actually supporting the load. This results in an increase of length of the contact between the wheel and the road. Such behavior is very close to that of a tire. This wheel presents, however, one major disadvantage. The different spokes buckle in their meridian planes, but have practically no possibility of circumferential deformation, for their section presents great inertia in the circumferential direction. Now, on rolling, considerable longitudinal forces are undergone by the external element in contact with the road, notably, in the area of contact, which leads to rapid deterioration of the previous nonpneumatic wheel. SUMMARY OF THE INVENTION The object of the invention is a deformable structure designed to constitute, with a disk, for example, a nonpneumatic wheel presenting the same advantages of comfort and performance, while solving the preceding problem. The deformable structure for a vehicle, according to the invention, designed to roll on an axis of rotation, comprises an annular internal element centered on the axis, an annular external element, flexible and appreciably inextensible, forming a tread, radially arranged externally relative to the internal element, a plurality of spokes arranged between the internal and external elements, each spoke being capable of opposing an appreciably constant force under a radial compressive stress beyond a given threshold, the annular external element having a length such that the spokes are prestressed in radial compression, as well as means for stabilizing the relative positions of the internal and external elements. This rolling structure is characterized in that the spokes are formed and arranged between the internal element and external element, in such a way that their flexibility in a meridian plane is well below their flexibility in a circumferential plane, and in that the means for stabilizing limit the amplitude of a circumferential relative rotation between the internal and external elements. The wheel obtained from the deformable structure according to the invention presents the following advantage: each spoke can be deformed in a circumferential direction, in particular during rolling, when it is in the zone of contact between the external element and the road. The spokes are preferably prestressed beyond their buckling load. The means of stabilization can also include elastic connections nonradially joining the internal and external elements, such as cables or slender beams. The means of stabilization are prestressed in extension in state of rest in order to exert a return force immediately upon a relative rotation displacement between the internal and external elements. The ends of the spokes can be fastened by embedding or by joints in the internal element and/or external element. The means of stabilization can also be a thin shell prestressed in radial extension. The deformable structure according to the invention can also constitute a safety insert designed to be mounted in an assembly consisting of a tire and a rim. DESCRIPTION OF THE DRAWINGS Several embodiments of the invention are now described by means of the following figures: FIG. 1 is an axial view of a wheel according to the invention consisting of a deformable structure fastened to a disk; FIG. 2 is a meridian section of the wheel of FIG. 1; FIG. 3 is a partial axial view of a wheel similar to that of FIGS. 1 and 2, equipped with stabilization means; FIG. 4 presents jointed double spokes in state of rest 4 a and in deformed state 4 b; FIG. 5 presents another embodiment of the spokes, double and embedded, in state of rest 5 a and in deformed state 5 b; FIG. 6 presents spokes of the wheel of FIG. 1 under load, outside area of contact 6 a and in area of contact 6 b ; and FIG. 7 presents means of stabilization of the wheel of FIG. 6 under load, outside area of contact 7 a and in area of contact 7 b. DESCRIPTION OF PREFERRED EMBODIMENTS FIGS. 1 and 2 present, in axial view and in meridian section, respectively, a nonpneumatic wheel consisting of a deformable structure 1 according to the invention, attached to a disk 2 . The deformable structure 1 includes an internal element 3 connected to the disk 2 , an annular external element 4 and spokes 5 joining the internal element 3 and the external element 4 . The spokes 5 are distributed in two sets of 60 elements arranged axially side by side (FIG. 2 ). The spokes 5 have a parallel epipedal shape with a small thickness relative to their length and width. This shape makes it possible to bend them easily in the direction of their thickness. The spokes 5 have their two longitudinal ends fastened, respectively, to the internal element 3 and to the external element 4 by joints 51 . The spokes are so arranged between the internal element 3 and external element 4 that their length is in a radial direction, their width is in an axial direction, and their thickness is in a circumferential direction. Consequently, the spokes 5 can bend under a radial compression of their longitudinal ends. The bending is circumferential. The flexibility of the spokes 5 in a meridian plane is therefore much less than their flexibility in a circumferential plane. In the embodiment of FIGS. 1, 2 and 4 , the joints 51 consist of two parts 511 and 512 (see FIG. 4 ), fastened to each other by a pin 513 . That method of fastening makes possible a free rotation between both parts 511 and 512 of the joints 51 . The pins 513 are arranged in the axial direction of the wheel. The method of connection allows a rotation of the spokes 5 relative to the internal and external elements in the plane of the wheel. The spokes 5 are, for example, made of a fiberglass-reinforced polymer material. The annular external element 4 comprises a thin metal hoop (in the order of 0.1 to 1 mm thick) covered with an elastomer layer designed to come in contact with the road (the elastomer layer is not shown in FIG. 2 ). The external element thus has a low flexural strength and is appreciably inextensible. The circumferential length of said external element 4 is such that the spokes 5 are all prestressed in axial compression beyond their buckling load. All such spokes 5 are therefore in postbuckling state. Consequently, the reaction force they oppose to the internal element 3 and external element 4 is appreciably constant and independent of their radial compression. The wheel, as presented in FIGS. 1 and 2, is in unstable state of equilibrium, and the energy stored in the spokes 5 tends to be released by a rotation displacement of the external element 4 relative to the internal element 3 . In order to limit the relative rotation between the internal element 3 and the external element 4 , the deformable structure 1 is provided with means of stabilization presented in FIG. 3 . The means of stabilization consist, for example, of cables 6 joining the internal element 3 and the annular external element 4 . In FIG. 3, the cable 61 is shown fastened at A to the internal element 3 and fastened at B to the external element 4 . O being on the axis of rotation of the wheel, the angle AOB=α is, in the example represented and at rest, equal to 30 degrees. The angle AOB can vary from 1 to 45 degrees and preferably between 25 and 35 degrees. The cables 6 are formed and arranged to be taut at rest. Said cables 6 thus contain the rotational displacement of the annular external element 4 relative to the internal element 3 , even though punctual relative displacements in the area of contact remain possible. The stiffness, arrangement, extension prestressing and number of those cables influence the propensity to maintain, on the whole, the position of equilibrium shown in FIG. 1 . On the other hand, the cables make it possible to adjust the circumferential stiffness of the wheel according to their particular stiffness in extension, as well as depending on their inclination relative to the circumferential direction. The cables can also be of several different thicknesses on both sides of their anchoring point in the internal element and external element, which entails a variation of response of the wheel to a torque applied circumferentially. The angles of inclination can also be changed on both sides of their anchoring points in order to obtain such asymmetry of mechanical response. The cables can also be substituted by more monolithic elements or any equivalent means of stabilization. FIGS. 4 and 5 present other methods of arrangement and connection of the spokes to the internal element 3 and external element 4 . FIG. 4 shows two spokes 52 and 53 with their joints 51 . As previously, the joints 51 contain two parts, the first 511 , where a longitudinal end of the spoke 52 , 53 is embedded, and the second 512 , rigidly fastened to the internal element or external element. Those two parts are joined by a pin 513 , placed, wheel mounted, in the axial direction of the deformable structure 1 . In the embodiment of FIG. 4, the spokes are arranged between the internal and external elements circumferentially in pairs with, as before, their bending plane oriented circumferentially. The longitudinal ends of the spokes 52 and 53 are embedded in supports 511 , so that the distance D separating the two spokes is greater than the distance d separating the two pins 513 . Consequently, on an axial compression, a torque is applied on the spokes and imparts a circumferential bending of the two spokes in two opposite directions, so that their center parts diverge (FIG. 4 b ). This design has the advantage of facilitating buckling of the spokes always in the same direction. FIG. 5 presents a double spoke 56 embedded in a support 57 . In contrast to the preceding embodiments, this support 57 comprises only one part rigidly connected to the internal or external elements. Spoke 56 consists of two parallel epipedal half-spokes 561 and 562 arranged circumferentially side by side and embedded in supports 57 . Supports 57 are fastened to the internal and external elements. The half-spokes are separated circumferentially by a plate 563 . The plate orients, as previously, the circumferential bending of the two half-spokes in two opposite directions, so that their center parts diverge (FIG. 5 b ). FIGS. 6 and 7 illustrate schematically the behavior of a wheel containing a deformable structure upon being crushed on a flat road. The wheel contains two sets of spokes 5 similar to those of FIGS. 1, 2 and 3 and stabilization means 7 consisting of two sets of polyurethane square-section beams. The two sets of beams 7 have a nonradial inclination and are arranged symmetrically on both sides of the radial direction, as illustrated on FIG. 3 . The modulus of extension of the beams is in the order of 20 MPa. The orientation of the beams 7 is similar to that of the cables 6 presented in FIG. 3 . In FIGS. 6 b and 7 b only, the external element 4 has been represented with a layer of elastomer material assuring contact with the road 8 . The layer has a thickness of approximately 10 mm. For the sake of clarity of presentation, the course of behavior of only one of the two sets of spokes 5 outside the area of contact ( 6 a ) and in the area of contact ( 6 b ) is represented in FIGS. 6 a and 6 b , and the course of just one of the two sets of beams in ( 7 b ) and outside the area of contact ( 7 a ) is represented in FIGS. 7 a and 7 b. Upon crushing of the wheel 1 on a road 8 , one finds that the spokes 5 all remain in postbuckling state, but with marked variations of radial compression. Three cases arise: outside the areas of contact ( 6 a )—spokes R 1 —the spokes show a slight radial compression; in the area of contact, between points E and F, the spokes R 2 show a markedly greater radial compression; in proximity to entry and exit from the area of contract, the spokes R 3 show an intermediate radial compression. The radial compression of the spokes 5 directly depends on the radial distance between the internal element and external element and, therefore, on the deflection of the wheel upon being crushed on the road. As each spoke is in a postbuckling state, it exerts an appreciably constant reaction force on the external element 4 . In the zone of contact between the ground and the wheel, the area of contact, the external element or tread therefore exerts an appreciably constant mean pressure on the ground. The force is practically unaltered by the amplitude of the radial compression supported by the spoke 5 , and the pressure exerted by the annular external element in the corresponding zone is thus appreciably independent of the amplitude of the deflection assumed by the crushed wheel. This behavior is thus very close to that of a tire. It makes it possible to absorb the unevennesses of the road without entailing harsh reactions transmitted to the wheel disk, or generating significant variations of the surface of contact between wheel and road. This behavior is very close to that of a tire. FIG. 7 illustrates the course of just one of the two sets of beams in ( 7 b ) and outside the area of contact ( 7 a ). Three cases arise: the beams whose points of anchoring to the internal and external elements are outside the area of contact ( 7 a )—beams H 1 —are in a slightly taut state; the beams—beams H 2 —whose points of anchoring to the external element are in the area of contact, between points E and F, are in a state of buckling; the beams arranged on entry and exit from the area of contact—beams H 3 —are in an intermediate state. One thus finds that the beams, one anchoring point of which is in the area of contact, have their tension relaxed by the radial compression of the external element which brings the anchoring points of the beams together between the internal element and the external element. Consequently, the beams, whose section is small, buckle and only weakly oppose that radial compression of the external element in the area of contact or on running over an obstacle. The wheel presented also has the advantage of excellent homogeneity of contact pressures between the annular external element and a flat road in the axial direction, owing to the symmetry of construction of the spokes appearing in FIG. 2 . An external element 4 can easily be made by vulcanizing a thickness of rubber on a belt. The belt can be a flat steel sheet of width L and 0.1 mm thick. The deformable structure according to the invention can also be provided with means to limit radial compression of the spokes, such as stops. For example, it is possible to provide between the two axially juxtaposed set of spokes of FIGS. 1 to 3 an annular stop fastened to the internal element, of such outer diameter that it limits the maximum axial compression of those spokes to approximately 50%. In the examples presented in FIGS. 1 to 3 , two sets of axially juxtaposed spokes have been arranged, but it is entirely possible to increase that number of axially juxtaposed sets appreciably, in order to improve the behavior of the wheel or insert formed on an uneven road. The external element can likewise be formed by one or more axially juxtaposed elements.
A deformable structure for a vehicle, designed to roll on an axis of rotation, including an annular internal element centered on the axis, an annular external element, flexible and appreciably inextensible, forming a tread radially arranged externally relative to the internal element, a plurality of spokes arranged substantially radially between the internal element and the external annular element, each spoke being capable of opposing a radial compressive stress, beyond a given threshold, an appreciably constant force, the external element having a circumferential length such that the spokes are preloaded in radial compression, and in which provision is made for stabilizing the relative positions of the internal element and external element, characterized in that the spokes are formed and arranged between the internal and external elements, in such a way that their flexibility in a meridian plane is well below their flexibility in a circumferential plane, and in that the of stabilization limits the amplitude of a circumferential relative rotation between the internal element and the external element.
1
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] This invention relates generally to a motor vehicle driveline, which in operation transmits power continually to a first wheel set and selectively to a second wheel set. [0003] 2. Description of the Prior Art [0004] All-wheel-drive (AWD) systems tend to reduce vehicle fuel economy due to increased driveline parasitic losses, even when AWD is not activated. Driveline disconnect systems improve fuel economy by disconnecting as many of the driveline rotating parts as possible, as close to the transmission output and the secondary drive wheels as possible, when all-wheel-drive is not activated. [0005] In virtually all front-wheel-drive (FWD) vehicles and many rear-wheel-drive (RWD) vehicles that produce all-wheel drive (AWD) or four-wheel drive (4WD), operation in two-wheel-drive (2WD) is not provided. In such vehicles, 2WD operation is produced in response to being manually selected by the vehicle operator. But requirement that 2WD operation be manually selected creates an inconvenience for operators, who may expect fully automatic operation of the driveline. It also decreases fuel economy for operators who leave the vehicle in AWD/4WD mode, or in vehicles that provide no selectable 2WD operation. [0006] A need exists in the industry for a control method that automatically switches between 2WD and AWD or 4WD modes to save fuel while minimizing or eliminating any disruptions that the vehicle occupants might notice. SUMMARY OF THE INVENTION [0007] A method for controlling a vehicle driveline includes using current conditions to estimate wheel slip probability and the likelihood that AWD torque transfer will be required to support vehicle handling performance, producing two-wheel drive operation, if said slip probability is low, handling support is not required and a condition for forced driveline connection is absent, and producing four-wheel drive operation, if said slip probability is high and/or handling support is required and a condition for forced driveline disconnection is absent. [0008] The control provides a method for automatically switching between 2WD and AWD/4WD modes to improve fuel economy while minimizing or eliminating any disruptions that the vehicle occupants might notice. [0009] The control monitors numerous vehicle signals and preemptively produces shifts from 2WD to AWD/4WD when wheels slip is likely to occur and/or handling support is required. The control uses a rule based or fuzzy logic control system to anticipate the likely occurrence of wheel slip, and performs the shift at a connect speed that is determined to not produce excessive noise, vibration or harshness. [0010] The scope of applicability of the preferred embodiment will become apparent from the following detailed description, claims and drawings. It should be understood, that the description and specific examples, although indicating preferred embodiments of the invention, are given by way of illustration only. Various changes and modifications to the described embodiments and examples will become apparent to those skilled in the art. DESCRIPTION OF THE DRAWINGS [0011] The invention will be more readily understood by reference to the following description, taken with the accompanying drawings, in which: [0012] FIG. 1 is a schematic diagram of a motor vehicle driveline having primary and secondary road wheels; [0013] FIG. 2 is a cross section showing a drive system that connects a power source continually to a primary wheel set and selectively to a secondary wheel set; and [0014] FIG. 3 is diagram showing information flow and method steps for engaging the driveline of FIG. 1 . DESCRIPTION OF THE PREFERRED EMBODIMENT [0015] The driveline 10 of FIG. 1 includes a power source 12 , such as an internal combustion engine or an electric motor, and a transmission 14 that produces a variable ratio between the speed of its output 16 , which is continually driveably connected through a differential mechanism 18 to the primary road wheels 20 , 22 , and the speed of the transmission input, which is driveably connected to the power source. [0016] The primary wheels 20 , 22 are driven continually by the engine during torque transfer conditions. The secondary wheels 26 , 28 are undriven road wheels, except that they are driven by the engine during torque transfer conditions when AWD is operating. [0017] A power transfer unit (PTU) 24 transmits power from the transmission output 16 selectively to the secondary road wheels 26 , 28 . A driveshaft 30 transmits rotating power from the PTU 24 to a rear drive unit (RDU) 32 . [0018] The PTU 24 comprises a coupler 34 , such as a dog clutch or synchronizer, whose input is driveably connected to the transmission output 16 ; a bevel ring gear 36 connected to the output of the PTU coupler 34 , and a bevel pinion gear 38 meshing with the bevel ring gear 36 and connected to driveshaft 30 . The PTU coupler 34 disconnects the rotating components of the PTU and driveline components downstream of the PTU from the transmission output 16 . [0019] The RDU 32 includes a bevel pinion gear 40 , secured to driveshaft 30 ; a bevel ring gear 42 , meshing with pinion 40 , a differential mechanism 44 , and a low-drag coupling 46 . The secondary wheels 26 , 28 are driven by halfshafts 48 , 50 though coupling 46 and differential 44 . Coupling 46 alternately connects and disconnects halfshafts 48 , 50 from the rotatable components of the RDU 32 . [0020] FIG. 2 illustrates details of the power path that connects the transmission output 16 continually to the halfshafts 60 , 62 for the primary wheels 20 , 22 through differential 18 , and to the PTU input shaft 64 , which is connected to bevel ring gear 36 . [0021] A compound planetary differential 18 includes a sun gear 72 , secured through a spline 74 to axle shaft 62 ; a carrier 76 , secured through a spline 78 to axle shaft 60 ; a ring gear 80 , engaged with an pinion 82 formed on the transmission output shaft 16 ; first planet pinions 84 supported on the carrier and meshing with the ring gear 80 ; and second planet pinions 85 supported on the carrier 76 and meshing with the sun gear 72 and the first planet pinions 84 . One side of ring gear 80 is secured to a disc 86 and supported at a bearing 88 ; the other side of ring gear 80 is secured to a disc 90 and supported at a bearing 92 . Disc 90 is formed with an internal spline 93 , which engages an external spline formed on a coupler sleeve 94 . [0022] Disc 90 forms a cylinder 96 , which contains a piston 98 , actuated by pressurized hydraulic fluid carried to cylinder 96 through a passage 100 . A compression return spring 102 restores piston 98 to the disengaged position shown in the FIG. 2 . Piston 98 is secured to coupler sleeve 94 such that they move along an axis 103 and rotate about the axis as a unit. [0023] The volume 104 enclosed by piston 98 and spring retainer 106 forms a balance dam containing hydraulic fluid supplied from source of hydraulic lubricant 108 through a lube circuit, which includes passages 110 , 112 , 114 , 116 . [0024] In operation, fluid from a source of line pressure is carried to a valve, which is controlled by a variable force solenoid. The valve opens and closes a connection between the line pressure source and passages 126 , 128 , which carry piston-actuating pressure to cylinder 96 depending on the state of the solenoid. When passages 126 and 128 are pressurized, piston 98 and coupler sleeve 94 30 move leftward, causing frictional contact at the conical surface between a member 130 and a synchronizing ring 132 . Member 130 is rotatably secured by spline 134 to PTU input shaft 64 . As the speed of member 130 is synchronized with the speed of ring gear 80 , the internal spline of coupler sleeve 94 engages the dog teeth on synchronizing ring 132 and the clutch teeth 136 on the radial outer surface of connecting member 130 , thereby driveably connecting ring gear 80 and PTU input shaft 64 . [0025] When passages 126 and 128 are vented, piston 98 and sleeve 94 move rightward to their disengaged positions, causing connecting member 130 to disengage the ring gear 80 , thereby disconnecting ring gear 80 from PTU input shaft 64 . [0026] Although the description refers to the speed of connecting member 130 being synchronized with the speed of ring gear 80 using a synchronizer, a connection between ring gear 80 and PTU input shaft 64 can be completed using a coupler, such as a clutch, instead of a synchronizer. [0027] In the disconnected state, the RDU coupling 46 and PTU coupling 34 are open, causing the rotatable RDU components, driveshaft 30 , and rotatable PTU components to be disconnected from the secondary wheels 26 , 28 and halfshafts 48 , 50 . [0028] In the connected state, the PTU coupler 34 is closed, causing driveshaft 30 to rotate with the primary wheels 20 , 22 and transmission output 16 . The RDU coupling 46 has a variable torque transmitting capacity, which may produce a fully engaged connection or a defined speed difference between driveshaft 30 and the secondary wheels 26 , 28 , as required to produce AWD operation. [0029] FIG. 3 shows the method steps of a rule-based or fuzzy logic type control system for engaging and disengaging 2WD, and AWD/4WD in the driveline of FIG. 1 . The probability of vehicle wheel slip occurring or handling support being required under current conditions is estimated with reference to the current vehicle, road and weather conditions, which may include without limitation, vehicle operator driving patterns evidenced by driver control of the vehicle, terrain detection, terrain response mode, temperature, GPS data, weather data, coefficient of friction detection methods such as comparing amount of tire rotation for driven vs. undriven wheels, difference in left-to-right tire rotation during turns vs. steering wheel angle, and actual yaw vs. intended yaw. [0030] At step 150 a controller reads various driveline sensors incorporated in software modules. The output for each module is in a range between 0 and 1, zero representing a low probability that wheel slip will occur due to the sensed variable corresponding to a respective module, unity representing a high probability that wheel slip will occur due to the current value of the sensed variable. For example, certain sensors indicate the degree to which the following current conditions indicating that wheel slip is probable or imminent and/or that handling support is required: (i) the vehicle is travelling on a rough road 152 , (ii) anti-lock brake system (ABS), brake traction control system (BTCS) or electronics stability control (ESC) intervention is currently active 154 ; (iii) wheel slip is occurring 156 ; (iv) vehicle handling is challenging 158 ; and (v) the vehicle is towing a trailer 160 . Other output signals 162 produced by vehicle sensors indicate the degree to which the following variables influence wheel slip and the weight attributed to the current value of the variable: the vehicle is turning on a road having a low coefficient of friction; vehicle speed is low; the status of BTCS/ESC over-ride switch, the status of the AWD terrain mode selector switch; detected gear in which the transmission is operating; estimated ambient temperature; weather conditions (either sensed directly or inferred from an external wireless data transmission such as a weather report); hill or incline detected; GPS vehicle location data; driving resistance; AWD torque transfer; estimation of tire to road friction; road curve detected; axle articulation (either measured directly via sensors located on the vehicle or inferred from calculation of various vehicle state conditions); radar sensor information. In this way a weighted sum is produced indicating the probability that wheel slip will occur under current conditions. [0031] “Terrain Mode” is the operating mode selected in a Terrain Management system. Different modes can be selected by the driver for different driving situations, e.g. Normal, Grass/Gravel/Snow, Mud/Ruts, Sand. Terrain Mode is independent of ESC, but can change ESC modes. Axle articulation is the movement of the suspension. When driving off-road, for example, the wheels might go from being at full droop, i.e., fully extended, to being at full compression. We look at all four wheels. Wheel travel sensors, fitted to all four wheels with active damping, would be used to measure wheel position, and it would be tracked over time to assess the road/ground conditions. [0032] A controller monitors these signals and changes preemptively the operating state of the driveline 10 between 2WD and AWD/4WD in accordance with the weighted sum. [0033] At step 166 the sum of the module outputs is determined. [0034] At step 170 , signals 152 , 154 , 156 , 158 are used to evaluate noise, vibration and harshness (NVH) and vehicle body movement to determine whether the vehicle occupants will notice a fast engagement of AWD/4WD. Reconnecting the AWD system too quickly can result in audible clunks, tactile vibrations, or a drop in vehicle acceleration that can be felt or heard by vehicle occupants as objectionable NVH. This step recognizes that various NVH events, such as driving on a rough road, will mask what would normally be perceivable NVH resulting from the rapid engagement of the AWD system on a smooth road, thereby allowing a much faster engagement time than would normally be considered acceptable. [0035] At step 172 , signals 156 , 158 are used to evaluate need for a fast engagement of AWD/4WD. The need for a fast engagement may result from the need for AWD to immediately reduce wheel slip or influence vehicle handling to maintain acceptable vehicle driveability. [0036] At step 174 a test is made to determine whether the sum determined at step 166 is equal to or greater than a reference, such as 1 . 0 . [0037] If the result of test 174 is logically false, at step 176 , the controller determines the history of changes in driveline state between 2WD and AWD/4WD. [0038] At step 178 a test is made to determine whether changes in driveline state between 2WD and AWD/4WD have occurred at a high rate, e.g., a rate that exceed a reference rate. [0039] If the result of test 178 is true indicating frequent changes in driveline state, or if test 174 is true indicating a high probability of wheel slip and/or that handling support is required, control advances to step 180 where the controller determines whether a condition is present that would require a disconnect regardless of connect input, i.e., require that the driveline produce 2WD. Conditions that would require a disconnect regardless of connect input may include an ESC event in progress, a reported failure mode, and the current gear produced by the transmission 14 . [0040] If the result of test 178 is false, at step 184 the controller determines whether there are special conditions that would force a connect, i.e., require that the driveline produce AWD/4WD. Conditions that would require a connect regardless of disconnect input may include a driver disabled ESC system or has selected a special Terrain Response mode, very low vehicle speed or a reported failure mode. [0041] If the result of test 180 is true, or the result of test 184 is false, at step 182 the controller disconnects the transmission output 16 from the RDU 32 , thereby producing 2WD. [0042] If the result of test 180 is false indicating that a disconnect would not be forced, or test 184 is true indicating that a connect would be forced, at step 186 , a test is made to determine whether a fast connect is possible or required. [0043] If the result of test 186 is true, at step 188 a fast connection is executed by connecting transmission output 16 through PTU input shaft 64 and bevel ring gear 36 to the RDU 32 , thereby producing AWD/4WD. [0044] If the result of test 186 is false, at step 190 a connection between the transmission output 16 and the RDU 32 is executed at normal speed, thereby producing AWD/4WD. [0045] The speed of connection can be continuously variable depending on current conditions as represented by the outputs signals of the sensors. For example, during a “normal connect,” the AWD system can be connected with “good NVH” in a much shorter time at lower speeds than if the vehicle is traveling at higher speeds. Similarly, at higher operating temperatures a “normal connect” can occur much quicker than at lower temperatures. A fast connect would be around 100 ms, and a slow connect about 400ms. [0046] If preemptive measures of FIG. 3 fail, traction control and/or stability control would be used to maintain acceptable vehicle performance during the first AWD/4WD engagement. [0047] Powertrain controls can be used to increase torque during each 2WD to AWD/4WD shift to compensate for the loss of power due to inertia and spin resistance of the secondary drive path. [0048] The driveline system will disconnect, i.e., shift from AWD/4WD to 2WD, using similar inputs, potentially including ignition cycles and cruise control status. [0049] In a FWD-based application, a low loss clutch with limited capacity can be placed in front of the PTU 24 to synchronize the PTU, rear driveshaft 30 and front end of the AWD clutch under many conditions while assistance will be required from the AWD clutch will be required under more severe conditions such as operating at high vehicle speed or low temperature. Alternately, if vehicle packaging permits, a high capacity clutch may be placed in front of the PTU to synchronize the secondary driveline under all conditions while a simple dog clutch is utilized to lock and unlock the secondary driveline from the rear wheels. [0050] In accordance with the provisions of the patent statutes, the preferred embodiment has been described. However, it should be noted that the alternate embodiments can be practiced otherwise than as specifically illustrated and described.
A method for controlling a vehicle driveline includes using current conditions to estimate wheel slip probability and vehicle dynamics handling support requirements, producing two-wheel drive operation, if said slip probability and handling support requirement is low and a condition for forced driveline connection is absent, and producing four-wheel drive operation, if said slip probability and/or handling support requirement is high and a condition for forced driveline disconnection is absent.
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[0001] This application claims priority from U.S. Provisional Patent Application No. 60/995,238, filed Sep. 26, 2007, the contents of which are hereby incorporated by reference in their entirety. FIELD OF THE INVENTION [0002] The invention relates to nanoparticle for one or more molecules of interest, which can be contacted to cells or directly to an animal to produce a desired biological effect, where the nanoparticle contains at least two carrier materials with multivalent ionic moieties associated with an ionizable cargo. The invention relates to nanoparticles useful for biomedical applications including immunization and therapeutics. The invention further relates to nanoparticles comprising optionally one carrier material for the delivery of antigens as vaccines. BACKGROUND OF THE INVENTION [0003] A major need exists for new or improved vaccines including prophylactic vaccines for potential bioterrorism infectious organisms and therapeutic vaccines such as for cancer. For example, mailed powder containing anthrax material killed unsuspecting office workers and caused major disruption due, in part, to lack of a good and safe vaccine. The migration of avian flu is a major concern given lack of an effective vaccine. There exists a need for rapid development of vaccines toward emerging infectious agents such as SARS or bioterrorism developments. Therapeutic vaccines also are needed. [0004] Anthrax is an infectious bacterial disease caused by Bacillus anthracis and occurs in domestic animals and humans exposed to infected animals, tissue, or spores. The virulence of B. anthracis is dependent on Anthrax Toxin (AT) and poly-gamma-D-glutamic acid capsule (PGA). PGA provides the bacteria a way to evade immune cells by providing a ‘stealth’ cover. PGA also is not very immunogenic. AT is composed of three entities: Protective Antigen (PA) (the binding subunit of AT), Lethal Factor (LF) and Edema Factor (EF) (Mikesell et al., Infect. Immun. 39:371-76, 1983; Vodkin et al Cell 34:693-97, 1983). PA is an 83 kDa protein that is the main protective constituent of anthrax vaccines. A currently approved human vaccine for Anthrax, which is manufactured from a cell free extract of un-capsulated Bacillus Anthracis (AVA, BioPort Corporation, Lansing Mich.), has several limitations including a requirement for six vaccinations over eighteen months followed by yearly boosters (Pittman et al., Vaccine 20:1412-20, 2002; Pittman et al., Vaccine 20:972-78, 2001) and is associated with undesirable reactions (Pittman et al., Vaccine 20:972-78, 2001). PA is necessary for vaccine immunogenicity (Ivins et al., Infect. Immun. 60:662-68, 199 Welkos and Friedlander, Microb. Pathog. 5:127, 1998) and can inhibit germination of spores (Welkos eta., Microbiology 147:1677-85, 2001). Current efforts for development of a new vaccine focus on using PA as the antigen. [0005] In order to have an effective prophylactic vaccine against capsulated bacteria and its toxin, a combined immune response against PA and the PGA will be advantageous. Late stage clinical development by VaxGen of an experimental vaccine based on recombinant PA has been put on hold. [0006] Anthrax toxins are formed by PA, lethal factor (LF), and edema factor (EF), which are secreted separately as nontoxic monomers. Binding of LF or EF to PA produces active toxin. PA along with bound LF or EF is internalized by cells by receptor mediated endocytosis in a heptameric form. In the endosome, PA undergoes a pH-induced conformational change, producing a pore in the endosomal membrane permiting toxin translocation into the cytoplasm and toxicity. The conjugation of PA to gamma-D-PGA has been suggested as a means to obtain simultaneous immune responses (Rhie et al. PNAS 100, 10925 2003, Schneerson et al. WO 2005/000884). Antigenic constructs that can provide presentation of PA and PGA to antigen presenting cells and also prevent the multimerization and pore formation of PA molecules, will be advantageous in preventing the infection and the effect of toxin. [0007] Many viral infections are not managed adequately, requiring new or better vaccines, including avian flu. The major viral antigens of influenza, including N, HA, and M proteins, change rapidly, limiting the benefit of each vaccine. Also current production relies on growth in eggs with severe commercial limitations. An effective and safe vaccine not dependent on biological manufacturing and that is rapidly adaptable for rapidly changing antigens is needed. [0008] The purpose of a therapeutic vaccine is not only to induce an immune response but to induce a response that is beneficial for patients already exposed to an infectious agent or who have ongoing infection or disease. One major interest for potential application of therapeutic vaccines is for treatment of cancer patients. However, commercially successful products have encountered several hurdles, including the difficulty of identifying antigens, finding antigens that are broadly applicable, and identifying adjuvants that achieve an effective immune response. Despite the recent achievements using nanoparticles to improve immune response, a need clearly exists for more effective and safe prophylactic and therapeutic vaccines as well as further improvements in nanoparticles to address needed capabilities. [0009] Most candidate therapeutic classes, from large proteins such as antibodies, to small molecules such as chemotherapy, are limited by pharmacological barriers that potentially can be overcome using drug delivery. Production of pharmaceutically active polypeptides and nucleic acids is adequate (Biomacromolecules 2004;5:1917-1925), but their use remains limited by many barriers, including absorption, diffusion into cells, degradation, etc. (J. Control. Release 1996;39:131-138). Small molecules also can face similar barriers, such as toxicity from widespread biodistribution, and these severely limit their development as seen by annual decreases in new drug approvals even though delivery systems often are incorporated. Another growing clinical need is for combinations of approved products, again pointing to a need for better delivery systems with capabilities for two or more active ingredients. [0010] Nanoparticles have benefited several commercialized therapeutics, but the extensive research revealed numerous barriers and challenges hampering further application. Major challenges include a need for better manufacturing, control of particle size and homogeneity, cargo loading, cargo release at the target cell or tissue, biocompatibility, and disease selectivity. Improvement is needed for broad commercial application. [0011] Hydrophilic polymer conjugates of active ingredients to improve pharmacological activity have been reported. These materials are nanoscale but are soluble and thus are not nanoparticles. Commercialization limitations include a need for all functions, such as targeting ligands, to be coupled effectively to the large carrier and difficulty for the carrier to meet all the strict regulations applied to the active ingredient, exacerbated as the carrier size increases. Adaptation of hydrophilic carriers for use in nanoparticles has been disclosed frequently by conjugation with poorly soluble material such as lipids, polylactides, etc., and further comprising association of active ingredient either covalently or non-covalently. In this case the conjugate forms or associates with a micelle, liposome, or solid colloid. A limitation of such compositions is that to obtain the nanoparticle benefits, the carrier mass and components is increased, reducing commercial utility due to increased costs, lower drug loading, great product heterogeneity. Although development of nanoparticles has led to improved products, the current compositions fail to address the needs of many vaccine and therapeutic applications. Therefore, a need exists for effective and safe vaccines and therapeutics. SUMMARY OF THE INVENTION [0012] The invention provides polyelectrolyte nanoparticles comprising charged carriers or carrier domains in a complex with a cargo. The nanoparticle optionally can further comprise targeting ligands and/or a protective surface. The nanoparticle can be contacted to cells or administered directly to an animal for biomedical applications including vaccination and delivery of therapeutics. One embodiment of the invention relates to prophylactic vaccines for infectious agents including Bacillus anthracis, avian influenza, and other potential “bioterrorism” organisms. Another embodiment relates to therapeutic vaccines for disease including DNA cancer vaccines. Yet another embodiment relates to therapeutics including antiangiogenic and anticancer treatments including squalamine, mitomycin C, and mitoxantrone. DETAILED DESCRIPTION OF THE INVENTION [0013] The invention provides polyelectrolyte nanoparticles comprising at least two carrier molecules or two separate domains of a single molecule comprising ionizable moieties or domains of moieties or at least one multivalent charged domain with sufficient size, shape and charge to form complexes with a charged or zwitterionic cargo, preferably multivalent charge. A cargo is defined herein as a molecule that is biologically active following delivery by a delivery material or method to an intended cell. [0014] Nanoparticles can be formed from interactions between the carrier materials or carrier domains and between the carriers or carrier domains and the cargo. Carrier materials or carrier domains can be comprised of oppositely charged domains. In a preferred embodiment, a carrier or carrier domain is substantially homogenous in charge. Carrier can be a single material having separate but linked oppositely charged domains, preferably where the linkage allows the two domains to freely move one another to associate with other domains or with the cargo. Largely independently of the ratio of materials forming the nanoparticle, the interior of the nanoparticle comprises polyelectrolyte complexes of nearly equal charge ratio and largely lacking solvent Net surface charge of the nanoparticle is substantially determined by ratio of carrier to cargo, the ionization state of surface moieties, etc. and can be influenced by adsorbed ions, and polymers, The net surface charge can therefore be adjusted by modifying the above parameters. The nanoparticle preferably has a net surface charge which may be either positive or negative. [0015] Nanoparticles can comprise an anionic carrier or domain and a cationic carrier or domain with cationic or anionic cargo, or vice versa. A nanoparticle may contain more than one cargo and the different cargos may either be anionic or cationic. The same nanoparticle may contain both an anionic and a cationic cargo. A large range of ionizable cargo materials can be used, including bacterial surface components, poly-gamma-D-glutamate, toxins, antigens, viral surface antigens, phosphorylated molecules, nucleic acids, anionic peptides, cationic peptides, polyamines, inhibitors of polyamine pools, squalamine, polyamine sterols, and cationic anticancer agents including mitoxantrone. A nucleic acid may comprise a sequence for expression and may comprise a sequence inhibiting expression of genes including RNA or expression of RNA including antisense and RNAi factors. The nucleic acid of the invention may comprise chemical analogues. [0016] The nanoparticle preferably comprises biocompatible, or preferably biodegradable, carrier materials. The biocompatible carrier of the invention reduces non-specific toxicity and biodegradable carrier can be degraded into components of cellular metabolism or excreted. The nanoparticle preferably is degraded or disassembles during its biomedical application, permitting desired cargo biological activity and permitting carrier material to be metabolized and/or excreted. Nanoparticle disassembly can be achieved by selection of carrier material comprising moieties with a range of binding affinites with the cargo from weak to strong where the affinity selected within that range permits nanoparticle disassembly, or whose affinity is reduced response to biological conditions. The selection of the bio-responsive moieties or groups depends on the chemical or structural nature of the moieties of the cargo and the biological compartment where disassembly is desired. [0017] The nanoparticle may further comprise a second carrier domain opposite in charge to the first carrier. The second carrier material preferably exhibits weaker affinity with the first carrier than with the cargo during nanoparticle formation and storage, and optionally can undergo a change to stronger affinity so as to facilitate release of cargo from the nanoparticle. [0018] The nanoparticle may further comprise additional cargo materials and/or biological modifiers. The nanoparticle of the invention may comprise two or more “active ingredients”, for applications when their simultaneous activity is desired, for example antibody responses against multiple antigens or inhibition of redundant biochemical pathways. The nanoparticle optionally may further comprise one or more biological modifiers including surface exposed targeting ligand, encapsulated ligand, adjuvant, intracellular binding motif, bio-responsive material or moieties such as membrane fusing agent, membrane penetrating agent, pH or redox labile or responsive moieties, and protective coating. [0019] The invention provides for vaccines for the prevention and treatment of infection. In this embodiment, the invention provides for 1) in vivo administration of nanoparticles of the invention including local administration or 2) ex-vivo treatment including application of nanoparticles of the invention to antigen presenting cells in culture. In this embodiment, the nanoparticles of the invention preferably have an average particle size of about 0.1 micron to about 1 micron. For local in vivo administration, the nanoparticles of this embodiment preferably have an average particle size of about 0.2 micron to about 1 micron. For systemic in vivo administration, the nanoparticles of this embodiment preferably have an average particle size of about 0.1 micron to about 0.2 micron. For ex-vivo administration, the nanoparticles of this embodiment preferably have an average particle size of about 0.2 micron to about 1 micron. Nanoparticles with an average particle size of about 1 micron are advantageously used in cell culture to contact adherent cells. Nanoparticles with an average particle size of no more than about 0.2 micron are advantageously produced with sterilization by terminal filtration. Nanoparticles of the invention optionally can be contacted with cells in culture with the aid of centrifugation or other means to facilitate cell contact. [0020] In this embodiment, the nanoparticle comprises only a cationic carrier and an antigen. The cationic carrier may be selected from a wide range of material including a lipid, polyamine, polyimine, dendrimer, or polypeptide. The carrier may be a cationic derivatized polyaspartate or polyglutamate, including modified polyasparagine or polyglutamine. The carrier preferably comprises a cationic polypeptide and optionally may comprise about 10 to 100% lysine, preferably with a size of about 1,000 to 50,000 daltons, and may be linear or preferably comprises branching of about 10 to 100% of the amino acid residues. The carrier preferably comprises a “dendrimer” polypeptide formed using lysine based branching. The preferred embodiment comprises antigen of about 1,000 to about 100,000 Molecular Weight (MW), preferably about 1,000 to about 10,000 MW. The nanoparticle optionally further comprises an adjuvant. The adjuvant may be selected from a wide range of material including inulin, a “CpG” oligonucleotide, and lipopolysaccharide. The embodiment may further comprise unbound materials including adjuvant. In this embodiment, the invention provides for airway administration including nasal spray and aerosol inhalation. In this embodiment, the invention provides for an initial “prime” application followed by at least one “boost” application and in a preferred embodiment subsequent “boost” administration less frequently than once a year. [0021] In one specific embodiment, the nanoparticle comprises a cationic carrier and an antigen comprising poly-gamma-D-glutamate (gamma-D-PGA). The carrier optionally comprises a biodegradable polycation and preferably comprises a lysine rich polypeptide. The nanoparticle of this embodiment preferably comprises low surface exposure of PGA. The nanoparticle of this embodiment preferably further comprises an antigenic portion of anthrax “protective antigen” (PA) and optionally may comprise surface exposure of PA. In a preferred embodiment the nanoparticle optionally comprises both PA and PGA and may further comprise PA chemically coupled to PGA. The nanoparticle optionally comprises an adjuvant and preferably a “CpG” oligonucleotide and optionally may comprise, in a preferred embodiment, the CpG covalently coupled to the PGA antigen. In this embodiment, the nanoparticle is administered by subcutaneous injection, intravenous injection and preferably by airway administration including nasal spray and aerosol inhalation. [0022] The invention provides for therapeutic vaccines in the treatment of chronic infection or disease lasting longer than the time to achieve an adequate immune response, often at least two weeks. In this embodiment, the invention provides for antigen in a wide range of forms including polypeptide, polysaccharide, and nucleic acid. Optionally, the nucleic acid may comprise a sequence for expression or for inhibiting expression and optionally comprises sequences of RNA or expression of RNA including antisense factors. The nucleic acid of the invention optionally may comprise chemical analogues. [0023] In a specific embodiment, the nanoparticle of the invention comprises an ionic carrier and an antigenic polypeptide. In a preferred embodiment, the antigen comprises at least one tumor antigen and in a preferred embodiment comprises at least two different tumor antigens. The tumor antigen or antigens may be selected from proteins selectively expressed by tumors, such as HER2 and 5T4, and/or selectively exposed on the surface of tumor cells, such as gp96 or other human tumor antigens recognized by T cells can be used as antigens in the invention. In one specific embodiment the invention comprises antigenic sequences from the extracellular domain of HER2 and optionally further comprises antigenic sequences of MUC-1. The antigen optionally further comprises a calreticulin polypeptide exhibiting immune stimulation activity. The carrier preferably comprises a cationic carrier, and optionally is the same carrier provided for by embodiments for prophylactic anthrax vaccines. The preferred embodiment comprises antigen of at least about 10,000 MW. The nanoparticle of this embodiment preferably lacks surface exposure of PGA and optionally preferably lacks a protective surface. A preferred embodiment of the invention optionally further comprises surface exposure of anthrax PA sufficiently to permit binding to antigen presenting cells. [0024] In yet another specific embodiment, the nanoparticle comprises a cationic carrier and a nucleic acid. The cationic carrier preferably lacks arginine and guanidinium and has endosomolytic property. The carrier optionally may be a carrier provided for by embodiments of the invention for prophylactic anthrax vaccines. The cationic carrier preferably is rich in histidine, imidazole, lysine, and amines, and preferably comprises branched structure. The cationic carrier may be linear or branched PEI, preferably large linear PEI or small branched PEI. The cationic carrier may comprise a lysine-rich polypeptide, preferably branched with at least 50 % of the cationic ionizable groups comprising histidine or imidazole. The nanoparticle optionally comprises a hydrophilic polymer exposed on the surface and/or comprises an exposed ligand for antigen presenting cells. The hydrophilic polymer, when present, is preferably PEG. The exposed ligand, when present, is preferably a polypeptide and more preferably comprises an APC binding portion of anthrax protective antigen or comprises an RGD peptide. The nucleic acid may comprise a sequence for expression and optionally comprises sequences of antiangiogenic factors, tumor antigens, immune stimulatory factors. In a preferred embodiment, the nucleic acid comprises sequences of multiple factors. The nucleic acid may comprise single or multiple expression cassettes. In a preferred embodiment, the nucleic acid comprises sequences of at least one tumor antigen and sequences of GM-CSF, and optionally further comprises sequences of at least one tumor antigen fused to a calreticulin sequence exhibiting immune stimulation and/or antiangiogenic activity. The nanoparticle of this embodiment optionally may further comprise surface exposure of anthrax PA. [0025] The invention provides for therapeutic treatment of disease. In this embodiment, the invention provides for in vivo administration of nanoparticles of the invention including local or systemic administration. In this embodiment, the nanoparticles of the invention preferably have an average particle size less than about 0.2 micron. [0026] In a specific embodiment, the nanoparticle comprises a cargo associated with an ionic carrier and preferably comprises an anionic carrier. The carrier may be synthetic or of bacterial or mammalian origin, including hyaluronate, chitin, heparin sulfate, and polyglutamate. In one preferred embodiment, the carrier comprises a poly-glutamate polymer (PGA). A PGA polymer of this embodiment is preferably about 2,000 to about 300,000 daltons and more preferably of about 5,000 to about 100,000 daltons. A PGA carrier may be linear or preferably comprises a branched structure. The nanoparticle of this embodiment optionally further comprises PGA exposed on the surface and preferably comprises a protective PGA surface layer. [0027] The nanoparticle of this embodiment may further comprise a second carrier material. In this embodiment, the cargo optionally is coupled to the carrier. Coupled cargo may be cationic, anionic, or neutral/zwitterionic. The cargo may comprise at least one cationic moiety, and preferably multiple cationic moieties. A nanoparticle of this embodiment may comprise a carrier electrostatically associated with a cationic cargo including a peptide, polyamine, inhibitor of polyamine pools, squalamine, polyamine sterol, and cationic anticancer agent including mitoxantrone. Cargo coupling may be non-covalent or optionally may be covalent. When cargo association with carrier by non-covalent coupling is insufficient to maintain association during storage a covalent coupling is preferred. Coupling to a cargo moiety can include coupling via an amine, alcohol, aldehyde or carboxylic acid. In a preferred embodiment the coupling is reversible and optionally the coupling can provide tissue selective release. A preferred embodiment provides coupling with a dithiol benzyl that exhibits reduction mediated release, one form of which was disclosed by Zalipsky (See U.S. Pat. No. 7,238,368) for 1) coupling to some non-ionic polymers (but lacking any teaching for use with ionic polymers including PGA) and 2) methods to determine release. In a preferred embodiment, a nanoparticle comprises branched PGA and squalamine and optionally further comprises a nanoparticle forming material with reduced water solubility such as a lipid or a polymer. [0028] In a specific embodiment, the nanoparticle comprises squalamine. In this embodiment the nanoparticle has a squalamine content from about 1% to about 30% w/w and optionally comprises a ratio of PGA charge to squalamine charge from about 1:2 to about 10:1 and preferably from about 1:1.5 to about 5:1. [0029] In another preferred embodiment, the cargo comprises at least one chemotherapeutic agent. In this latter embodiment, the cargo comprises mitomycin C and optionally comprises a linkage to an amine. [0030] In another preferred embodiment, the cargo comprises at least two agents. In a specific embodiment, the cargo comprises mitomycin C and squalamine. In this embodiment the nanoparticle comprises a mitomycin C to squalamine ratio from about 3:1 to about 1:10 and preferably from about 1.5:1 to about 5:1. [0031] The invention provides nanoparticle compositions for ex-vivo treatment including application to antigen presenting cell culture. In this embodiment, the nanoparticles of the invention preferably have an average particle size of about 0 . 2 micron to about 1 micron. [0032] The invention provides nanoparticle compositions for ex-vivo treatment including application to immune cell culture including b-cell and t-cell culture. In this embodiment, the nanoparticles of the invention preferably have an average particle size of about 0.2 micron to about 1 micron. Example 1 Conjugation of Protective Antigen (PA) of Bacillus Antharacis with Poly-Gamma-D-Glumatic Acid (PGA) [0033] Recombinant PA is produced in bacteria culture by fermentation of E - Coli expressing a plasmid encoding the PA. The expressed protein is purified by standard chromatographic techniques. PGA is prepared from Bacillus Licheniformis or Bacillus subtilis according to the procedures described in Perez-Camero, G. et al, Biotechnol. Bioeng. 63, 110 (1999) or Kuboto, H et al, Biosci Biotech Biochem, 57, 1212 (1993). Sonication is used to reduce the molecular weight of the polymer. [0034] Conjugation of the PA molecule to PGA is carried out using standard coupling agents, such as water soluble EDC, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride which couples the carboxylic acid of PGA to the PA protein by formation of an amide bond. Other standard coupling reagents also can also be used to prepare a substantially equivalent conjugate. The resulting conjugates are purified by standard column chromatography and characterized by Mass Spectrometry. Example 2 Preparation of Nanoparticle Comprising the PA-PGA Conjugate [0035] Nanoparticle comprising the PA-PGA conjugate is prepared by combining and mixing the poly-anionic PGA moiety with a poly-cationic material such as poly-lysine, polyethyleneimine, Histidine-Lysine co-polymers, or Histidine and Lysine containing linear or branched peptides, to effect the self-assembly of the nanoparticle. A solution containing PA-PGA conjugate is mixed with a solution containing a polycation to form nanoparticles. Mixing is carried out by simple addition of the solution giving excess charge ratio to the other, followed by vortexing of the combined solutions, or by using a static mixer where the two solutions are pumped into a static mixer to be mixed within the helical mixing element of a static mixer. Electrostatic interaction between the anionic PGA with the polycation lead to self assembly and formation of nanoparticles. The molar ratio of PGA to polycation may be adjusted to obtain particles with net negative, neutral or positive surface charge. Particles with net surface charge will provide increased colloidal stability to the nanoparticle formulation. In order to further enhance stability, surfactants optionally will be added to one or both of the solutions. Samples may be prepared with added pluronic surfactant. Nanoparticle samples may be prepared so that some of the PA molecules are exposed on the surface of the particle to facilitate the uptake of the particle by antigen presenting cells and thereby elicit an immune response against PA and PGA. Example 3 Chemical Synthesis of Gamma-D-Glutamic Acid Oligomeric Peptides (GDGP) and their Conjugation to PA [0036] Peptides containing from 10 to 15 consecutive D-Glu residues coupled through the gamma carboxylic acid of the side chain to the alpha amino group of the neighboring C-terminal residue are synthesized by solid phase synthesis using D-Glu derivatives. 3 to 5 amino acid residues of Gly, Serine, Lysine, Ala or beta-alanine are incorporated into the N-terminus of the peptide to provide conjugation site through the alpha-amine, as well as to provide spacing between the D-Glu block and the conjugated protein. To enable conjugation through a sulfhydryl group, a Cys residue is incorporated at the N-terminus of the peptide. The synthesized peptide is purified by HPLC and characterized by MALDI. Conjugation of Gamma—D-Glutamic Acid Oligopeptide (GDGP) to PA. [0037] D-Glu peptides containing Cys at the N terminus are coupled to the Protein (PA) through a sulfhydryl containing side-chain. The protein in aqueouhs solution at pH between 7 and 8 is reacted with sulfosuccinimidyl-4-(N-maleimidomethyl)cyclohexane-1-carboxylate (Sulfo-SMCC). The maleimide activated protein is purified using a desalting column to remove excess sulfo-SMCC. To the purified protein conjugate, Cys containing peptide is added and the pH is adjusted to between 6.6 and 7.5. The maleimide coupling with the —SH group of the Cys side chain yields a PA-peptide conjugate which is further purified by standard column chromatography. The conjugate is characterized by Mass Spectrometry to determine the number of peptide molecules coupled to the PA molecule. [0038] A similar coupling procedure is used to couple the N-terminus amine of the peptide to PA amines. In this case, first the peptide is reacted with an excess (2-3 molar excess) of a homobifunctional cross linker, DSG (disuccinimidyl glutarate) under anhydrous conditions. The reaction is carried out in dry DMSO or DMF in the presence of 1-2 equivalents of base. NHS ester reacts with the N-terminal amino group of the peptide. Once the reaction is complete, the derivitized peptide is precipitated using dry ether and the solid material recovered and stored under anhydrous condition. This peptide with a NHS active terminus is used in a subsequent step to react with PA in aqueous buffer, pH 7-8, to prepare the conjugate of PA-peptide. This conjugate is purified by column chromatography and characterized by Mass Spectrometry. The number of peptides conjugated per PA molecule is determined by Mass Spectrometry. Preparation of Nanoparticle Comprising the PA-GDGP Conjugates: [0039] Nanoparticle comprising the PA-GDGP conjugates is prepared by the self-assembly of the poly-anionic GDGP moiety with a poly-cationic material such as poly-lysine, polyethyleneimine, Histidine-Lysine co-polymers, or Histidine and Lysine containing linear or branched peptides. A solution containing PA-GDGP conjugate is mixed with a solution containing a polycation to form nanoparticles. Mixing is carried out by simple addition of the solution giving excess charge ratio to the other followed by vortex, or using a static mixer where the two solutions are pumped into a static mixer to be mixed within the helical mixing element of a static mixer. Electrostatic interaction between the anionic GDGP with the polycation leads to self assembly of particles. The molar ratio of GDGP to polycation is adjusted to obtain particles with net negative, neutral or positive surface charge. Particles with net surface charge provide colloidal stability to the nanoparticle formulation. In order to further enhance the stability, surfactants optionally are added to one or both solutions. Samples are prepared with pluronic surfactant (Sigma). Nanoparticle samples are prepared so that some of the PA molecules are exposed on the surface of the particle, to facilitate the uptake of the particle by antigen presenting cells to elicit an immune response against PA and GDGP. Example 4 Synthesis of Branched Gamma-D-Glutamic Acid (bGDGP) and its Conjugation to PA [0040] Branched peptides with 2 or more arms, with each arm consisting of peptides containing 10 and 15 consecutive D-Glu residues coupled through the gamma carboxylic acid of the side chain to the alpha amino group of the neighboring C-terminal reside are synthesized by solid phase synthesis using D-Glu derivatives. 3 to 5 amino acid residues of Gly, Ala or beta-alanine are incorporated into the C-terminus terminus of the sequence to provide spacing between the D-Glu block and the conjugated protein. To enable conjugation through a sulfhydryl group, a Cys residue also may be incorporated at the C-terminus of the peptide. Branching is introduced by incorporation of Lysine residues in the sequence N-terminal to the spacer amino acids. Insertion of one Lys in the linear sequence can provide a branching point since further addition of amino acid residues can proceed through both α and ε amino groups of the Lys residue. A second Lys coupling can increase the number of branches to 4. The G-Glu derivatives can then be coupled to the 4 branches simultaneously through the activated gamma carboxylic acid, to generate the branched peptide. The synthesized peptide is purified by HPLC and characterized by MALDI. [0000] Conjugation of Gamma—D-Glutamic Acid Oligopeptide (bGDGP) to PA: [0041] bGDGP containing Cys at the C terminus is coupled to the Protein (PA) through the sulfhydryl side-chain of Cys and amino groups on the PA. Briefly, the protein in aqueous solution of pH between 7 and 8 is reacted with sulfosuccinimidyl-4-(N-maleimidomethyl)cyclohexane-1-carboxylate (Sulfo-SMCC). The succinimidyl group reacts with amino group on the protein to form a stable amide bond. The maleimide-activated protein is purified by a desalting column to remove excess sulfo-SMCC. To the purified protein conjugate, Cys containing peptide is added and the pH is adjusted to between 6.5 and 7.5. The maleimide coupling with the —SH group of the Cys side chain yields a PA-bGDGP conjugate which is further purified by column chromatography. The conjugate is characterized by Mass Spectrometry to determine the number of peptide molecules coupled to the PA molecule. Preparation of Nanoparticle Comprising the PA-bGDGP Conjugates: [0042] Nanoparticle comprising the PA-bGDGP conjugates is prepared by the self-assembly of the poly-anionic GDGP moiety with a poly-cationic material such as poly-lysine, polyethyleneimine, Histidine-Lysine co-polymers, or Histidine and Lysine containing linear or branched peptides. A solution containing PA-GDGP conjugate is mixed with a solution containing a polycation to form nanoparticles. Mixing is carried out by simple addition of one solution to the other followed by vortex or using a static mixer, where the two solutions are pumped into a static mixer to be mixed within the helical mixing element of a static mixer. Electrostatic interaction between the anionic bGDGP with the polycation leads to the formation of particles. The molar ratio of bGDGP to polycation is adjusted to obtain particles with net negative, neutral or positive surface charge. Particles with net surface charge provide colloidal stability to the nanoparticle formulation. In order to further enhance the stability, surfactants optionally are added to one or both solutions. Samples are prepared with pluronic surfactant. Nanoparticle samples are prepared so that some of the PA molecules are exposed on the surface of the particle, to facilitate the uptake of the particle by antigen presenting cells to elicit an immune response against PA and bGDGP. Example 5 Preparation of Nanoparticle Comprising HK Polymer and PGA Polymer [0043] Nanoparticle comprising HK polypeptide polymers and PGA is prepared by self-assembly of the poly-anionic PGA moiety with a poly-cationic Histidine-Lysine co-polymers of linear or branched form. A solution containing PGA is mixed with a solution containing HK polymer to form nanoparticles. Mixing is carried out by simple addition of the solution giving excess charge ratio to the other followed by vortex, or using a static mixer where the two solutions are pumped into a static mixer to be mixed within the helical mixing element of a static mixer. Electrostatic interaction between the anionic PGA with the polycation lead to self assembly of particles. The molar ratio of PGA to polycation is adjusted to obtain particles with net negative, neutral or positive surface charge. Particles with net surface charge provide colloidal stability to the nanoparticle formulation. In order to further enhance the stability, surfactants optionally are added to one or both solutions. Samples are prepared with pluronic surfactant. Nanoparticle samples are prepared so that some of the PGA molecules are exposed on the surface of the particle, to protect the nanoparticle from phagocytic cell uptake. Example 6 Preparation of Nanoparticle Comprising Squalamine and PGA [0044] Nanoparticles comprising cationic Squalamine are prepared by self assembly of Squalamine poly-anionic GDGP, bGDGP or PGA. A solution containing Squalamine is mixed with a solution containing a polyanion to form nanoparticles. Mixing is carried out by simple addition of one solution to the other followed by vortex or using a static mixer, where the two solutions are pumped into a static mixer to be mixed within the helical mixing element of a static mixer. Electrostatic interaction between the anionic glutamic acid with the cationic Squalamine leads to the formation of particles. The molar ratio of polyanionic species to Squalamine is adjusted to obtain particles with net negative, neutral or positive surface charge. Particles with net surface charge provide colloidal stability to the nanoparticle formulation. In order to further enhance the stability, surfactants or hydrophilic polymers such as PEG are incorporated into the nanoparticle through covalent bonding or by non-covalent interaction. Example 7 Preparation of Nanoparticle Comprising Squalamine Conjugated to Cationic Polypeptide [0045] The amino group of Squalamine is conjugated to cationic polypeptides consisting Lys, or His and Lys amino acids through using homobifunctional cross linkers described in Example 3, or through coupling with a dithiol benzyl that exhibits reduction mediated release of Squalamine as described in U.S. Pat. No. 7,238,368 which is herein incorporated by reference. [0046] The Squalamine-Polycation conjugate is mixed with PGA,GDGP or bGDGP to form nanoparticles. Mixing is carried out by simple addition of one solution to the other followed by vortex or using a static mixer, where the two solutions are pumped into a static mixer to be mixed within the helical mixing element of a static mixer. Electrostatic interaction between the anionic glutamic acid with the cationic Squalamine-polycation conjugate leads to the formation of particles. The molar ratio of polyanionic species to Squalamine-polycation conjugate is adjusted to obtain particles with net negative, neutral or positive surface charge. Particles with net surface charge provide colloidal stability to the nanoparticle formulation. In order to further enhance the stability, surfactants or hydrophilic polymers such as PEG are incorporated into the nanoparticle through covalent bonding or by non-covalent interaction.
Polyelectrolyte nanoparticle compositions for biomedical applications are provided comprising at least two carrier domains comprising multivalent ionic domains and an agent exhibiting biological activity when contained within the nanoparticle or on the nanoparticle surface. The multivalent ionic domains may be contained in two separate molecules or in separate but linked domains of a single molecule. The nanoparticle optionally can further comprise an exposed targeting ligand and/or protective surface. The nanoparticle can be contacted to cells or administered directly to an animal for biomedical applications including therapeutics and immune response. The nanoparticle may alternatively be comprised of a carrier material capable of delivering various medically important antigens as vaccine.
0
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation-in-part of U.S. patent application Ser. No. 11/703,966, filed Feb. 8, 2007, the entire specification of which is incorporated herein by reference. BACKGROUND OF THE INVENTION TECHNICAL FIELD [0002] This invention generally relates to storage and transportation materials. More particularly, the invention relates to mailing and storage boxes and envelopes. Specifically, the invention relates to boxes and envelopes that are made of a plurality of different layers that have protective materials incorporated therein or applied thereto to protect the article from a variety of different threats. BACKGROUND INFORMATION [0003] Offices and individuals frequently need to store materials such as files and papers for long periods of time. Typically, these materials are placed in some sort of storage box for safekeeping. These boxes may take a variety of forms including plastic tubs or corrugated cardboard boxes with lids. Plastic tubs are convenient and protect the materials stored therein from dangers such as liquid exposure, but can be relatively expensive if large volumes of materials need to be stored. Cardboard boxes on the other hand are inexpensive and convenient, but they are vulnerable to dangers such as water damage, fire, insects and mold. [0004] There is therefore a need in the art for an improved corrugated cardboard box that is less vulnerable to threats that may damage the contents of the box. SUMMARY OF THE INVENTION [0005] The device of the present invention comprises a packaging article for protectively storing perishable paper products that includes protective materials that protect the packaging article and its contents from any of a number of threats including water damage, fire damage, mold, insects, bacteria, fungi and theft. The packaging article comprises a bottom wall, side walls and a closure that surround and define an interior cavity in which the paper products are stored or transported. Each of the bottom wall, side walls and closure are made from a plurality of layers. Protective materials are applied to one or more of the bottom wall, side walls and closures by impregnating a paper or cardboard layer with a suitable chemical, applying a film thereover, spraying a coating thereover or sandwiching the protective material between two adjacent layers. Suitable chemicals that produce the desired properties include, but are not limited to wax, oil, plastic, polybrominated diphenyl ether, polybrominated biphenyl, brominated cyclohydrocarbons, boric acid and hydrogen peroxide. A radio frequency identification tag may also be received within the wall of the packaging article to protect the same against theft. BRIEF DESCRIPTION OF THE DRAWINGS [0006] The preferred embodiments of the invention, illustrative of the best mode in which applicant has contemplated applying the principles, are set forth in the following description and are shown in the drawings and are particularly and distinctly pointed out and set forth in the appended claims. [0007] FIG. 1 is a perspective view of a corrugated cardboard box known in the prior art; [0008] FIG. 2 is a cross-sectional top view through line 2 - 2 of FIG. 1 ; [0009] FIG. 3 is a perspective view of a corrugated cardboard box in accordance with the present invention; [0010] FIG. 4 is a cross-sectional top view of a first embodiment of a side wall taken through line 4 - 4 of FIG. 3 ; [0011] FIG. 4A is a cross-sectional, top view of a second embodiment of the side wall of the storage box of FIG. 3 ; [0012] FIG. 4B is a cross-sectional top view of a third embodiment of the side wall of the storage box of FIG. 3 ; [0013] FIG. 4C is a cross-sectional top view of a fourth embodiment of the side wall of the storage box of FIG. 3 ; [0014] FIG. 5 is a cross-sectional top view of a fifth embodiment of the side wall of the storage box of FIG. 3 ; [0015] FIG. 6 is a cross-sectional top view of a sixth embodiment of the side wall of the storage box of FIG. 3 and showing the incorporation therein of a security tag; [0016] FIG. 7 is a perspective view of a mailing envelope in accordance with the present invention; [0017] FIG. 8 is a cross-sectional top view of the mailing envelope taken through line 8 - 8 of FIG. 7 and showing the structure of the front wall of the envelope; [0018] FIG. 8A is a cross-sectional top view of a second embodiment of the front wall of the envelope; [0019] FIG. 8B is a cross-sectional top view of a third embodiment of the front wall of the envelope; and [0020] FIG. 9 is a cross-sectional top view of a fourth embodiment of the front wall of the envelope showing the incorporation therein of a security tag. DETAILED DESCRIPTION OF THE INVENTION [0021] FIGS. 1 and 2 show a corrugated cardboard box 10 known in the prior art. Box 10 has a bottom wall (not shown) and four side walls 12 that define an interior cavity 14 for holding a plurality of files or papers 16 . A lid 18 is provided for closing off access to cavity 14 . Lid 18 may take any one of a number of different forms, such as four panels as shown in FIG. 1 , or a single panel (not shown) or a completely separate lid unit (not shown). The bottom wall, side walls 12 and lid 18 are all made from corrugated cardboard. As shown in FIG. 2 , the side wall 12 comprises two planar sheets 20 , 22 which sandwich a corrugated cardboard sheet 24 thereinbetween. The cardboard used in box 10 is vulnerable to water damage, fire damage, may permit mold to grow thereon if it is subjected to high moisture environments and is susceptible to paper-eating insets such as silverfish and the like. [0022] FIGS. 3-5 show a storage box in accordance with the present invention and generally indicated at 50 . Box 50 is similarly formed to box 10 in that it has a bottom wall (not shown), side walls 52 that surround and define an interior cavity 54 for holding a plurality of files or papers 56 therein. A lid 58 is provided for closing off access to cavity 54 . Lid 58 shown in FIG. 3 comprises four panels that are secured together with an adhesive tape of the like. It will be understood by those skilled in the art that the shape, size and configuration of box 50 , as shown in the attached drawings, is by way of illustration only. Any shape, size and configuration of the box and lid may be used without departing from the spirit of the present invention. [0023] In accordance with a specific feature of the present invention, each of the bottom wall, side walls 52 and lid 58 of box 50 are manufactured from a corrugated cardboard that has been specially treated with one or more of several protective materials as will are hereinafter described. [0024] Referring to FIG. 4 , there is shown a portion of side wall 52 comprising a first and a second planar sheet 60 , 62 of cardboard which sandwich a corrugated sheet 64 of cardboard thereinbetween. It will be understood by those skilled in the art, that the bottom wall, side walls 52 and lid 58 of box 50 may be made up from any number of a plurality of planar and corrugated sheets that are layered and bonded together to form a unitary member of the required strength, without departing from the spirit of the present invention. The following illustrations show a box wall 52 made from two planar sheets and one corrugated sheet for the sake of clarity only. FIG. 4 illustrates a first embodiment of the side wall 52 in which one or more of sheets 60 , 62 and 64 are impregnated with a protective material as will be hereinafter described. [0025] FIG. 4A shows a second embodiment of side wall 152 that includes layer of protective material 166 therein. In this instance, layer 166 is applied over second sheet 162 and, because second sheet 162 forms the exterior surface of side wail 152 , protective layer 166 forms the external surface of the storage box. [0026] Referring to FIG. 4B , there is shown a third embodiment of a side wall of the box, being generally indicated at 252 . Side wall 252 comprises first and second planar sheets 260 , 262 of cardboard which sandwich a corrugated layer 264 thereinbetween. Protective layer 266 is applied over first sheet 260 and thus forms the interior surface of the box in accordance with the present invention. [0027] Referring to FIG. 4C , there is shown a fourth embodiment of a side wall for the box, being generally indicated at 352 . Side wall 352 comprises first and second planar sheets 360 , 362 of cardboard which sandwich a corrugated layer 364 thereinbetween. A first protective layer 366 is applied over sheet 362 and a second protective layer 368 is applied over sheet 360 . The protective layers 366 , 368 therefore form both the exterior and interior surfaces of the box. [0028] Referring to FIG. 5 , there is shown a fifth embodiment of a side wall for the box, being generally indicated at 452 . Side wall 452 comprises first and second planar sheets 460 , 462 of cardboard which sandwich a corrugated layer 464 thereinbetween. A protective layer 466 is applied over second sheet 462 and another planar sheet of cardboard 470 is applied over protective layer 466 . Thus, protective layer 466 is sandwiched between two layers of untreated cardboard. [0029] Referring to FIG. 6 , there is shown a sixth embodiment of a side wall for the storage box, being generally Indicated at 552 . Side wall 552 comprises first and second planar sheets 560 , 562 of cardboard which sandwich a corrugated layer 564 thereinbetween. A protective layer 566 is applied over second sheet 562 . In accordance with another specific feature of the present invention, side wall 552 further incorporates an RFID (Radio Frequency Identification) tag 580 . Tag 580 is sandwiched between corrugated layer 564 and planar sheet 562 . Tag 580 may be used to rapidly locate a particular storage box. Tag 580 may also be used as a security device to set off an entryway alarm if the box is removed from a storage facility by unauthorized personnel. In this way, tag 580 is incorporated as a protective material against the threat of theft. [0030] In accordance with one of the specific features of the present invention, one or more layers of the bottom wall, side walls 52 and lid 58 of box 50 include protective materials that impart improved protective properties to the storage box 50 . In a first instance, shown in FIG. 4 , any or all of sheets 60 , 62 and 64 may be impregnated with a protective material. Thus, any and all of sheets 60 , 62 and 64 constitute a protective layer of box 50 . [0031] With reference to FIGS. 4A-6 , the protective layer will be referred to in the following description as layer 66 for the sake of clarity, but it will be understood that any and all of the protective layers 66 , 68 through to 466 includes one or more protective materials that impart improved protective properties to the storage box. Protective layer 66 may be one of a planar or corrugated sheet of cardboard that is impregnated with the protective material. Alternatively, protective layer 66 may comprise a film that is bonded onto a planar sheet of cardboard. Furthermore, protective layer 66 may constitute a separate thin film. Finally, protective layer 66 may constitute a powder or liquid coating that is sprayed or otherwise deposited onto one of the sheets in the box. [0032] The protective layer 66 may constitute cardboard that is impregnated with a chemical that renders that layer water impervious or water repellant. The chemical may render the layer fire resistant or fire retardant. The chemical may be a fungicide that prevents mold from growing, or a pesticide that kills insects such as silverfish or that repels such insects because of an odor or taste associated therewith. A wide variety of chemicals are known to produce these properties, but have not been previously applied to corrugated cardboard or have not been applied in combination with each other to cardboard. So, for instance, a wide variety of chemicals and chemical components may be used for these purposes. These include, but are not limited to, a wax, or an oil may be impregnated into the layer, or a plastic film may be used to create a water repellant or resistant layer. Chemicals such as aluminum hydroxide and diammonium phosphate, polybrominated diphenyl ether, polybrominated biphenyl or brominated cyclohydrocarbons can be sprayed or otherwise applied to a one of the layers 60 , 62 or a separate cardboard sheet in order to create a fire retardant layer. Boric acid or hydrogen peroxide may be used in layer 66 to act as a pesticide or fungicide. So, for example, in FIG. 4 , one or more of sheets 60 , 62 and 64 may be impregnated with a suitable insecticide to repel insects such as silverfish from box 50 . Or, in FIG. 4A , layer 166 of a suitable fire-retardant chemical may be applied over the outer sheet 162 of the box. Or, in FIG. 4B , a fungicide may be applied as layer 268 over the interior sheet 260 of the box. Or, in FIG. 4C , layer 366 may be a suitable water repellant and layer 368 may be a fire retardant. Or, in FIG. 5 , a fire-retardant layer 466 may be sandwiched between two sheets 462 , 470 of cardboard. [0033] It will be understood by those skilled in the art that one or more or all of these and other chemical compounds may be applied to the cardboard in one or more layers in order to protect the box from one or more of water, fire, insects and mold. Furthermore, any other chemical or substance may be applied to the interior or exterior of box 50 , or may be impregnated into the cardboard layers thereof in order to give the materials thereof the protective qualities that are desired. [0034] FIGS. 7-9 illustrate a mailing envelope in accordance with the present invention and being generally indicated at 700 . Envelope 700 comprises a pouch 702 and a flap 704 . Flap 704 includes an adhesive layer 706 over which a protective paper cover (not shown) is applied. The paper cover is removed from layer 706 when the envelope 700 has been stuffed and is to be closed. Flap 704 is folded over into abutting contact with wall 710 and adhesive layer 706 secures flap 704 to wall 710 . Preferably, both the pouch 702 and flap 704 incorporate protective materials therein. The protective materials are applied therein to secure the envelope 700 against threats such as fire, water, insects, mold, fungi, bacteria and theft. [0035] In accordance with one of the specific features of the present invention, walls 710 and 712 are manufactured from a plurality of layers. One or more of those layers include materials that impart protective properties to envelope 700 . Walls 710 and 719 may be integrally formed or may be secured together in some suitable manner. Walls 710 and 712 surround and define an interior cavity 714 into which the articles to be mailed are placed. [0036] FIG. 8 shows a first embodiment of the structure of wall 710 . Wall 710 comprises a first layer 716 , a second layer 718 and a third layer 720 . First layer 716 may be manufactured from any material, such as a paper or cardboard product. Second layer 718 is applied onto a first surface of first layer 716 . Second layer 718 is manufactured from a plastic blister-type material and is thus waterproof. Second layer 718 additionally provides cushioning for the articles retained within the cavity 714 . Third layer 720 is applied to a second surface of first layer 716 . Third layer 720 is provided to protect first layer 716 from a different threat to that of second layer 718 . So, for instance, third layer 720 may include a fungicide or a fire-retardant material. As previously described in relation to the storage box, if first layer 716 is a paper product, a protective material may be impregnated directly into that layer. Second and third layers 718 , 720 may be applied as a film or sprayed onto first layer 716 . The structure of wall 710 is shown by way of illustration only. Any suitable layering of different materials may be utilized to protect the articles within pouch 702 from a variety of different threats such as water damage, fire damage, mold, bacteria, fungi, insects and theft. [0037] FIG. 8A shows a second embodiment of a possible structure of the envelope wall, said wall being generally indicated at 810 . Wall 810 again is made up from a first layer 816 , a second waterproof blister-type layer 818 and a third layer 820 . In this instance, third layer 820 is applied onto second layer 818 instead of onto the first layer 816 . Third layer 820 may include a fire-retardant that protects the blister type second layer 818 from melting. [0038] FIG. 8B shows a third embodiment of the possible structure of the envelope wall, being generally indicated at 910 . Again, wall 910 comprises a first layer 916 , a plastic blister-type material second layer 918 applied to a first surface of first layer 916 , a third layer 920 applied to a second surface of first layer 916 , and a fourth layer 922 applied to a second surface of the second layer 918 . Again, each one of the first, second, third and fourth layers 916 - 922 provides protection against a different threat. [0039] Finally, FIG. 9 shows a fourth embodiment of the structure of the envelope wall being generally indicated at 1110 . The structure of wall 1110 is substantially identical to that of the first embodiment 710 thereof, with the exception that the wall includes a pouch 1112 that surrounds and retains an RFID tag 1114 therein to protect envelope 700 from the threat of theft. [0040] As with the storage box, the protective layers in envelope 700 may be impregnated into the material of the layer, applied as a film, applied as a spray coating or may be sandwiched between the various layers within envelope 700 . [0041] In the foregoing description, certain terms have been used for brevity, clearness, and understanding. No unnecessary limitations are to be implied therefrom beyond the requirement of the prior art because such terms are used for descriptive purposes and are intended to be broadly construed. [0042] Moreover, the description and illustration of the invention are an example and the invention is not limited to the exact details shown or described.
A packaging article for protectively storing perishable paper products that includes protective materials that protect the packaging article and its contents from any of a number of threats including water damage, fire damage, mold, insects, bacteria, fungi and theft. The packaging article comprises a bottom wall, side walls and a closure that surround and define an interior cavity in which the paper products are stored or transported. Each of the bottom wall, side walls and closure are made from a plurality of layers. Protective materials are applied to one or more of the bottom wall, side walls and closures by either impregnating a paper or cardboard with a suitable chemical, applying a film thereover, spraying a coating thereover or sandwiching the protective material between two adjacent layers. Suitable chemicals that produce the desired properties include, but are not limited to wax, oil, plastic, polybrominated diphenyl ether, polybrominated biphenyl, brominated cyclohydrocarbons, boric acid and hydrogen peroxide. A radio frequency identification tag may also be received within the wall of the packaging article to protect the same against theft.
1
BRIEF SUMMARY OF THE INVENTION This invention relates to to devices for securing together elongated objects, particularly the segments of a fishing pole, and to fishing poles which employ such devices. Fishing poles of any length are usually made in two or more segments joined by ferrules. When a pole is not in use, the segments can be separated so that the pole can be more conveniently stored or transported. When the pole is in use, fishing line extends through line guides on the pole segments. Fishing tackle, including a hook and other equipment, such as swivels, leaders, lures and bait are attached to the free end of the line. Before a pole can be broken down for storage, it is necessary to disconnect such tackle, which would otherwise become entangled in the separated pole segments. Once the tackle is removed, the line is fully reeled in, likewise to avoid tangling. Because it takes considerable time to rig a fishing pole, i.e. to thread the fishing line through the line guides and attach tackle at the free end, it is very inconvenient to separate the pole segments if the user intends to carry the pole only a short distance, or store it for a short period of time. There is thus a need for a way to separate the segments for convenience of transportation and storage without derigging the pole. The present invention is a connector device which allows the pole segments to be stored alongside one another in generally parallel alignment without derigging the pole. The connector is used to hold the pole segments in a fixed, side-by-side relationship. Additionally, the connector is adapted to hold fishing line or leader which may extend outwardly from the tip of the pole. It is an object of the present invention to provide a connector which allows fishing pole segments to be conveniently stored side-by-side without derigging. Another object is to provide a fishing pole with at least one such connector. An additional object is to provide such a connector which is simple to use and easy to manufacture. One specific object is to provide a hinge connector for joining two elongated objects, such as fishing pole segments. Other objects and advantages of this invention will become apparent to those skilled in the art upon reading the following description. BRIEF DESCRIPTION OF THE DRAWINGS In the drawings: FIG. 1 is a side elevational view of a fully rigged fishing pole that comprises two segments held in side-by-side relationship by a first connector according to the present invention; FIG. 2 is an enlarged, isometric view of the connector shown in FIG. 1; FIG. 3 is a side elevational view of a second connector according to the present invention, a portion being broken away to show internal detail, the connector having arms positioned to hold fishing pole segments in end-to-end alignment and having a locking sleeve in a locked position; FIG. 4 is a vertical sectional view of the connector of FIG. 3, showing one arm of the connector located in a lowered and rotated position to hold the pole segments in side-by-side alignment with the locking sleeve in an unlocked position. FIG. 5 is a top isometric view of the second connector positioned as shown in FIG. 4, with the locking sleeve in an unlocked position; FIG. 6 is a bottom isometric view of the second connector positioned as shown in FIG. 4, with a portion broken away to show internal detail and with the locking sleeve shown in a locked position; and FIG. 7 is a sectional view taken along line 7--7 of FIG. 4. DETAILED DESCRIPTION FIG. 1 shows a fishing apparatus 10, which is a pole comprising two pole segments 12, 14 on which are mounted line guides 16, 17 respectively. A fishing reel 18 is mounted near the butt end 20. Fish line 22 extends from the reel 18 through the line guides 16, 17, including the line guide at the tip 24 of the pole. An inner length 25 of the line extends from the reel 18 to the tip 24. An outer length 26 extends outwardly from the tip. Fishing tackle is attached to the distal end of the outer length 26. During normal usage, the pole segments 12, 14 are joined by means of a ferrule. Specifically, at a connection end of the segment 12 is a female portion 30 of the ferrule which receives the male portion 32 located at a connection end of pole segment 14. The female portion 30 is slightly flared and the male portion 32 is tapered at the same angle to provide a tight frictional fit. Different poles and portions of poles will have ferrules of different diameters and taper angles, depending on the manufacturer and pole size. When it is desired to move the pole for more than a short distance or to place it in a vehicle, the two ferrule portions are separated and the pole segments placed side-by-side for easier handling. In order to accomplish this task, without intolerable tangling of the fishing tackle, it is necessary to remove the tackle from the line 22 and reel the line in completely onto the reel 18. By using a transport and storage connector according to the present invention, placing the segments in side-by-side relationship is a much easier process. In one embodiment, shown in FIGS. 1 and 2, a connector 40 comprises a male coupling 42 which is shaped to be received by the female portion 30 of the ferrule, and a female coupling 44 shaped to receive the male portion 32 of the ferrule. The couplings 42, 44 are spaced apart and both attached to an interconnecting member 46 in such an orientation that the couplings extend from a first side 48 of the body in substantially the same direction and in substantially parallel alignment. A second, opposite side 50 of the body 46 defines a channel 52 which is adapted to receive and hold the fish line 22 and/or leader taut when the ferrule portions 30, 32 are engaged by the respective couplings and the pole segments 12, 14 are positioned adjacent one another along their respective lengths, as shown in FIG. 1. The inner length 25 of the line 22 can, but need not, be placed in the channel 52, depending on the preference of the user. To use the connector 40, one separates the ferrule portions 30, 32 and pushes them into engagement with the couplings 42, 44 respectively. The line guides 16 of the segment 12 and the line guides 17 of the segment 14 should extend away from each other as shown, so that the line 22 can extend directly through the channel 52. Once the line 22 is in the channel 52, the user can wind the reel 18 to take up slack in the line 22. A hinged embodiment of the connector, which need not be removed when the pole is in use, is shown in FIGS. 3-7. Features of the hinged connector that are common to features of the connector of FIGS. 1 and 2 bear the same reference numerals incremented by one hundred. The hinged connector has two bodies which serve as couplings 142, 144. In the illustrated embodiment, the interior of the female coupling 144 is slightly flared and the exterior of the male coupling 142 is tapered to provide a tight frictional fit with mating ferrel segments of the pole. One of the bodies, the male coupling 142 in the illustrated embodiment, is pivotally connected to the interconnecting member 146. In particular, the interconnecting member 146 defines an elongated opening 156. A pivot pin 158 is received in the opening for slidable and pivotal movement as shown in FIG. 4. When the two pole sections 12, 14 are coupled to the connector 140, the pole sections can be moved between a generally end-to-end position as shown in FIG. 3 and a generally side-by-side position as shown in FIG. 4 by pivoting the male coupling 142. To assure that the line 22 will be properly held in the channel 152, the connector 140 should be oriented such that, when the segments are in the side-by-side position, the line guides 16 extend in the opposite direction from the line guides 17, as shown in FIG. 4. An end locking mechanism is provided for rigidly securing the coupling means in end-to-end alignment as shown in FIG. 3. The end locking mechanism includes a slidable sleeve 162 for encircling portions of both couplings 142, 144 when aligned end-to-end. The exterior of the connector 140 is tapered and the interior of the sleeve 162 is flared such that when the sleeve is moved toward the interconnecting member 146, it frictionally engages the connector 140 and is thus retained in a locked position. The sleeve 162 defines a slot 164 for receiving a portion of the interconnecting member 146 when the sleeve engages both the couplings aligned end-to-end. A stop ring 166 is provided on the female coupling 144 to prevent the sleeve 162 from inadvertently sliding off the connector 140. The stop ring may be permanently secured, or merely press fit to allow for removal of the sleeve 162 when desired. If press fit, preferably both the exterior of the connector 140 is turned and the ring 166 is bored to provide tapers of 1.5 degrees. A side locking mechanism is provided for rigidly securing the couplings 142, 144 in side-by-side alignment. In the embodiment of FIGS. 3-7, interlocking devices are provided on both the male coupling 142 and the sleeve 162. In particular, at least a portion of the slot 164 is tapered to form a dovetail groove, and a flared dovetail tongue 170 extends from the male coupling 142, as best seen in FIG. 7. When the pole segments 12, 14 lie side by side, as illustrated in FIG. 4, the couplings 142, 144 can be locked together simply by sliding the sleeve 162 to the position shown in FIG. 6, such that the dovetail tongue and groove engage one another. Because the hinged connector 140 of FIGS. 3-7 need not be removed from the pole when fishing, the connector should be made from the same material as the pole to preserve the action of the pole. Such materials may include fiberglass, leaded glass, carbon fiber, graphite and plastic. Operation of the hinged connector will be apparent from the foregoing description. To move a pole from the extended position shown in FIG. 3 to the folded position shown in FIG. 4, the procedure is simple. First, one slides the sleeve 162 away from the pivot point, i.e. to the right in FIG. 3, to the unlocked position, shown by broken lines, where it no longer surrounds both the axially aligned couplings 142, 144. Next, one pushes the female coupling 144 downwardly to the position shown by the lowest set of broken lines in FIG. 4 and then rotates the coupling 144 about the pivot pin 158 until the coupling 144 is in the position shown by solid lines in FIG. 4. Finally, the sleeve 162 is moved back toward the pivot to the position shown in FIG. 6 so that the dovetail tongue and groove are engaged. The procedure is reversed to unfold the pole segments. When the pole segments are moved from the extended to the folded position, the user may place the fishing line and/or leader in the connector channel and then wind the reel 18 to take up any slack in the line 22. The distal end of the fishing line and any associated tackle are secured to the pole at any convenient position, usually by engaging a hook with a convenient attachment point on the pole. Depending on the length of the leader, the attachment point could be a line guide 16, 17 on either of the segments 12, 14, a special eyelet near the reel 18, a cork hand grip portion, or a part of the reel. In some circumstances, the leader will be sufficiently long that the leader or other tackle will extend from the tip 16 through the channel on the connector, with the hook secured to a portion of the pole segment 12, as illustrated in FIG. 1. Having shown and described preferred embodiments of my invention, it will be apparent to those skilled in the art that changed and modifications may be made without departing from my invention in its broader aspects. For example, a fishing pole according to the present invention could include more than two segments. Such a pole could advantageously employ multiple connectors. Connectors according to the present invention could be used to join elongated objects other than fishing pole segments. The hinged embodiments of FIGS. 3-7 could have bodies that are permanently secured to the pole segments, or the bodies could be formed as integral parts of the pole segments.
A connector to a fishing rod object in side-by-side alignment is disclosed. The connector includes a channel to receive fishing line and/or leader so that the segments can be held side-by-side, for storage or transportation, without removing tackle and reeling in all the line.
0
TECHNICAL FIELD This invention is in the field of oligonucleotide synthesis. More particularly, it concerns a group of benzazoles and corresponding benzazolides and their use as activators in phosphate triester oligonucleotide synthesis schemes. THE PRIOR ART An article "Making Genes With Machines" by B. H. Cole, appearing in High Technology, Vol. 1, No. 1, pages 60-68 provides a general overview of three fundamental processes presently of interest in the fabrication of oligonucleotides in precisely defined sequences. These three processes are known as the phosphate diester process, the phosphate triester process and the phosphite triester process. The "phosphite triester" process generally involves reaction of a suitably protected nucleoside, a phosphitylating reagent (for example, methoxydichlorophosphine) and a second protected nucleoside that optionally is immobilized on a solid support, followed by mild oxidation. (This general process for oligonucleotide synthesis is described in K. K. Ogilvie, et al Can. J. Chem., 58, 1389 (1980) and 58, 2686 (1980) and Tetrahedron Letters, 21, 4159 (1980); as well as M. H. Caruthers, et al Nucl. Acids Res. Symposium Series #7, 215 (1980), S. L. Beaucage, et al, Tetrahedron Letters, 22, 1859 (1981), and European Patent Application No. 035,719 (16,09,81) all of which for brevity are incorporated herein by reference. These references teach that it is advantageous to add a mild acid activator to the reactions and that benzimidizole or more commonly 1-H-tetrazole can be employed in this role. In working with both of these systems for nucleotide oligomerization certain fundamental shortcomings related to the art-taught tetrazole activators become apparent. For one, tetrazole is only marginally soluble in usual reaction solvents. This tendency of tetrazole to crystallize causes undesirable dilution and poses risks of clogging the microscale equipment usually employed. For another, simple triazoles and tetrazole cannot be easily modified to enhance their solubility, reactivity and/or stability so that less than optimum life of very expensive reagents is observed and/or less than complete reaction often takes place. This latter failing is very serious in a multi-step oligonucleotide synthesis where usually acceptable conversion losses quickly multiply to given an unreasonable result. It is an object of this invention to provide an advanced and improved family of activators for the phosphite triester oligonucleotide syntheses. STATEMENT OF THE INVENTION It has now been found that benzotriazoles of the formula ##STR1## wherein Y is H or an acidic leaving group and A, B, C and D are each independently selected from hydrogen and aromatic ring substituent groups, give superior results as activators in the phosphite triester oligonucleotide preparation route. These benzotriazoles or the corresponding benzimidazoles can also form phosphinedibenzazolides of the formula ##STR2## wherein X is N or CH and R is a phosphite protecting group which themselves react to form benzazolides. The materials function as activators in the phosphite triester synthesis schemes. The benzotriazoles form new benzotriazolide intermediates with protected deoxynucleosides and deoxynucleotides. These intermediates have the formula ##STR3## wherein A, B, C and D and X are as previously defined, R is a phosphite protecting group and Nu is a nucleoside, a nucleotide or an oligonucleotide (all with or without protecting groups). In other aspects, this invention relates to improved phosphite triester oligonucleotide preparation processes employing the subject benzotriazoles or derivatives thereof and, alternatively, the phosphinedibenzazolides. BRIEF DESCRIPTION OF THE DRAWING This invention will be described with reference to the drawing wherein FIG. 1 is a graph comparing the coupling efficiency with time of a oligonucleotide-forming reagent when activated by either a compound of this invention or by a material of the prior art. DETAILED DESCRIPTION OF THE INVENTION The benzotriazoles employed in this invention, have the structure ##STR4## wherein Y is H or an acidic leaving group. In both cases the aromatic rings contain A, B, C and D groups on their 5, 6, 7 and 8 carbons. These may all be hydrogens or they may independently each be aromatic ring-substituenting groups known to the art of organic chemistry. The ability to make these substitutions is one of the major advantages of the present invention as it permits the solubility and reactivity/stability of the materials to be finely tuned. The substituents placed on the ring should be chemically inert under the reaction conditions encountered in oligonucleotide syntheses. Examples of suitable ring-substituenting groups include halogens, such as chloro, bromo, iodo or fluoro; lower alkyls of 1 to 4 carbons such as methyl, ethyl, propyl or the like; simple substituted alkyls such as chloromethyl, trifluoroethyl, and the like; aromatics and substituted aromatics such as benzyl, phenyl, and substituted benzyl or phenyl; lower alkoxies of 1 to 4 carbons such as methoxy, ethoxy, and n and isopropoxy; nitro, nitroso, sulfonato, amino and cyano. As previously mentioned, the exact A, B, C and D's employed will be at least in part dictated by the properties sought. For example, when a less polar reaction medium is being employed it will often be of advantage to add relatively non-polar A, B, C and D groups, such as the lower alkyls and aromatics, to enhance solubility. Similarly, with these phosphite activating agents, it is believed that, to at least an extent, reactivity is a function of the electronegativity of the nitrogen to which H is attached such that the more "acidic" this proton the more effective the compound is as an activating agent. Conversely, the less "acidic" this proton is, the more stable the system. Thus, by adding electron-donating or withdrawing groups such as F, NO 2 , C(CH 3 ) 3 OCH 3 (alkoxy) and the like to A, B, C or D positions, the system's reactivity/stability can be tailored. Preferred groups, because of their ready synthesis, include those having each of A, B, C and D as hydrogens, and those having at their "5" carbon (that is, as A) Cl, Br, NO 2 , CH 3 , or O--CH 3 . Other A, B, C and D substituents may be employed, as well, if desired. These benzotriazole materials react with nucleotides protected nucleotides to give new compounds of the formula ##STR5## wherein A, B, C, D and X are as previously defined, R may be hydrogen but usually is a suitable base-liable phosphite protecting group. This protecting group is an organic group such as a simple aliphatic or aromatic group, for example, a 1 to 4 carbon lower alkyl or a substituted or unsubstituted aromatic (6 to 12 carbon aryl, alkaryl or aralkyl) such as phenyl, 2-chlorophenyl, 2-methylphenyl, 2-bromophenyl, 4-chlorophenyl, 2,4-dichlorophenyl or the like. Other phosphite triester blocking groups taught by the art to be equivalent may be used as well. Nu is a nucleoside, nucleotide or oligonucleotide particularly one having its "5" hydroxyl and, if appropriate, its base protected. It should be noted that the symbol "Nu" and the term "nucleoside" are defined to include deoxynucleosides and likewise the term "nucleotide" includes deoxynucleotides as these are the materials usually of most interest. Thus, these intermediates can be represented (with deoxy materials) by the formulae I and II. ##STR6## wherein A, B, C, D, X and R are as previously described. P g is a selectively removable protecting group for the nucleoside's '5 carbon hydroxyl, such as levulinyl and (most commonly) acid labile groups like trityl (triphenylmethyl) and DMT (4,4-dimethoxytrityl). B* and B*' are each bases selected from 1-thyminyl, 1-(N-protected)cytosinyl, 9-(N-protected)adeninyl or 9-(N-protected)guaninyl. The N-protecting groups are materials known in the art and typically include benzoyl groups, isobutyryl groups and anisoyl groups with the benzoyl group being the group of choice with adenine and cytosine and isobutyryl being the group of choice with guanine, and n is an integer, usually 1 but also higher numbers such as 2,3,4,5 up to 10 or 12 or more, if desired. In these higher mer unit materials B* will be selected independently in each repeat unit. It will also be appreciated that nucleosides and nucleotides can simply replace the deoxy materials shown here. These activated species may be prepared by reacting an optionally protected nucleoside phosphite (or, as particularly shown, phosphoramidite) and the benzotriazole such as ##STR7## This reaction may be carried out in solution in a suitable organic aprotic reaction solvent such as acetonitrile, pyridine, tetrahydrofuran, dimethylformamide, 1,4-dioxan, methylene chloride, chloroform, ethyl acetate, acetone, diethyl ether, benzene and mixtures thereof. A substantial (2 to 20 times) molar excess of the benzotriazole is usually used. This reaction is rapid and is usually complete in 1 to 20 minutes at temperatures from -20° C. to 50° C. These active species can be used as building blocks in the growth of oligonucleotides. For instance they can be used to couple to a second nucleoside that has been attached through its 3' hydroxyl group to a solid support, denominated S s in the following formula ##STR8## In the subsequent oxidation step, iodine or a similarly effective oxidation agent, e.g. hydrogen peroxide or alkyl or arylperoxides or peroxyacids, such as m-chloroperbenzoic acid, can be used. This product can have its 5' hydroxyl deblocked and be further reacted with additional active species to add yet further nucleotide units. Thereafter the entire oligonucleotide is removed from the support, the bases are unblocked and the phosphate protecting group can be removed. Alternatively, the nucleoside benzazolide can be prepared by reaction of a nucleoside with the corresponding phosphineditriazolide or diimidazolide, that is ##STR9## wherein A, B, C and D and X are as previously defined and R is a phosphite protecting group as previously described. The dibenzotriazolides and dibenzoimidazolides can be formed by reaction of the benzazole with a dihalogen-substituted oxy-phosphorus compound such as phosphorodichloridite, e.g., p-chlorophenylphosphorodichloridite or the like. ##STR10## Other organo groups can replace the chlorophenyl groups--for example, lower alkyls of 1 to 4 carbons and aryls of 6 or 10 carbons all with optional substituents such as halo's, alkyls, so too other halogens can replace the chloros attached to the phosphorous. The reaction is typically carried out for from 10 to 30 minutes at low temperature (e.g., -70° C. to +10° C.) in an organic solvent such as pyridine, dioxan, tetrahydrofuran, acetonitrile, chloroform or the like, in the presence of an excess of the benzazole or optionally a suitable organic base, particularly an organic testing amine especially pyridine or a substituted pyridine such as collidine or lutidine. The in situ-generated dibenzazolide intermediate is generally used without isolation. It is firstly reacted with a 5' protected derivative to give a monobenzazolide, which is further reacted with a hydroxyl component HOR'. ##STR11## When HOR' is a 5' or 3' protected nucleotide either in solution or attached to a solid support, an internucleotide bond is generated without recourse to an external coupling reagent. Subsequent oxidation with an oxidizing agent as previously described gives the protected phosphate-nucleotide bond. The materials of this invention and their use in the two oligonucleotide synthesis techniques are further illustrated by the following Examples. These are presented to illustrate the invention and are not intended to limit the invention's scope. EXAMPLE I Use of Benzazoles as Activators in Phosphite Triester Synthesis and Comparison with 1-H Tetrazole N-Benzoylcytidine linked from the 3' hydroxyl group via a hemisuccinate bridge to aminopropyl-substituted HPLC-grade silica (Vydac) was used as the solid-phase support. Samples (100 mg each; 10 micromoles) were shaken in sealed test tubes in acetonitrile (1 ml) with each of the four 5'-dimethoxytrityl-deoxynucleoside-3'-dimethylaminophosphoramidites and either tetrazole (1 mmole) or benzotriazole (600 micromoles) to form the tetrazolide or benzotriazolide-phosphite active species, the latter being a compound of this invention. After thorough washing by repeated centrifugation and subsequent decanting, and oxidation with 0.01M iodine, the support was treated with 2.75% (w/v) trichloroacetic acid in methylene chloride (10 ml) for 5 minutes. Spectrophotometric assay of the dimethoxytrityl carbonium ion produced in the supernatant demonstrated that all couplings had proceeded to greater than 95% of theoretical yield. This test system was also used to show that 5-nitro- and 5-chloro-1,2,3-benzotriazole were as efficient amidite activators as tetrazole and unsubstituted benzotriazole. Additionally, using this method and a 30-fold excess of the corresponding G-amidite, it was shown that solutions activated with 1,2,3-benzotriazole gave efficient coupling up to 3 hours after their preparation at room temperature, whereas at the corresponding stage tetrazole-activated solutions gave 20% coupling yields. (See FIG. 1 where this is shown graphically.) EXAMPLE II Syntheses of Test Deoxynucleotide 5'GTTAAC3' The syntheses were performed using a BIOSEARCH Synthesis Automation Module (SAM 1) consisting of a microprocessor-controlled array of solenoid-actuated valves sampling reagents and solvents which were pumped through N-benzoyl-cytidine-substituted Vydac (150 mg) packed in a Whatman guard column. Mixing of amidites with benzotriazole wre performed in-line. The basic synthesis program used consisted of: (i) CH 3 CN (4 min, 4 ml/min); (ii) 2.75% (w/v) trichloroacetic acid in methylene chloride (5 min, 2.5 ml/min); (iii) CH 3 CN wash (2 min, 4 ml/min); (iv) DMT-nucleoside-phosphoramidite (10 equivalents) in acetonitrile (2.5 ml) and benzotriazole (60 equivalents) in acetonitrile (2.5 ml) sampled alternately at 0.5 second intervals at an overall flow rate of 0.5 ml/min for 10 minutes; (v) CH 3 CN wash (2 min, 4 ml/min); (vi) oxidation with 0.01M iodine in 40% (v/v) THF/water (3 min, 2.5 ml/min); (vii) CH 3 CN wash (2 min, 4 ml/min); and (viii) 0.5 M solution of a mixture of equivalent amounts of acetic anhydride and dimethylaminopyridine in THF (5 min, 1 ml/min). On completion of the five addition cycles a trichloroacetic acid treatment and a final wash step were performed. The support was unpacked and treated with concentrated ammonia for 1 day at room temperature. The supernatant was heated at 50° for one day and the ammonia evaporated. The residue was dissolved in water (5 ml) and a portion (0.25 ml) purified on a calibrated Whatman SAX column eluted at 2 ml/min with a gradient over 30 minutes from 0.03M to 0.3M potassium phosphate buffer (pH 6.1) containing 20% (v/v) acetonitrile. The main peak, eluting after 10 ml, was collected, desalted and shown by standard methods to be the desired homogeneous hexanucleotide isolated in 33% overall yield based on the original level of substitution of the Vydac support. In a second synthesis using tetrazole activation under similar conditions, a 25% yield of identical product was obtained. EXAMPLE III Preparation and Use of Methoxyphosphine Dibenzotriazolide A 0.5M solution of methoxyphosphine dibenzotriazolide was prepared by the addition at -20° of a solution of methyl-phosphorodichloridite (1.01 ml) in THF (9 ml) to a solution of benzotriazole (4.76 g, 50 mmoles) and pyridine (2 ml) made up to 10 ml with THF. After 15 minutes the solution was cooled to -60° and aliquots (0.9 equivalents) added to 0.18M solutions of the DMT-nucleosides in THF. Synthesis of GTTAAC was performed in a manner similar to that described in Example II. The isolated nucleotide (30% yield) was identical to that obtained in Example II.
Benzotriazoles are employed in phosphite triester oligonucleotide synthesis. The benzotriazoles also form phosphinedibenzazolides. Processes employing these reagents are also disclosed.
2
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a novel lactic acid-forming microorganism which exhibits excellent probiotic properties. The present invention also relates to the uses of the novel microorganism as a probiotic in food, beverage, animal feed and/or dietary supplement compositions, and as a medicament in controlling the colonization of undesirable intestinal microorganisms in the alimentary tract of a mammal. [0003] 2. Description of the Related Art [0004] The oral administration of large numbers of Lactobacillus rhamnosus , such as L . ( casei subsp.) rhamnosus GG (ATCC 53103), to a mammal has been found helpful to maintain or even enhance the healthy state of the mammal. It is believed that L. rhamnosus , when ingested, would colonize transiently on the intestinal mucosa, which results in inhibition of the growth of pathogenic bacteria and viruses (such as rotavirus), stabilization of gut permeability, and suppression of allergic reactions in food hypersensitivity. The bacterium is particularly effective in alleviating the symptoms of gastroenteric disorders, such as diarrhea, by eliciting nonspecific humoral immune response in hosts. [0005] L. rhamnosus , reported in 1989 as a new species derived from L. casei , shares similar phenotypes with two other members of the Lactobacillus genus, i.e., L. casei and L. paracasei . The three species can be further distinguished in terms of the differences in the genes encoding ribosomal RNAs. Approaches have been conducted based on this finding. For example, Rodtong et al. recognized the species-uniqueness of 16S rDNA and developed a ribotyping process to differentiate Lactobacillus strains (Rodtong, S. and Tannock, G. W. (1993) Applied and Environmental Microbiology 59: 3480-3484). Taking advantage of the convenience and effectiveness of polymerase chain reaction (PCR), Ward et al. and Alander et al., on the other hand, used different sets of primers to identify L. rhamnosus based on the sequence polymorphism of 16S rDNA (Ward, L. J. H., and Timmins, M. J. (1999) Letters in Applied Microbiology 29: 90-92; and Alander, M. et al., Applied and Environmental Microbiology 65: 351-354). [0006] According to the present invention, the inventor has identified a novel strain of L. rhamnosus (hereinafter referred to as strain Tcell-1) which is phylogenetically distinct from the published strains in the species and exhibits excellent probiotic properties. SUMMARY OF THE INVENTION [0007] It is a primary object of the present invention to provide a novel strain of L. rhamnosus . In the experiments performed in the invention, the inventor has characterized the phylogenetic distinction of the bacterial strain and demonstrated the desired probiotic properties thereof. [0008] Another object of the present invention is to provide a composition containing the bacterium strain according to the invention and a suitable excipient for the manufacture of foodstuffs, such as beverages, food, animal feed, and dietary supplements. [0009] Still another object of the present invention is to provide a pharmaceutical composition comprising the bacterium strain according to the invention, as well as to provide a method for the treatment or prophylaxis of gastroenteric disorders in a subject by administering such a composition to the subject. BRIEF DESCRIPTION OF THE DRAWINGS [0010] These and other features and advantages of this invention will become apparent from the following detailed description of this invention, with reference to the accompanying drawings, in which: [0011] FIGS. 1 A-C demonstrate the enteroscopic sampling from the upper jejunum and rectum tissues of a volunteer; [0012] FIG. 2 is a fermentation profile of the bacterial strain according to the present invention; [0013] FIG. 3A is a restriction map of the chromosomal DNA from the bacterial strain according to this invention; [0014] FIG. 3B shows the result of Southern analysis of FIG. 3A using E. coli MRE600 16S+23S rDNA as the probe; [0015] FIG. 4 shows the result of PCR analysis using the primers designed by Ward & Timmins, in which the DNA extracted from the bacterial strain according to the invention (lane 2) and water (lane 3; as a negative control) was subjected to PCR; [0016] FIG. 5 shows the result of PCR analysis using the primers designed by Alander et al., in which two sets of the species-specific primers, rham-rham2 (lanes 2-3) and rham-casei (lanes 4-5) were used in the PCR; and DETAILED DESCRIPTION OF THE INVENTION [0017] In accordance with the present invention, a strain of L. rhamnosus was isolated from the intestinal specimens donated by domestic volunteers. In a preliminary process, the microorganisms from the specimens were screened by a series of selective media, among which MRS agar medium and Rogosa SL agar medium exclusively allow the proliferation of Lactobacillus . The bacteria selected according to the above procedure were subjected to a four-step screening strategy for identifying L. rhamnosus: Step 1: fermentation patterning using an API 50CHL kit (BioM'erieux, Lyon, France); Step 2: ribotyping according to the method described in Rodtong et al. (supra), in which the total DNAs extracted from the microorganisms were treated with restriction enzymes EcoRI, BclI, BglII or HindIII and detected by the rDNA probe of Escherichia coli subsequent to Southern blotting, so that the restriction fragment fingerprints of the suspected microorganisms can be obtained and compared with those derived from the L. rhamnosus DNA; Step 3: PCR analysis according to the method described in Ward et al. (supra), in which a universal primer Y 2 (5′-CCCAC TGCTG CCTCC CGTAG GAGT-3′) and a species-specific primer rham (5′-TGCAT CTTGA TTTAA TTTTG-3′) were used in the reaction such that a major product of 290 bp will be produced when the chromosomal DNA of L. rhamnosus appears in the reaction mixture; and Step 4: PCR analysis according to the method described in Alander et al. (supra), in which a pair of species-specific primers, rham (as indicated in Step 3) and rham2 (5′-CCGTC AATTC CTTTG AGTTT-3′), will amplify a specific product of 863 bp in the presence of L. rhamnosus DNA. [0022] Accordingly, the bacterial strain according to this invention was identified to belong to the species L. rhamnosus . However, sequencing of the 863 bp product obtained in the Step 4 leads to a surprising finding that the bacterial strain according to this invention is phylogenetically distinct from all the published strains in the species L. rhamnosus. [0023] The bacterial strain thus identified was designated as “ Lactobacillus rhamnosus Tcell-1” and was deposited in the Culture Collection and Research Center (CCRC) of the Food Industry Research and Development Institute (FIRDI), Hsinchu, Taiwan, R.O.C. under the accession number CCRC 910145 (on Apr. 14, 2000). The bacterium was also deposited at the American Type Culture Center (ATCC) with accession number PTA-2406 on Aug. 22, 2000 under the terms of the Budapest Treaty on the International Recognition of the Deposit of Microorganism for the Purpose of Patent Procedure. [0024] Further studies concerning the probiotic properties of the strain Tcell-1 were also conducted. The results reveal that the bacterial strain according to the present invention can survive and grow well even in the stringent environment that an ingested bacterium would encounter in the gastrointestinal tracts, including extremely acidic pH and a high level of bile. The ability of L. rhamnosus Tcell-1 to resist certain antibiotics is apparently beneficial to administration of the bacterium to a subject who is required to take antibiotics. The superiority of the bacterial strain is further reinforced by its capability of inhibiting the growth of various enterobacteria. [0025] In view of the advantageous properties mentioned above, the bacterial strain according to the present invention is suitable for acting as a probiotic. According to the present invention, the strain Tcell-1 can be formulated into a broad variety of edible materials, including beverages, such as fluid milk, fermented milk, yogurts, fruit juices and sports drinks; food, such as ice cream, cheese and snacks; animal feed; dietary supplements; and infant formulas. Apparently, it is appreciable to those skilled in the art that the bacterial strain of this invention can be formulated in any suitable form by conventional methods for human or non-human animal's uptake. More preferably, the bacterial strain of this invention is formulated into the edible material in combination with other probiotic organisms, such as L. acidophilus, L. brevis, L. casei, L. plantarum, L. salivarius, L. bifidus, L. bulgaricus, L. causasicus, Streptococcus lactis and other strains of L. rhamnosus , or a combination thereof. In addition, L. rhamnosus Tcell-1 is preferably formulated together with lactosucrose, chitin, chitosan, manitol, yogurt powder or a combination thereof. [0026] L. rhamnosus Tcell-1 can also be used alone or with other active ingredients as a medicament in controlling the colonization of undesirable intestinal microorganisms in the alimentary tract of a mammal, to alleviate the conditions caused thereby. The composition can be formulated in solution, emulsion, powder, tablet, capsule or other adequate forms for oral administration. [0027] The following examples are given for the purpose of illustration only and are not intended to limit the scope of the invention. THE PREFERRED EMBODIMENTS OF THE INVENTION Example 1 Isolation of L. rhamnosus Tcell-1 [0028] Six healthy adults, aged from 25-45 and having no addiction to alcohol or smoking or chronic use of a drug, participated voluntarily in this experiment. None of them are vegetarians nor have abnormal dietary habit. The voluntary donors were subjected to fasting for 12 hours before enteroscopic sampling. Three biopsy specimens, each about 2 mm 2 in size, were picked up from different sites in the upper jejunum and rectum of each donor (FIGS. 1 A-C). The tissue specimens were then washed with physical saline (0.9% NaCl in distilled water) and stored in an ice-cold storage solution (0.9% NaCl, 0.1% Peptone, 0.1% Tween-80 and 0.02% Cysteine) for further analysis. The specimens were treated in an ultrasonic bath for 5 minutes and agitated vigorously for an additional 2 minutes. The obtained suspensions were undiluted or diluted in five- or ten-fold, and aliquots of the preparations were spread on the following solid media to obtain the profiles of enterobacteria contained therein (see also Johansson et al., Applied and Environmental Microbiology 59(1): 15-20). [0029] 1. Brain heart infusion agar (purchased from Difco) which is an enriched medium for aerobically or anaerobically culturing the entire population of enterobacteria at 37° C. for 3 days; [0030] 2. MRS agar (Difco) for anaerobically culturing Lactobacillus at 37° C. for 5 days; [0031] 3. Phenol ethanol agar (Difco) for aerobically or anaerobically culturing the Gram(+) bacteria at 37° C. for 3 days; [0032] 4. Azide blood agar (purchased from Oxoid) for aerobically culturing Streptococcus at 37° C. for 2 days; [0033] 5. Slanetz-Bartley agar (Oxoid) for anaerobically culturing Enterococcus at 37° C. for 2 days; [0034] 6. Violet red bile glucose agar (Oxoid) for culturing Enterobacteriaceae at 37° C. for 2 days; [0035] 7. Rogosa SL agar (Difco) for anaerobically culturing Lactobacillus at 37° C. for 5 days; and [0036] 8. Reinforced clostridial agar (Difco) for anaerobically culturing L. bifidus at 37° C. for 5 days. [0037] The results are shown in Table 1. TABLE 1 In the upper jejunum specimens: Name Medium † of the BHIA MRS PEA ABA SBA Donor 1x ‡ 5x 10x 1x 5x 10x 1x 5x 10x 1x 5x 10x 1x 5x 10x JF 3 0 0 0 0 0 0 0 0 1 0 0 0 0 0 JS M § 30 1 0 0 0 0 0 0 M 26 0 52 6 3 HK 0 0 0 0 0 0 0 0 0 0 0 6 0 0 0 V 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 B 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 RG 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Name Medium of the VRBGA RA RCA Donor 1x 5x 10x 1x 5x 10x 1x 5x 10x JF 0 0 0 0 0 0 M 0 0 JS 0 0 0 0 0 0 M 0 21 HK 0 0 0 0 0 0 0 0 0 V 0 0 0 0 0 0 0 0 0 B 0 0 0 0 0 0 0 0 0 RG 0 0 0 0 0 0 0 0 0 In the rectum specimens: Name Medium of the BHIA MRS PEA ABA SBA Donor 1x 5x 10x 1x 5x 10x 1x 5x 10x 1x 5x 10x 1x 5x 10x JF M 47 6 M 23 1 0 9 0 M 1 0 28 0 0 JS M 15 1 M 8 0 0 12 0 M 0 1 0 1 0 HK M 1 0 0 0 0 0 0 0 12 0 0 0 0 0 V M 0 0 0 0 0 0 0 0 30 0 0 0 0 0 B M 28 11 M 67 3 0 10 0 M 14 0 M 4 4 RG M 0 0 0 0 0 0 0 1 0 0 0 0 0 Name Medium of the VRBGA RA RCA Donor 1x 5x 10x 1x 5x 10x 1x 5x 10x JF M M M 0 0 0 M M M JS M 15 0 0 0 0 M M 0 HK 0 0 0 0 0 0 M 0 0 V 0 0 0 0 0 0 M 0 0 B M M M M 0 0 M M M RG 0 0 0 0 0 0 M 0 0 † The abbreviation BHIA represents brain heart agar; MRS represents MRS agar; PEA represents phenol ethanol agar; ABA represents azide blood agar; SBA represents Slanetz-Bartley agar; VRBGA represents violet red bile glucose agar; RA represents Rogosa SL agar; and RCA represents reinforced clostridial agar. ‡ 1X, 5X and 10X are the dilution folds of the bacterial suspensions. § The letter M indicates that the number of bacterial colonies on the medium plate is higher than 100. [0038] As shown in Table 1, the profiles of enterobacteria in the upper jejunum and rectum specimens are quite different. Example 2 Isolation of Lactobacillus [0039] From the MRS and Rogosa SL agar media in Example 1, 200 colonies were picked up randomly and transferred separately to fresh MRS agar media containing 1% CaCO 3 . After incubation, the colonies surrounded by clear zones were picked up, and each of them was transferred to a basal MRS agar medium supplemented with 1% rhamnose and 0.05% chlorophenol red. Finally, the yellowish colonies, presumably constituted by Lactobacillus , were picked up and further transferred to fresh MRS broth and incubated anaerobically at 37° C. for 2 days for further analysis. Example 3 Identification of L. rhamnosus Tcell-1 as a New Strain [heading-0040] (a) Fermentation Pattern [0041] The Lactobacillus broth prepared in Example 2 was precipitated, washed with distilled water and resuspended in a defined amount of distilled water. The bacterial suspensions thus obtained were investigated using an API 50CHL kit according to the protocol provided by the manufacturer. Upon this procedure, a strain of L. rhamnosus was identified based on the fermentation pattern specific to the species ( FIG. 2 ) and designated as L. rhamnosus Tcell-1. [0042] Total DNA of the strain Tcell-1 was prepared from a 3 ml culture growing in the mid-log phase according to a conventional method described by Sambrook et al. (Sambrook, J. et al., Molecular Cloning, A Laboratory Manual, 2 nd ed., Cold Spring Harbor Laboratory Press, 1989), and resuspended in 50 μl of TE buffer (1 mM EDTA, 10 mM Tris-HCl, pH 8.0). The DNA solution thus obtained was used in the following analyses for further investigation of the strain Tcell-1. [heading-0043] (b) Ribotyping Analysis [0044] 10 μl aliquots of the DNA were digested by restriction endonucleases, EcoRI, BclI, BglII and HindIII, respectively, for 3 hours. The digested products were loaded into the wells of a 0.8% agarose gel, and electrophoresis was carried out at 5 V/cm for 2 hours. The gel was then stained with ethidium bromide, and an image of the gel was obtained as shown in FIG. 3A . The DNAs on the gel were denatured and transferred to a nylon-based membrane (Hybond-N + , Amersham) as described by Sambrook et al. (supra). To prepare the probe for Southern analysis, 1 μl of E. coli MRE600 16S+23S rRNA (purchased from Boehringer Mannheim) was used as the template which was amplified via incorporation of [α- 32 P] dCTP by AMV reverse transcriptase (Bethesda Research Laboratories) and random primers. Blots were hybridized at 68° C. for 16-24 hours in a hybridization solution containing 5×SSC, 1× Denhardt's solution, 1% SDS and 100 mg/ml of Harpin sperm DNA, washed properly to enhance the signal-to-noise ratio, and subjected to autoradiography. As shown in FIG. 3B , the ribotype of the strain Tcell-1 was in perfect agreement with the typical pattern of L. rhamnosus as described by Rodtong et al. (supra). [heading-0045] (c) PCR Analysis Using the Ward & Timmins' Primers [0046] To an 1 ml eppendorf, 1 μl of Tcell-1 DNA harvested in Example 3(a), 1 μl of primer Y 2 , 1 μl of primer rham, 0.5 μl of DynaZymeII (Finnzymes Oy) and each dNTP (dATP, dTTP, dCTP and dGTP) at 100 μM were added. The reaction mixture was added with distilled water to a final volume of 50 μl and further overlaid with mineral oil. The reaction mixture was placed in a GeneAmp® PCR System 2400 thermocycler (Perkin Elmer) and thermocycled under the following conditions: Initial condition: 94° C. for 3 min. 45° C. for 45 sec. 72° C. for 1 min. Thermocycling: 94° C. for 45 sec. 45° C. for 45 sec. 72° C. for 1 min. Number of thermocycles: 30 Chain extension: 94° C. for 45 sec. 45° C. for 45 sec. 72° C. for 5 min. [0047] Following thermocycling, the amplified products were separated on a 0.2% agarose gel. The gel was stained with ethidium bromide, and a major amplicon of 290 bp was observed on the gel under a UV light source ( FIG. 4 ) [heading-0048] (d) PCR Analysis Using the Alander's Primers [0049] The PCR in Example 3 (c) was repeated except that the Ward & Timmins' primers were replaced with the rham and rham2 primers designed by Alander et al. (supra). The electrophoresis analysis on a 0.2% agarose gel revealed that the amplified products contain a major band of 863 bp ( FIG. 5 ), which, as described above, was reported to be a critical indicator to identify L. rhamnosus. [0050] The experiments conducted in Examples 3(a)-(d) conclude that the biochemical and genetic traits of the strain Tcell-1 matched with those considered belonging to species L. rhamnosus. [heading-0051] (e) Differentiation of Strain Tcell-1 from other L. rhamnosus Strains [0052] Using TOPO TA cloning™ kit (Invitrogen), the 863 bp product obtained in Example 3(d) was cloned into a pCR-TOPO™ vector according to the protocol provided by the manufacturer. The resultant plasmid was then introduced into TOP10 One Shot™ electrocompetent cells (Invitrogen) by electroporation. Following proliferation of the transformants in a selective medium, the plasmid was harvested and the 863 bp insert was sequenced. [0053] The sequence was used as a query sequence and searched against a nucleotide sequence database in the GenBank (http://www.ncbi.nlm.nih.gov:80/entrez/query.fcgi?CMD=search&DB=nucleotide). The sequence alignment shown in Table 2 suggests that the strain Tcell-1 is phylogenetically distinct from all the six L. rhamnosus strains available in the GenBank based on the 16S rDNA sequences. The Tcell-1 DNA sequence shown in Table 2, which is 776 bp in size, was designated as SEQ ID No.1. TABLE 2 symbol comparison table: genetiq.dat; gap penalty: 4 1       10        20        30        40        50 TCELL1  TATACACTGGTACCTCCCTAAGTGGGATACATTGAAACAATCTATCCGCATAATCAAGA            *** ***            *   *     * *    * *  *  * AF21761    TTGTACACACCGCCC.GTCACACCATGAGAGTTTGTAACA...CCCGAAGCCGGTG    *************** ************************   ************* E08782   CTTGTACACACCGCCC.GTCACACCATGAGAGTTTGTAACA...CCCGAAGCCGGTG    *   *   * *   * *  *  *     **       ***   * **** * AF18273 CCTTTCTAAGGAAACAGACTGAAAGTCTGACGGAAACCTGCACA...CACGAAACTTTGT                        *  * *** ****     ** A61362                  CTAAGGAAACAGACTGAAAGTCTGACG................                  *************************** U32966                  CTAAGGAAACAGACTGAAAGTCTGACG................                    ************************* AF12120                    AAGGAAACAGACTGAAAGTCTGACG................                    1       10        20 consens             A C  CC A GA ACAGAC GAAA TCT AC    C C  A 1       10        20        30        40        50        60         70        80        90       100       110 TCELL1 CCGCATGTCTTGCTAAGATGCGTAACTATCGCTTTGGATGACCCCGCGTATAGCTAGTTG  ** *       *     *  * * * *              **  *  * AF21761 GCGTAA......CCCTTTTAGGGAGCGA.............GCCGTCTAAGGTGGGACAA ******      ** ***  **                    *     * *  **   ** E08782 GCGTAA......CCTTTTAGGGAGCGAG.............CCGTCTAAGGTGGGACAAA                **        *                        * AF18273 TTAGTTTTGAGGGGATTACCCTCAAGCACCC.........TAGCGGGTGCGACTTTGTTC A61362 ............................................................. U32966 ............................................................. AF12120 ............................................................. consens         70        80        90       100       110       120         130       140       150       160       170 TCELL1 TAAGTAACGCTCACCAAGCAATGATGCTAGCCAACTAAGTTGATCGCCACATTGGACTAA     * * * * *    * **  * *    *  *  *       ** *    *   ** AF21761 ATGATTAGGGTGAAGTCGTAACAAGGTAGCCGTAGGAGAACCTGCGGCTGGATCACCTCC     *  **   *      ***************************************** E08782 TGATTAGGGTGAAGTCGT.AACAAGGTAGCCGTAGGAGAACCTGCGGCTGGATCACCTCC *    *   ** *              *    *   *   **     *     *   * AF18273 TTTGAAAACTGGATATCATTGTTGTAAATGTTTTAAATTGCCGAGAACACAGGCTATTTG A61362 ............................................................ U32966 ............................................................ AF12120 ............................................................ consens             A                       A          C         T         130       140       150       160       170       180           190       200       210       220       230 TCELL1 ACACGGCC.CAAACTCTACGGAGGCAGCAGTAGGAATCTTCCACAATGGACGCAAGTCTG    *      ****   ** **                   *  **        *  * AF21761 TTTCTAAG.GAAACAG.ACTGAAAGTCTGA...........CGGAAACCTGCACACACGA ******** ******* *************           ******************* E08782 TTTCTAAG.GAAACAG.ACTGAAAGTCTGA...........CGGAAACCTGCACACACGA * *        ** *  *   *    *                ** * * * **  ** * * AF18273 TATGAGTTTCTAATAATAGAAATTCGCAT............CGCATAACCGCTGACGCAA                                             * * * **  ** * * A61362 ...........................................GAAACCTGCACACACGA                                            ***************** U32966 ...........................................GAAACCTGCACACACGA                                            ***************** AF12120 ...........................................GAAACCTGCACACACGA                                               30        40 consens            AA    A   A                   C GAAACCTGCACACACGA        190       200       210       220       230       240          250       260       270       280       290 TCELL1 ATGGAGCAACGCCGCGTGACTGAAGAAGGCTTTCGGGGCGTAAAACTCTGTTGTTGGAGA *                    **  *            *       *         ** AF21761 AACTTTGTTTAGTTTTGAGGGGATTACCCTCAAGCACCCTAGCGGGTG.......CGACT ************************ **************** ******       ***** E08782 AACTTTGTTTAGTTTTGAGGGGATCACCCTCAAGCACCCTAACGGGTG.......CGACT   *  *      *         *   * * *            **          *** AF18273 GTCAGTACAGGTTAAGTTACAAAGGGCGCACGGTGGATGCCTTGGCACTAGGAGCCGATG   *  *      *         *   * * *            ** A61362 AACTTTGTTTAGTTTTGAGGGGATTACCCTCAAGCACCCTAGCGGGTG............ ************************************************ U32966 AACTTTGTTTAGTTTTGAGGGGATTACCCTCAAGCACCCTAGCGGGTG............ ************************************************ AF12120 AACTTTGTTTAGTTTTGAGGGGATTACCCTCAAGCACCCTAGCGGGTG............       50        60        70        80        90 consens AACTTTGTTTAGTTTTGAGGGGATTACCCTCAAGCACCCTAGCGGGTG        GA        250       260       270       280       290       300          310       320       330       340       350 TCELL1 AGAATGGTCGGCAGAGTAACTGTTGTCGGCGTGACGGTATCCAACCAGAAAGCCACGGCT                  *****                **      *     * *   * AF21761 TTGT.....TCTTTGAAAACTGGATATCATTGTTGTAAATGTTTTAAATTGCCGAGAACA ****     ************************  *** ********************* E08782 TTGT.....TCTTTGAAAACTGGATATCATTGTATTAATTGTTTTAAATTGCCGAGAACA   *      **   *    *     **   *   **   **      *   *  ** AF18273 AAGGACGGAACTAATACCGATATGCTTCGGGGAGCTATAAGTAAGCTTTGATCCGGAGAT                                   ** *             *    * A61362 ...............................CGACTTTGTTCTTTGAAAACTGGATATCA                                ***************************** U32966 ...............................CGACTTTGTTCTTTGAAAACTGGATATCA                                ***************************** AF12120 ...............................CGACTTTGTTCTTTGAAAACTGGATATCA                                       100       110 consens                     T           GACT T T CTTT AAAA TCGA A CA        310       320       330       340       350       360          370       380       390       400       410 TCELL1 AACTCAGTGCCAGCAGCCGCGGTAATACGTAGGTGGCAAGCGTTATCCGGATTTATTGGG  *     *               *  * AF21761 CAGCGTATTTGTATGAGTTTCTAATAA..............................TA *****   **        **     **                                * E08782 CAGCG.TATTTGTATGAGTTTCTGAAA..............................AA    **      * *      *    * AF18273 TTCCGAATGGGGGAACCCAGTACACATCAGTGTATT.....................GC ** A61362 TTGTTGTAA.................................................AT *********                                                 ** U32966 TTGTTGTAA.................................................AT *********                                                 ** AF12120 TTGTTGTAA.................................................AT                                                          130 consens TTGT  TA                                                  A        370       380       390       400       410       420          430       440       450       460       470 TCELL1 CGTAAAGCGAGCGCAGGCGGTTTTTTAACTCTGATGTGAAAGCCCTCGGCTTAACCGAGG    *     * ****                        ** * **      *  * AF21761 GAAATTCGCATCGCA.......................TAACCGCTGACGCAAGTC.... ***************                       ****************** E08782 GAAATTCGCATCGCA.......................TAACCGCTGACGCAAGTC....          *   **                       ** *   * AF18273 CTGCAAGTGAATACA.......................TAGCTTGTTGGCGGCAGACGCG  *   *        * A61362 GTTTTAAATTGCCGA................................................ *************** U32966 GTTTTAAATTGCCGA................................................ *************** AF12120 GTTTTAAATTGCCGA................................................        140 consens GTT TA   AGC CA                       A     T        430       440       450       460       470       480          490       500       510       520       530 TCELL1 AAGTGCATCGGAAACTGGGAAACTTGAGTACAGAAGAGGACAGTGGAACTCCATGTGTAG *    **    *       *      *     ** *          *    * AF21761 AGTACCAGGTAAGTTACAAAGGGCGCACGGTGGATGCCTTGGCACTAGGAGC.......C *****  * *******************************************       * E08782 AGTACAGGTTAAGTTACAAAGGGCGCACGGTGGATGCCTTGGCACTAGGAGC.......C  * *   *  *  *  **     **** *  *          * * *    *       * AF18273 GGGAACTGAAACATCTCAGTACCCGCAGGAAGAGAAAGAAAACTCGATTCCCATAGTAGC   ****  *      *             ** *  *  **  * * A61362 ..GAACACAGCGTATTTGTATGAGTTTCTAATAATAGAAATTCGCATC............   ********************************************** U32966 ..GAACACAGCGTATTTGTATGAGTTTCTAATAATAGAAATTCGCATC............   ********************************************** AF12120 ..GAACACAGCGTATTTGTATGAGTTTCTAATAATAGAAATTCGCATC............     150       160       170       180       190 consens GAACA AG   ATT G A G  T ACTAA AATA  AA  C C A    C        490       500       510       520       530       540          550       560       570       580       590 TCELL1 CGGTGAAATGCGTAGATATATGGAAGAACACCAGTGGCGAAGGCGGCTGTCTGGTCTGTA      *     * *   ***  **    *  * * *    *                  * AF21761 GATGAAGGACGGAACTAATACCGATATGCTTCGGGGAGCTATA................A *******************************************                * E08782 GATGAAGGACGGAACTAATACCGATATGCTTCGGGGAGCTATA................A *   **  ** *     *   ** * *       *   *** AF18273 GGCGAGCGAAGTGGGAAGAGCCCAAACCGAGAAGCTTGCTTCTCGGGGTTGTAGGACTGG              * *  * * *  **  *      * * A61362 .............GCATAACCGCTGACGCAAGTCAGTACAGG              ***************************** U32966 .............GCATAACCGCTGACGCAAGTCAGTACAGG              ***************************** AF12120 .............GCATAACCGCTGACGCAAGTCAGTACA                    200       210       218 consens              GCATAA CGCA ACGCA   G GT CA        550       560       570       580       590       600          610       620       630       640       650 TCELL1 ACTGACGCTGAGGCTCGAAAGCATGGGTAGCGAACAGGATTAGATACCCTGGTAGTCCAT      *  ***  *    *               *       *  **** *      ** AF21761 GTAAGCTTTGATCCGGAGATT...........TCCGAATGGGGGAACCCAGTA....CAC *********************           *********************    *** E08782 GTAAGCTTTGATCCGGAGATT...........TCCGAATGGGGGAACCCAGTA....CAC   *         **  ** *             *  * * *  *    * * *      * AF18273 ACATTGGAGTTACCAAAGTTCG..........ACGTAGTCGAAGTCAGCTGGAAAGCTGC A61362 U32966 AF12120 consens              C                                  C G        610       620       630       640       650       660          670       680       690       700       710 TCELL1 GCCGTAAACGATGAATGCTAGGTGTTGGAGGGTTTCCGCCCTTCAGTGCCGCACTAACGC   *          * ***  *    ** *    *  *                *  **** AF21761 ATCAGTG.....TATTGCCTGCAAGTGAATACATAGCTTGT......TGGCGGCAGACGC *******       *  *    **   *   *    *              * *    * E08782 ATCAGTGTGTTGCTTGTCAGTGAATACATAGCTGGCCGGCG......GCCAGACGCGGGG   **  *          *  ** * **  * * *                  * * AF18273 GCCATAGAAGGTGAAAGCCCTGTAAACGAAACGGCGGACTC....TCCGTCCAGGATCCT A61362 U32966 AF12120 consens   C              C        670       680       690       700       710       720          730       740       750       760       770   776 TCELL1 ATTAAGCATTCCGCCTGGGGAGTACGACCGCAAGGTTGAAACTCAAAGGAATTGACGG     * *                        **   *  ** AF21761 GGGGAACT......................GAAACATCTAAG      *                         *   *  ** E08782 AACTGAAA......................CATCTAAGTACCCGGA  * *                           *     * *     * AF18273 GAGTACGGCGGAACACGTGAAATTCCGTCGGAATCCGGGAGGACCATCT A61362 U32966 AF12120 consens                                A       A        730       740       750       760       770   778 Example 4 Characterization of L. rhamnosus Tcell-1 [heading-0054] (a) Tolerance of Acid [0055] MRS liquid media were prepared at pH 2, 3, 4, 5 and 6, respectively, and supplemented with 0.3% bile salt. To 1.5 ml of each medium, 10 6 Tcell-1 cells were inoculated and incubated anaerobically at 37° C. Samples were collected at 0 and 4 hours after the inoculation, and the populations of the microorganisms in each culture were assessed with reference to the optical density at 620 nm. The results are shown in Table 3. TABLE 3 Incubation OD 620 time pH2 pH3 pH4 pH5 pH6 0 hour 0.01 0.018 0.010 0.014 0.012 4 hour 0.01 0.018 0.016 0.025 0.030 [0056] As shown in Table 3, the growth rate of L. rhamnosus Tcell-1 remarkably reduced as the cultures were acidified to a pH at which the ingested substances would encounter in an animal stomach, i.e., a pH of below 3. Surprisingly, the cells incubated in such an acidic environment for 4 hours can still restore their normal growth if transferred to a fresh MRS medium at pH 6.0 (data not shown). The data indicate that L. rhamnosus Tcell-1 can tolerate the attack of gastric acid. [heading-0057] (b) Tolerance of Bile Salt [0058] Example 4(b) was repeated except that the MRS liquid media contained bile salts at concentrations of 0.1, 0.2, 0.3 and 0.4%, respectively, while the pH of the media was constantly set at 2.5. The results are shown in Table 4. TABLE 4 Incubation OD 620 time 0.1% 0.2% 0.3% 0.4% 0 hour 0.011 0.010 0.013 0.018 4 hour 0.028 0.025 0.023 0.032 [0059] From Table 4, it is demonstrated that the growth of L. rhamnosus Tcell-1 was sustained at a high level of bile. [heading-0060] (c) Resistance to Antibiotics [0061] 2-3 ml aliquots of a bacterial suspension from an overnight culture of L. rhamnosus Tcell-1 were spread on MRS agar media added with 10 μg/ml of kanamycin, vancomycin, chloramphenicol or ampicillin. After incubation, L. rhamnosus Tcell-1, while its growth was attenuated in the media containing chloramphenicol or ampicillin, was found to be tolerant of kanamycin and vancomycin. [heading-0062] (d) Inhibition of the Colonization of Other Bacteria [0063] 2-3 ml aliquots of a bacterial suspension from an overnight culture of L. rhamnosus Tcell-1 were spread on MRS agar media. Each of the plates was incubated at 30° C. for 22 hours, on which 7 ml of soft agar mixed with 100 μl suspension from one of the nine enterobacterial strains listed in Table 5 (purchased from the FIRDI) was poured. TABLE 5 Bacterium Medium Enterobacter aerogenes DIFCO 0001 Clostridium perfringens brain heart infusion (anaerobically cultured) Klebsiella pneumoniae DIFCO 0001 Yersinia enterocolitica brain heart infusion Listeria monocytogenes brain heart infusion Streptococcus mutans brain heart infusion Citrobacter freundii DIFCO 0001 Shigella dysenteriae DIFCO 0001 Yersinia ruckeri DIFCO 0001 [0064] The obtained cultures were incubated for an additional 48 hours at 37° C. and observed with bare eyes. Based on the presence of inhibition rings around the colonies of L. rhamnosus Tcell-1, the inventor found that the strain Tcell-1 can significantly suppress the growth of E. aerogenes, C. perfringens, L. monocytogenes, S. mutans and C. freundii . The results strongly suggest that L. rhamnosus Tcell-1 exhibits promising probiotic properties for controlling or inhibiting the colonization of the undesired bacteria in the bowel. Example 5 Probiotic Formulations Containing L. rhamnosus Tcell-1 [0065] L. rhamnosus Tcell-1 can be utilized in various forms of foodstuffs, two examples of which are described as follows: [heading-0066] Formula 1: [heading-0067] Ten Strains of Lactic Acid-Forming Bacteria: [none] L. acidophilus, L. brevis, L. casei, L. plantarum, L. salivarius, L. bifidus, L. bulgaricus, L. causasicus, Streptococcus lactis and L. rhamnosus Tcell-1; Excipients: lactosucrose oligo, manitol, chitin & chitosan, yogurt powder; Natural Condensates: alfalfa, barley and wheat grass juice powder, pure soya lecithin, carrot juice powder, phosphatidyl choline, Hawaiian Spirulina pacifica, apple pectin powder, phosphatidyl inositol CGF chlorella, non-dairy probiotic culture: rhamnosus, acidophilus in a base of FOS, peace river bee pollen powder, stevia, freeze-dried mango, black currant, dandelion root extract 4:1, beetroot extract, Siberian ginseng extract 0.4%, pacific kelp 4:1 extract, artichoke 4:1 extract 2%, soya extract, bilberry extract 5:1, pineapple extract, cranberry juice extract 18:1, rosehip extract 4:1, lycopene, Milk Thistle Phytosome™, Ginkgo Biloba Phytosome™ and Grape Seed Phytosome™; Other Ingredients: Vitamin C, calcium, magnesium, zinc. Formula 2: Nine Strains of Lactic Acid-Forming Bacteria: L. acidophilus, L. brevis, L. casei, L. plantarum, L. salivarius, L. bifidus, L. bulgaricus, L. causasicus and L. rhamnosus Tcell-1; Other Ingredients: calcium lactate, lactosucrose oligo, lactose, dextrose, powered milk, vegetable oil and small amounts of an emulsifier and natural seasonings [0080] The formulation is coated on peanut and raisin granules to make up a probiotic healthy dessert. [0081] With this invention thus explained, it is apparent that numerous modifications and variations can be made without departing from the scope and spirit of this invention. It is therefore intended that this invention be limited only as indicated by the appended claims.
A novel strain of Lactobacillus rhamnosus is disclosed, which is phylogenetically distinct from the published strains in the species and exhibits excellent probiotic properties. The medical and nutritional uses of the bacterial strain are also disclosed.
0
BACKGROUND OF THE INVENTION I. Field of the Invention The present invention relates generally to a femoral hip prosthesis and, more particularly, to a femoral component which can be stress tailored to the femur in which it is implanted. II. Description of the Prior Art Based on the precepts of Wolff's Law which states that bone tissue will remodel in direct relation to the stress applied to it, it is desirable to stress bone at an optimal level to minimize and control remodeling. Usually some degree of proximal femur bone remodeling accompanies total hip replacement. Due to mechanical stiffness, metallic implants typically stress protect the proximal bone to some extent. In patients with relatively large intramedullary canals which require a large diameter implant for optimal fit, stress protection may be particularly problemsome. In the most extreme case, the proximal femoral bone may resorb to a small fraction of its original mass, possible causing a loss of support of the implant or implant breakage. It is unfortunate that implant flexural stiffness increases at an exponential rate, typically at powers between two and four, depending upon implant geometry, relative to linear increases in implant dimension. Further aggravating the situation is the fact that there is little correlation between the size of the patient and the diameter of the intramedullary canal. That is, a small, relatively light person may have a femur with a large diameter canal and a much larger person may have a femur with a smaller diameter canal. Therefore, it is desirable to produce an implant, especially a large diameter implant, with greatly reduced stiffness in relation to its mass. This can be accomplished in several ways. For example the use of materials which are inherently less stiff, that is, possess a lower flexural modulus might be considered. Thus, the use of titanium alloy or a carbon fiber reinforced polymer composite in lieu of the stiffer cobalt-chrome alloy might be considered. An implant can also be hollowed out. This method is marginally effective, however, due to the fact that the centrally located material contributes little to the stiffness of the implant. For example if an implant with a round stem of 16 mm diameter is hollowed to a wall thickness of only 2 mm, the resulting decrease in flexural stiffness is only 32% while the decrease in mass is 56%. Interestingly, a 16 mm diameter stem is 6.5 times stiffer than the 10 mm diameter stem. Morscher and Dick reported on nine years of clinical experience with a so-called "isoelastic" shaft prosthesis manufactured using polyacetal resin to transmit forces from the pelvis through the femoral head and neck into the femur in their paper: "Cementless Fixation Of `Isoelastic` Hip Endoprostheses Manufactured From Plastic Materials", Clinical Orthopaedics, June, 1983, volume 176, pages 77-87. They stated: "The optimal fixation of an implant depends mainly on its design and material. The insertion of an artificial joint induces remodeling of the bony structures. If stability is not achieved, the implant sooner or later will loosen. The elasticity, and consequently the deformation, of an implant depend on the elastic modulus of the material and on the prosthetic design. By adjusting the physical characteristics of the foreign material to that of the bone tissue, as well as the design of the prosthesis to the femoral shaft, the entire system would have the same elasticity as a normal femur. A more elastic hip endoprosthesis also may act as a shock absorber during walking, particularly in the hell/strike and toe/off phases." They proceeded to explain that this was the concept of the "isoelastic" hip endoprosthesis manufactured by Robert Mathys and implanted in 1973. In this instance, the prosthesis was composed of polyacetal resin which has an elasticity modulus approaching that of bone tissue, good durability, and tenacity for highly stressed components in combination with good tissue tolerance. To achieve the acquired structural strength in the neck portion, the component was reinforced by a metallic core that was tapered toward the tip to increase the elasticity of the stem, thereby allowing the stem of the prosthesis to follow the deformation of the bone. In commenting on the design, the authors further stated: "Isoelasticity implies the optimum approximation of the physical characteristics of an implant to those of the bone. An ideal isoelasticity, however, can never be achieved, since bone is anisotropic and the alloplastic materials used for joint arthroplasty show isotropic properties. In addition, there is no adaptation of the structures to the forces acting on the hip, as in the case in viable bone. Moreover, the variety of individual forms and strengths of human bone can never be imitated by an artificial joint. Use of more elastic materials, however, should avoid the disadvantages of the rigid materials used to date." U.S. Pat. No. 4,287,617 to Tornier discloses a hip prosthesis with a femoral stem which provides a measure of the elasticity spoken of by Morscher and Dick. A transverse section of the Tornier stem is in the form of a substantially rectangular tube of which one of the small sides is virtually cut away so as to leave a very large slot. The C-shaped section thus obtained is said to exhibit excellent transverse elasticity which facilitates the positioning of the pin in the medullary cavity by insertion. Other stated advantages are that the pin is not as heavy as solid designs, and that the cavity encourages bone growth. SUMMARY OF THE INVENTION An alternate approach to the foregoing is the subject of this disclosure. Briefly stated, the medial side of the length of the implant is milled out to form a channel shaped stem cross section. The amount of material removed determines the resulting decrease in stiffness of the implant. The outside geometry remains substantially unchanged with the exception of the open channel on the medial side of the implant. Because of the reduction of the moment of inertia of the implant stem, it is more flexible. It also exhibits higher stem stresses upon loading of the implant. Therefore, a careful balance must be achieved between the amount of material removed from the stem and the expected stress levels expected by the particular size implant. The resulting longitudinal channel lies generally in the coronal plane when the stem is in the implanted condition. The depth of the channel is variable between the proximal and distal ends of the femoral implant so as to affect the moment of inertia at any given location along a length of the stem to thereby achieve an optimal stem flexibility. That is, the stem is so formed that at specified locations along its length, it substantially correlates to the flexibility of the femur itself. However, for at least two excellent reasons, it is desirable that when the channel is formed, the resultant dimension of the stem in the lateral/medial direction be no smaller than approximately 70% of the original dimension or of the dimension in the anterior/posterior plane assuming the cross sectional shape is round. Reasons supporting this desirable relationship include the fact that the stem may otherwise lose its fitting relationship in the intramedullary canal, which is substantially round in cross section. Furthermore, the greater the width of the canal, the sharper become the longitudinal edges of the stem which are produced adjacent the channel. These could undesirably cut into the bone, traumatizing the bone and causing pain as well as a high point loading of the bone, possibly causing it to be chiseled away. Indeed, to preclude these potential difficulties, it is preferable that the final dimension in the lateral/medial direction will be no less than 85% of the dimension in the anterior/posterior plane. The femoral stem exhibiting the qualities of the invention may be composed of any of the common materials generally employed for implants including titanium, titanium alloy, cobalt-chromium alloy, and composite materials. However, the use of ceramics and sintered powdered metal constructions may also be considered. The channel itself may be formed during a molding process or by mechanical or chemical milling procedures, or in any other suitable fashion. Also, according to the invention, it is considered that there would be a standard size range of stems, perhaps seven to ten different sizes varying in outer diameter, length, depth of the channel, the amount of the taper from the proximal to the distal ends of the stem. The closest sizes would be determined radiographically prior to surgery, although the final size decided upon for implanting could be finally chosen during surgery. Other and further features, objects, advantages, and benefits of the invention will become apparent from the following description taken in conjunction with the following drawings. It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory but are not to be restrictive of the invention. The accompanying drawings which are incorporated in and constitute a part of this invention, illustrate one of the embodiments of the invention and, together with the description, serve to explain the principles of the invention in general terms. Like numerals refer to like parts throughout the disclosure. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side elevation view, certain parts being cut away and shown in section, of a hip prosthesis, including a femoral component embodying the invention; FIG. 2 is a cross section view taken generally along line 2--2 in FIG. 1; FIG. 3 is a bar graph indicating relative stiffness of a series of stems of varying diameters for femoral components which are currently available commercially; FIG. 4 is a cross section view of the stem of a femoral component having a circular cross section and awaiting modification according to the invention; FIG. 5 is, in part, a schematic side elevation view, partly in section, of a femoral component embedded in a femur and, in part, a graph presenting the resultant microstrain exhibited by each of one standard and four experimental femoral components as they are subjected to stress; FIG. 6 is a bar chart which presents in a different manner the information presented in FIG. 5; and FIG. 7 is a graph illustrating the relative flexibility of the series of femoral componenets which were presented in FIGS. 5 and 6. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Turn now to the drawings, and initially to FIG. 1, which illustrates a hip prosthesis 20 which embodies the invention. As illustrated, a femoral component 22 is suitably implanted in the femur 24 and is cooperatively engaged with an acetabular component 26. The latter component is suitably implanted in the acetabulum 28 of the pelvis 30. In customary fashion, the femoral component 22 has a taper 32 at its extreme proximal end adapted to fittingly receive thereon a ball 34. In turn, the ball is rotatably engaged with a bearing 36 of the acetabular component 26 which may be supported in a metal cup 38 which is generally fixed to the pelvis 30. The femoral component 22 further includes a shoulder 40, with the taper 32 being joined to the shoulder via a neck 42. A stem 44 extends away from the shoulder 40 to a distal or tip end 46. In a customary manner, the stem 44 is received in the intramedullary canal 48 of the femur 24. The stem 44 is formed with a longitudinal channel 50 which lies generally in the coronal plane of the body of the person in whom the prosthesis is implanted. The depth of the channel 50 (see especially FIG. 2) is variable between the proximal and distal ends of the femoral component 22, its purpose being to affect the moment of inertia of the femoral component at any given location along the length of the stem 44 to thereby achieve an optimal stem flexibility. It was previously mentioned as being unfortunate that implant flexural stiffness increases at an exponential rate, typically at powers between two and four, depending upon implant geometry, relative to linear increases in implant dimension. Graphic proof of this statement is presented in FIG. 3 which is a bar graph indicating relative stiffness of a series of stems of varying diameters which are currently available for implanting. It is noteworthy that the 18 millimeter diameter stem exhibits 16 times the stiffness of the 9 millimeter diameter stem. The invention serves to avoid this exponential increase and limits the increase in stiffness to an approximately linear relationship with increasing stem diameter. It will be appreciated that femoral hip implants are subjected predominately to a bending mode of loading based on biomechanical analyses. This loading gives rise to the highest stem stresses according to the formula: S.sub.max =Mc/I where S max is the maximum stress at any location of interest along the stem; M is the bending moment imparted to the structure at the particular location of interest; c is the distance from the neutral axis to the location of interest; and I is the moment of inertia about an anterior-posterior axis, a geometrical consideration. If the maximum allowable stress based on material limitations is known and if the loading condition of the implant based on biomechanical analyses is known, one can then solve for the necessary moment of inertia via the rearrangement of the above equation, as follows: I=Mc/S.sub.max It has been mentioned as desirable to limit the width of the femoral component 22 in the region of the channel 50 to no less than 70% the dimension of a similarly shaped stem in that plane not formed with the channel. As previously mentioned, the reasons for this relationship include a desire to maintain the fit of the stem 44 within the intramedullary canal 48 as well as the prevention of sharp edges 52 which would be produced adjacent the channel in the event the channel is made excessively wide. This is most clearly seen in FIG. 4 which is representative of the stem 44 having a circular cross section and before it is formed with the channel 50. PG,13 Based on the general criterion as just mentioned of maintaining the lateral-medial width of the femoral component 22 to no less than 70% of the anterior-posterior dimension, in the event the stem 44 is of circular cross section, or 70% of the lateral-medial width of an unchanneled stem, one can determine the channel depth necessary to satisfy the geometrical considerations of the moment of inertia, I. In the instance of stem 44 of circular cross section (see FIG. 4), the moment of inertia is determined as follows: I=πr.sup.4 /4 where r equals the stem radius. Now, at each location along the length of the stem, the depth of the channel 50 to be formed can be determined. In the first instance, the desired channel width is determined which assures the lateral-medial dimension being no less than 70% of the original dimension. Thus, the channel width as represented by the reference numeral 54 (FIG. 4) is a known quantity. Furthermore, stiffness of the desired implant at any given location along its length is a known quantity. This is determined from clinical experience. Stiffness is proportional to the moment of inertia, I, and therefore increases in proportion to the fourth power of the diameter of the stem. However, according to the invention, this increase would be limited to a fraction of what it would be for a solid implant and this fractional increase is achieved by means of the channel 50. With the aid of FIG. 4, it should be clear that I.sub.implantw/channel =I.sub.circle -I.sub.channel Based on the foregoing, the magnitude of I implant and of I circle are known, requiring that I channel be determined. However, I channel is a function of the width and depth of the channel. It was previously stated that the channel width 54 is a known quantity, requiring a solution, now, of the only remaining unknown, that is, the depth of the channel as represented by the reference numeral 56. If the channel, viewing FIG. 4, is approximated, in cross sectional shape with being that of a rectangle, then: I.sub.channel =bh.sup.3 /12 where b is the channel width 54 and h is the channel depth 56. This latest equation can be rearranged in order to solve for the quantity h. Of course, it will be recognized that by reason of the fact that the moment of inertia I channel is proportional to the third power of channel depth 56, the channel depth is a very critical value indeed. Thus, I implant w/channel is determined for various channel depths used to satisfy the aforementioned equation, namely: S.sub.max =Mc/I In the course of proving the desirability of the invention, five similarly sized femoral implants of different design were tested. Both the implant material and geometry was modified in four of the five implants used. A standard 15 mm AML® femoral component (a product of DePuy Division of Boehringer Mannheim Corporation of Warsaw, IN) which was fabricated from Co-Cr-Mo alloy was used as the control. The four experimental devices were fabricated from Ti-6A1-4V and porous coated. The material was chosen since its elastic modulus is almost half that of the Co-Cr-Mo alloy. One of the experimental implants remained unmodified. The other three experimental implants were modified as follows: The distal half of one of the implants was produced with a slot in a coronal plane of the distal stem. The third implant was fabricated with a hollow stem. The hole ran axially through the length of the shaft. The fourth implant was manufactured with an increasingly deep channel extending from below the proximal medial aspect to the distal tip 46 and was generally configured in accordance with FIG. 1 herein. For purposes of the investigation being described, a polysulfone analog femur was developed based on the mass properties of several nominally sized cadavaric femora. The analog femur approximated the flexural stiffness of an average sized natural femur. As indicated in FIG. 5 which is a schematic illustration of each of the test implants 58 and an associated resulting microstrain graph, the implant 58 is shown inserted into its mating analog femur 60. Seven strain gauges, numbered 62-68, consecutively, are located as illustrated on the femur and the section properties of each strain gauge location were calculated for each implant as shown. After each implant was inserted into the analog femur, the latter, in turn, was mounted into a mechanical testing machine. Thereupon, the implant was loaded at the head and the femur was allowed to flex in an unrestricted fashion in a coronal plane using a hinge at the distal end of the femur. Strain gauges were checked for linearity at three load levels and each implant was loaded in an identical fashion to the three load levels. Gauge measurements for each gauge were recorded and converted to microstrain and the trends were perfectly consistent at each of the load levels. The conclusion was reached that the channeled implant was the most effective of the implants tested in increasing proximal femur strains, and that the channeled implant was particularly effective when applied to the lower modulus material, namely, the titanium alloy. A bar chart presenting the identical information provided in FIG. 5, but in different form is presented in FIG. 6. Further, it will be noted that FIG. 5 also illustrates the shape of each cross section taken at the respective locations of the strain gauges 63, 65; 66; and 64, 67. It also presents the section modulus at each of these cross sectional locations. As was previously explained, the primary thrust of the invention is to prevent stress shielding at the proximal end of the femur 24 and, toward this end, to impart more stress and more strain into the femur. This desired result has been achieved as is seen in FIG. 7 which is illustrative of the relative flexibility of the test implant 58 at three of the cross sectional locations presented in the FIG. 5 graph. Specifically, the magnitude of the resultant values as determined by the strain gauges 63, 65, and 67 clearly demonstrate the effectiveness of the invention according to which the increased flexibility of the channeled stem results in significant increases in strain being imparted to the proximal portion of the femur. While a preferred embodiment of the invention has been disclosed in detail, it should be understood by those skilled in the art that various other modifications may be made to the illustrated embodiment without departing from the scope of the invention as described in the specification and defined in the appended claims.
A controlled stiffness elongated implant for use in the hip or other appropriate body joint. In the instance of the hip, a ball member fixed to the femur is rotatably engaged with a cup-shaped socket member fixed to the acetabulum of the pelvic bone. The ball member is mounted on one end of a femoral component which has an elongated stem receivable in the intramedullary canal of the femur. The stem has a longitudinal channel therein which lies generally in the coronal plane when the stem is in the implanted condition. The thickness of the stem laterally of the channel is variable between the proximal and distal ends so as to affect the moment of inertia at any given location along the length of said stem to thereby achieve stem flexibility which substantially correlates to the flexibility of the bone.
0
CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of provisional application Ser. No. 60/495,955 filed Aug. 18, 2003. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [[0002]] This invention was made with government support under Contract No. F33615-00-D-5008 awarded by the United States Air Force. The government has certain rights in the invention. BACKGROUND OF THE INVENTION [0003] This invention relates generally to thermal control coatings, and more particularly to polyaryleneetherketone phosphine oxide compositions incorporating cycloaliphatic units for use as polymeric binders in thermal control coatings and a method of synthesizing such compositions. [0004] Spacecraft such as satellites and deep-space craft are exposed to a wide range of thermal conditions. The high intensity of direct solar radiation can potentially raise temperatures to dangerous levels. Thermal control of spacecraft is therefore important to reduce the absorption of solar radiation as well as dissipate internal heat to proper levels. Temperature control has currently been attained with the use of radiators having thermal control coatings on their surface. Such thermal control coatings typically comprise a potassium silicate binder pigmented with zinc oxide. This white coating exhibits a good initial diffuse reflectance for 380-1000 nm wavelength radiation and a moderate degradation in reflectance upon space environmental exposure. However, potassium silicate is a brittle inorganic glass with very poor flexibility and impact resistance, often showing failures due to film cracking. Another commercially available thermal control coating comprises a methyl silicone binder coating. However, while such a coating has good mechanical properties, it exhibits poor stability in space. [0005] More recently, the use of certain polymers has been proposed for use as coatings in space environments. The use of polymers in thermal control coatings is desirable as they would provide significant weight reduction, good mechanical strength, and exhibit thermal and thermooxidative stability. However, in order to be used as thermal control coatings in space environments, such polymers must also be resistant to degradation by ultraviolet radiation and atomic oxygen. [0006] Accordingly, there is a need in the art for polymers having improved resistance to UV radiation and atomic oxygen degradation which may be used in thermal control coatings. SUMMARY OF THE INVENTION [0007] The present invention meets that need by providing polyaryleneetherketone phosphine oxide compositions incorporating cycloaliphatic units which may be used as polymeric binders in thermal coatings for use in space applications. Methods for synthesizing such compositions are also provided. [0008] The polymeric binders synthesized in accordance with the present invention have improved UV transparency and enhanced UV reflectance, reducing transfer of energy into unwanted heat. The polymeric binders may be used in thermal control coatings for use in low-earth-orbit satellite systems for the delivery of mobile satellite services. [0009] According to one aspect of the present invention, a composition is provided having the formula where n is greater than 1.0. [0011] According to another aspect of the invention, a composition is provided having the formula where n is greater than 1.0. [0013] According to another aspect of the invention, a composition is provided having the formula where n is greater than 1.0. [0015] According to yet another aspect of the invention, a composition is provided having the formula where n is greater than 1.0. [0017] In another embodiment of the invention, a polymeric binder composition is provided comprising a composition containing an aryleneetherketone block, a triphenylphosphine oxide block, and a cycloaliphatic or cycloaliphatic cage-hydrocarbon structure. In one embodiment of the invention, the polymeric binder comprises a trans-1,4-cyclohexane-based polyaryleneetherketone triphenylphosphine oxide composition. In another embodiment, the polymeric binder comprises a 4,9-diamantane-based polyaryleneetherketone triphenylphosphine oxide composition. In yet another embodiment, the polymeric binder comprises a 1,3-adamantane-based polyaryleneetherketone triphenylphosphine oxide composition. In yet another embodiment, the polymeric binder comprises a 1,4-bicyclo(2.2.2)octane-based polyaryleneetherketone triphenylphosphine oxide composition. [0018] In another embodiment of the invention, a thermal control coating is provided containing a polymeric binder comprising a composition containing an aryleneetherketone block, a triphenylphosphine oxide block, and a cycloaliphatic or cycloaliphatic cage-hydrocarbon structure. The polymeric binder may comprise a trans-1,4-cyclohexane-based polyaryleneetherketone triphenylphosphine oxide composition, a 4,9-diamantane-based polyaryleneetherketone triphenylphosphine oxide composition, a 1,3-adamantane-based polyaryleneetherketone triphenylphosphine oxide composition, or a 1,4-bicyclo(2.2.2)octane-based polyaryleneetherketone triphenylphosphine oxide composition. [0019] The present invention also provides a method of synthesizing a polyaryleneetherketone triphenylphosphine oxide composition incorporating cycloaliphatic or cage hydrocarbon structural units which comprises displacing activated aromatic fluoro groups in 4,4′-difluorotriphenylphosphine oxide with bisphenoxide ions derived from a bis(4-hydroxybenzoyl) hydrocarbon monomer. [0020] Preferably, the monomer is selected from the group consisting of trans-1,4-bis(4-hydroxybenzoyl)cyclohexane; 4,9-bis(4-hydroxybenzoyl)diamantane, 1,3-bis(r-hydroxybenzoyl)adamantane, and 1,4-bis(4-hydroxybenzoyl)bicyclo(2.2.2)octane. [0021] In one embodiment, the synthetic route is wherein n is greater than 1.0. [0023] In another embodiment, the synthetic route is wherein n is greater than 1.0. [0025] In yet another embodiment, the synthetic route is where n is greater than 1.0. [0027] In yet another embodiment, the synthetic route is wherein n is greater than 1.0. [0029] Accordingly, it is a feature of the present invention to provide polyaryleneetherketone phosphine oxide compositions incorporating cycloaliphatic units for use as polymeric binders in thermal control coatings, and to a method for synthesizing the compositions. These, and other features and advantages of the present invention will become apparent from the following detailed description, the accompanying drawings, and the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS [0030] FIG. 1 is a graph illustrating the TGA and DSC analyses of cyclohexane-based polyaryleneetherketone triphenylphosphine oxide; and [0031] FIG. 2 is a graph illustrating the UV-visible spectra of dilute solutions of the polymers in chloroform. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0032] Reference will now be made in detail to the preferred embodiments of the invention. In the synthesis of the polymeric binder of the present invention, three fundamental structures are used: an aryleneetherketone block, which imparts flexibility, processability and thermooxidative stability; a high temperature stable triphenylphosphine oxide block, which provides fire retardance and resistance to atomic oxygen in low earth orbit space environments; and a cycloaliphatic or cycloaliphatic cage-hydrocarbon structure for enhanced UV/visible transparency. This corresponds to the requirement of an absorption well below the solar absorption radiation maximum of 450 nm, as well as a desired overall UV reflectance due to little or no UV/visible absorptance in the 300-800 nm spectral range. [0033] The present invention relates to the synthesis and characterization of a series of polyaryleneetherketone triphenylphosphine oxides incorporating a cycloaliphatic unit (trans-1,4-cyclohexylene) or cycloaliphatic cage-like structural units such as 1,3-adamantane-diyl and 4,9-diamantane-diyl moieties. [0034] The present invention also relates to the synthesis of monomers trans-1,4-bis(4-hydroxybenzoyl)cyclohexane; 4,9-bis(4-hydroxybenzoyl)diamantane, and 1,3-bis(4-hydroxybenzoyl)adamantane. The respective cycloaliphatic diacid chloride, derived by the reaction of the corresponding diacid with excess thionyl chloride, may be reacted under Friedel-Crafts acylation conditions with anisole to yield the bis(4-methoxybenzoyl) compound which may be converted to the corresponding bis(4-hydroxybenzoyl) monomer by pyridine hydrochloride-mediated dealkylation. [0035] The preparation of trans-1,4-bis(4-hydroxybenzoyl)cyclohexane is illustrated below. [0036] The structures of the 4,9-diamantane and 1,-3-adamantane-based monomers synthesized in accordance with the present invention are shown below. [0037] Polyaryleneetherketone triphenylphosphine oxides incorporating cycloaliphatic or cage hydrocarbon structural units may be synthesized by the nucleophilic displacement of the activated aromatic fluoro groups in 4,4′-difluorotriphenylphosphine oxide by the bisphenoxide ions derived from the bis(4-hydroxybenzoyl)hydrocarbon monomers described above. The polymerization reaction scheme for the preparation of the various polymers of the present invention is exemplified below for the trans-1,4-cyclohexane-based system. [0038] The methodology described in this invention can also be applied to the preparation of other monomeric compositions, such as 1,4-bis(4 -hydroxybenzoyl)bicyclo(2.2.2)octane, and the polyaryleneetherketone triphenylphosphine oxide composition derived from the monomer. The chemical structures of the monomer and polymer incorporating the bicycloaliphatic system are shown below. [0039] The polymers obtained from this system have a high molecular weight as evidenced by their dilute solution viscosities in N,N-dimethylacetamide, and polymer films cast from chloroform are transparent, flexible and very tough. These high performance polymers are also suitable for high temperature use as indicated by their Tgs, which range from 192° C. to 239° C. The polymers also exhibit high thermal and thermooxidative stability as they have decomposition temperatures ranging from 468° C. for the cyclohexane-based polymer to 515° C. for the diamantane-based polymer, in TGA in a helium atmosphere, and 469° C. to 493° C. in TGA in air. The solution properties and thermal and thermooxidative characteristics of these polymers are shown below in Table 1. TABLE 1 Intrinsic Viscosity T g TGA (dL/g, 30° C., Film (° C., DSC, T d (max, T d (max, Polymer DMAc)* Solubility Properties N 2 )** ° C., He)*** ° C., air)*** cyclohexane- 1.18 CH 2 Cl 2 , transparent, 215 468 469 based CHCl 3 , colorless, DMAc, flexible, DMF very tough diamantane- 0.43 CH 2 Cl 2, transparent, 239 515 493 based CHCl 3 , colorless, DMAc, flexible, DMF very tough adamantane- 0.38 CH 2 Cl 2 , transparent, 192 510 491 based CHCl 3 , colorless, DMAc, flexible, DMF very tough *Initial concentration: 0.25 g/dL **Rescan after heating to 250° C. ***Maximum weight loss for the temperature region [0040] In order that the invention may be more readily understood, reference is made to the following examples of compositions within the scope of the present invention, which examples are intended to be illustrative of the invention, but are not intended to be limiting in scope. EXAMPLE 1 [heading-0041] Materials [0042] 4,4′-Difluorotriphenylphosphine oxide was purchased from Daychem Laboratories, trans-1,4-cyclohexanedicarboxylic acid and 1,3-adamantanedicarboxylic acid were purchased from TCI America, and 4,9-diamantanedicarboxylic acid was acquired from Fluorochem, Inc. Thionyl chloride, anhydrous anisole, aluminum chloride, potassium carbonate, pyridine hydrochloride, N,N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) were purchased from Aldrich Co. All starting materials were used as received. All the synthesized monomers were characterized by melting point determination as well as by IR, NMR, mass spectral and elemental analyses. [heading-0043] Preparation of trans-1,4-bis(4-methoxybenzoyl)cyclohexane [0044] A diacid chloride of trans-1,4-cyclohexanedicarboxylic acid was prepared by refluxing in thionyl chloride (SOCl 2 ) until a clear solution was obtained and then isolated by evaporation in vacuo. The crude product (6.33 g) was added slowly to a solution of AlCl 3 (9.7 g, 2.4 eq) and anhydrous anisole (33 g, 10 eq), chilled with an ice bath. The ice bath was removed and the reaction mixture was stirred overnight at room temperature under a nitrogen atmosphere. The thick orange mixture that resulted was precipitated in 0.1 M HCl and allowed to stir. The product was filtered, stirred in MeOH to remove traces of anisole, and the resulting fine white powder was vacuum-dried at 98° C. for 24 hours. The crude product was recrystallized from toluene to yield 9.52 g (89%) of the compound. (Melting point was 217-218° C.) EXAMPLE 2 [heading-0045] Preparation of trans-1,4-bis(4-hydroxybenzoyl)cyclohexane monomer [0046] The dimethoxy compound from Example 1 (9.0 g) was reacted neat with pyridine hydrochloride (29.5 g, 10 eq) for 3 hours at 225° C. The reaction mixture was cooled to 100° C., precipitated in 0.1 M HCl, and the crude product was recrystallized from MeOH (melting point 260-263° C.). Yield of the off-white platelet-like crystals was 6.2 g, 75%. EXAMPLE 3 [heading-0047] Preparation of 4,9-bis(4-methoxybenzoyl)diamantane [0048] The diacid chloride of 4,9-diamantanedicarboxylic acid was obtained by the reaction of the diacid with excess thionyl chloride under reflux conditions until a clear solution resulted. The solid was isolated by evaporation of the solvent in vacuo. The crude product (6.6 g, 0.0211 mole) was added slowly to a solution of AlCl 3 (6.75 g) and anhydrous anisole (22.8 g), chilled with an ice bath. The reaction mixture was stirred overnight at room temperature under a nitrogen atmosphere. The product was precipitated by pouring into aqueous HCl (0.1M) stirred and filtered. This was further stirred in methanol to remove anisole, and the resulting solid was recrystallized from about 700 ml toluene and 100 ml THF to yield 6.9 g (72%, melting point 213-214° C.). EXAMPLE 4 [heading-0049] Preparation of 4.9-bis(4-hydroxybenzoyl)diamantane monomer [0050] In a round-bottomed flask fitted with a condenser, 4,9-bis(4-methoxybenzoyl)-diamantane (13.0 g, 0.0285 mole) was demethylated by heating with excess pyridine hydrochloride (33 g, 0.2850 mole) to 225° C. for three hours and the mixture was cooled. The product was precipitated in 40 ml concentrated HCl diluted with 200 ml water. The resulting solid was filtered and dried. The crude product was dissolved in tetrahydrofuran (THF) and hexane was added to the hot THF solution until the solution became slightly turbid. The solution was then slowly cooled to obtain crystals of the monomer (melting point 313-315° C.). Isolated yield was 7.0 g (57%). EXAMPLE 5 [heading-0051] Preparation of 1,3-bis(4-methoxybenzoyl)adamantane [0052] 1,3-Adamantanedicarboxylic acid (10.0 g) was converted into its diacid chloride by refluxing with 40 ml thionyl chloride. The acid chloride was obtained by evaporating off excess thionyl chloride. The diacid chloride (0.0438 mole, 11.45 g) was added slowly to a solution of AlCl 3 (14.03 g, 0.1052 mole) in anhydrous anisole (47.41 g, 0.4384 mole), chilled with an ice bath. The reaction mixture was stirred overnight at room temperature under a nitrogen atmosphere. The mixture was worked up in about 400 ml of 0.2 M HCl, filtered and stirred in methanol to precipitate a crude white solid. The solid was recrystallized from toluene to yield 11.6 grams of the crystals (66%, melting point 148-150° C.). EXAMPLE 6 [heading-0053] Preparation of 1,3-bis(4-hydroxybenzoyl)adamantane monomer [0054] 11.0 g (0.0272 mole) of 1,3-bis(4-methoxybenzoyl)adamantane was placed in a 250 ml round-bottomed flask fitted with a reflux condenser, along with 31.5 g (0.272 mole) of pyridine hydrochloride. The slurry was heated to 225° C. for three hours and the product was precipitated in 40 ml concentrated HCl diluted with 200 ml water. The solid was filtered and dried. The solid was recrystallized from ethyl acetate. The isolated yield of the purified compound was 6.6 g (64%, melting point 208-209° C.). EXAMPLE 7 [heading-0055] Preparation of trans-1,4-cyclohexane-based polyaryleneetherketone triphenylphosphine oxide [0056] A mixture of trans-1,4-bis(4-hydroxybenzoyl)cyclohexane (1.2975 g), 4,4′-difluorotriphenylphosphine oxide (1.2571 g) and potassium carbonate (1.33 g, 2.4 eq) was added to a 100 ml three-neck round bottom flask equipped with a mechanical stirrer, nitrogen inlet/outlet, and a Dean-Stark trap. N-methylpyrrolidone (NMP, 16 ml) and toluene (about 30 ml) were added and the reaction mixture was allowed to reflux with stirring for at least 4 hours. Water was azeotroped off, and the temperature was raised to maintain reflux. After an hour, some of the NMP was collected in the Dean-Stark trap to remove any residual water and achieve a final concentration of 15% by weight. The polymerization was run at reflux temperature (about 215° C.) in NMP for 3 hours and was cooled to about 100° C. before precipitation into 400 ml of 50/50 MeOH/acetic acid (HOAc). The stringy solid was shredded in a blender, soxhlet-extracted with water, and then dried in a drying pistol at 100° C. under vacuum for 24 hours. The yield of the off-white polymer was 2.47 g (98%). The intrinsic viscosity of the polymer, measured in N,N-dimethylacetamide (DMAc) at 30° C. for an initial concentration of 0.25 g/dl, was 1.18. The polymer was redissolved in chloroform and reprecipitated in heptane. After filtration, the polymer was again vacuum dried at 100° C., and then cast into transparent, tough and flexible films of various thicknesses from the chloroform solutions. EXAMPLE 8 [heading-0057] Preparation of 4,9-diamantane-based polyaryleneetherketone triphenylphosphine oxide [0058] A mixture of 4,9-bis(4-hydroxybenzoyl) diamantane (1.3212 g) and 4,4′-difluorotriphenylphosphine oxide (0.9689 g) and potassium carbonate (1.022 g, 2.4 equivalents) was added to a 100 mL three-neck round-bottom flask equipped with a mechanical stirrer, nitrogen inlet/outlet, and a Dean-Stark trap filled with dry toluene. DMAc (7.2 ml) and toluene (15 ml) were added and the reaction mixture was allowed to reflux with stirring for at least 4 hours. After removal of the azeotrope and excess toluene, the temperature was raised to 165° C. and the polymerization was allowed to proceed for 16 hours at the reflux temperature of DMAc. The calculated final polymer concentration was about 23 wt %. The polymer was precipitated in water, shredded in a blender and filtered. The solid was dried under vacuum for 24 hours at 100° C. 1.98 g of the polymer was isolated (92% yield). The intrinsic viscosity of the polymer, measured in DMAc at 30° C., was 0.27 dl/g for an initial polymer concentration of 0.0632 g/25 ml. EXAMPLE 9 [heading-0059] Preparation of 4,9-diamantane-based polyaryleneetherketone triphenylphosphine oxide [0060] A mixture of 4,9-bis(4-hydroxybenzoyl)diamantane (1.3212 g), 4,4′-difluorotriphenylphosphine oxide (0.9689 g) and potassium carbonate (1.022 g, 2.4 equivalents) was added to a 100 mL three-neck round-bottom flask equipped with a mechanical stirrer, nitrogen inlet/outlet, and a Dean-Stark trap filled with dry toluene. NMP (7.2 ml) and toluene (15 ml) were added and the reaction mixture was allowed to reflux with stirring for at least 4 hours. After removal of the azeotrope and excess toluene, the polymerization was run for 16 hours at 165° C. The calculated final polymer concentration was about 23 wt %. The polymer was precipitated in water, shredded in a blender, and filtered. The solid was dried under vacuum for 24 hours at 100° C. The isolated yield of the polymer was 2.05 g (95%). The intrinsic viscosity of the polymer, measured in DMAc at 30° C., was 0.31 dl/g for an initial polymer concentration of 0.0625 g/25 ml. EXAMPLE 10 [heading-0061] Preparation of 4,9-diamantane-based polyaryleneetherketone triphenylphosphine oxide [0062] A mixture of 4,9-bis(4-hydroxybenzoyl)diamantane (2.5711 g, 6×10 −3 mole) and 4,4′-difluorotriphenylphosphine oxide (1.8856 g, 6×10 −3 mole) and potassium carbonate (1.99 g, 14.4×10 −3 moles) was added to a 100 mL, three-neck round-bottom flask equipped with a mechanical stirrer, nitrogen inlet/outlet, and a Dean-Stark trap. N-methylpyrrolidone (NMP, 23 ml) and toluene (about 50 ml) were added and the reaction mixture was allowed to reflux with stirring for at least 4 hours. After removal of the azeotrope and excess toluene, the reaction temperature was raised to 215° C. and the polymerization was run for about 5 hours. The calculated final polymer concentration was about 15 wt %. The mixture was cooled to about 100° C. before precipitation into 500 ml of 50/50 MeOH/HOAc. The stringy solid was shredded in a blender, soxhlet-extracted with water, and then dried in a drying pistol at 100° C. under vauum for 24 hours. The isolated yield of the polymer was 3.89 g (about 93%). The intrinsic viscosity of the polymer, measured in N,N-dimethylacetamide (DMAc) at 30° C. for an initial concentration of 0.25 g/dl, was 0.43. The polymer was redissolved in chloroform, treated with activated charcoal for 15 minutes and filtered. The polymer was reprecipitated in heptane and the filtered polymer was dried in a drying pistol at 100° C. under vacuum overnight. Elemental analysis of the polymer sample for C 46 H 39 O 5 P showed the following, calculated: C, 78.61; H, 5.60; P, 4.41, O, 11.38; found: C, 77.23; H, 5.48; P, 4.10, 0, 11.10. 0.03 g of the polymer was redissolved in 10 ml chloroform and a transparent, tough, flexible polymer thin film (about 5μ thick) was cast from the filtered polymer solution by evaporating the solvent from a flat casting dish. FT-IR spectrum of the polymer thin film was corroborative of the expected chemical structure of the polymer. The spectral features are indicative of an aromatic C—H stretch at 3058 cm −1 , the distinct diamantane secondary and tertiary C—H stretching frequencies at 2918 and 2874 cm −1 , an intense carbonyl stretch at 1667 cm −1 due to the aryl adamantyl ketone group, a strong aromatic C═C at 1587 cm −1 , a very intense asymmetric —C—O—C— stretch at 1241 cm −1 due to the diphenylether linkage and a strong P═O stretch at 1170 cm −1 due to the arylphosphine oxide unit. EXAMPLE 11 [heading-0063] Preparation of 1,3-adamantane-based polyaryleneetherketone triphenylphosphine oxide [0064] A mixture of 1,3-bis(4-hydroxybenzoyl)adamantane (2.2589 g, 6×10 −3 mole) and 4,4′-difluorotriphenylphosphine oxide (1.8856 g, 6×10 −3 mole) and potassium carbonate (1.99 g, 14.4×10 −3 mole) was added to a 100 mL, three-neck round-bottom flask equipped with a mechanical stirrer, nitrogen inlet/outlet, and a Dean-Stark trap. N-methylpyrrolidone (NMP, 23 ml) and toluene (about 50 ml) were added and the reaction mixture was allowed to reflux with stirring for at least 4 hours. After removal of the azeotrope and excess toluene, the reaction temperature was raised to 215° C. and the polymerization was run for about 3.5 hours. The mixture was cooled to about 100° C. before precipitation into 500 ml of 50/50 MeOH/HOAc. The stringy solid was shredded in a blender, soxhlet-extracted with water, and then dried in a drying pistol at 100° C. under vacuum for 24 hours. The isolated yield of the polymer was 3.7 g (about 95%). The intrinsic viscosity of the polymer, measured in N,N-dimethylacetamide (DMAc) at 30° C. for an initial concentration of 0.25 g/dl, was 0.38. A transparent, tough, flexible polymer film was cast from the filtered polymer solution in chloroform by evaporating the solvent from a flat casting dish. [0065] In the foregoing specification, the invention has been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the skill of the present invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.
Polyaryleneetherketone triphenylphosphine oxide compositions incorporating cycloaliphatic units are provided which may be used as a polymeric binders in thermal control coatings for use in space environments. A method is also provided for synthesizing the polyaryleneetherketone triphenylphosphine oxide compositions. A method is also provided for synthesizing the monomeric compositions used to make the polyaryleneetherketone triphenylphosphine oxide compositions.
2
BACKGROUND OF THE INVENTION The present invention relates to polyester resins especially useful in vapor permeation curable coatings and more particularly to an improved synthesis route for making phenol-functional polyester resins. Vaper Permeation Cure (VPC) is a method for curing polyhydroxy polymers with a multi-isocyanate curing agent by exposure thereof to a vaporous tertiary amine catalyst at room temperature. VPC characteristics include extremely rapid cure times often ranging from as low as about 15 to 30 seconds and the ability to effect complete polymer cure at room temperature. Exemplary uses of VPC which take advantage of these properties include the curing of foundry binder compositions (U.S. Pat. No. 3,409,579) where the speed of cure is important and in coating heat-sensitive substrates such as thermoplastic substrates (commonly assigned application of Blegen, U.S. Ser. No. 216,323, filed on Dec. 15, 1980). Of course, other particular adaptations of VPC technology exist as will be readily apparent to those skilled in the art. A typical VPC coating composition comprises a polyol in admixture with a multi-isocyanate curing agent. Aromatic hydroxyl-functional resins are preferred for this purpose. For example, U.S. Pat. No. 3,789,044 proposes a VPC curable coating composition wherein the resin is made by reaction of hydroxybenzoic acid with an epoxy resin. The phenol-functional reaction product then is admixed with the multiisocyanate and cured by exposure to a vaporous tertiary amine catalyst. U.S. Pat. No. 3,836,491 proposes to cap a polyester resin with a hydroxybenzoic acid which phenol-functional polyester is admixed with a multi-isocyanate curing agent and cured according to VPC techniques. With regard to the former patent, unfortunately the residual aliphatic hydroxyl groups from the oxirane rings in the epoxy resin diminish the pot life of the coating composition and retard the time to ultimate cure which is experienced when VPC cure is practiced. As to the latter proposal, it has been discovered that hydroxybenzoic acids are subject to decarboxylation when used in an attempt to form the phenol-functional polyester at typical polyesterification temperatures of greater than about 200° C., e.g., typically about 235° C. Thus, as regards hydroxybenzoic acid-capped polymers for use in VPC coatings, there exists a need in the art for overcoming the foregoing shortcomings of prior proposals. BROAD STATEMENT OF THE INVENTION The present invention is an improvement in a method for making a phenolfunctional polyester polymer wherein a hydroxybenzoic acid, a dibasic acid, and a polyol are subjected to a polyesterification reaction under polyesterification conditions to make said polymer. Such improvement comprises conducting the reaction in two stages. The first stage comprises forming an ester-alcohol adduct between said hydroxybenzoic acid and a monoepoxide. The second stage then comprises conducting the polyesterification reaction with said adduct and the remaining ingredients used to make the polyester polymer. The resulting polyester polymer is substantially free of residual reactive aliphatic hydroxyl groups and is ideally suited to be admixed with a multi-isocyanate curing agent for compounding a VPC coating composition. An applied film of the resulting coating composition comprising said polyester polymer, said curing agent, and a solvent therefor is curable by exposure thereof to a vaporous tertiary amine catalyst. Advantages of the present invention include the ability to synthesize a phenol-functional polyester polymer utilizing a hydroxybenzoic acid without subjecting such hydroxybenzoic acid to conditions amenable to decarboxylation thereof. A further advantage is that the resulting polyester polymer is substantially free of residual reactive aliphatic hydroxyl groups for providing superior pot life of a coating composition comprising said polyester polymer, said curing agent, and a solvent therefor. These and other advantages will become readily apparent to those skilled in the art based upon the disclosure contained herein. DETAILED DESCRIPTION OF THE INVENTION Suitable hydroxybenzoic acids for purposes of the present invention include para-hydroxybenzoic acid, meta-hydroxybenzoic acid, and ortho-hydroxybenzoic acid (salicylic acid). Of course, the aromatic ring of the hydroxybenzoic acid optionally may be substituted, e.g. with alkyl substituents or aromatic substituents, though the unsubstituted forms are preferred. The ester-alcohol adduct is formed between the hydroxybenzoic acid and an epoxy compound. While it is preferred that a mono-epoxide be used in the adduct formation, such epoxy compound can be a polyepoxide providing that the molar ratio of carboxyl groups from the hydroxybenzoic acid to the oxirane groups of the polyepoxide is restricted to be about 1:1, though such ratio can be varied, especially to leave residual epoxide groups for achieving special effects. Also, while terminal oxirane groups in the epoxy compound are preferred, such oxirane groups can be in the backbone of the epoxy compound for formation of the ester-alcohol adduct of the present invention. Accordingly, then, the epoxy compound can be an epoxy monomer, oligomer, or polymer, as is necessary, desirable or convenient. Accordingly, suitable epoxy compounds include the internal epoxide compounds such as epoxidized fatty compounds, various alicyclic epoxides, and terminal epoxides such as glycidyl-containing compounds. Such epoxidized fatty compounds include epoxidized fatty oils, epoxidized fatty acid esters of monohydric alcohols, epoxidized fatty acid esters of polyhydric alcohols, epoxidized fatty nitriles, epoxidized fatty amides, epoxidized fatty amines, and epoxidized fatty alcohols. Suitable alicyclic epoxide and polyepoxide materials include dicyclopentadiene diepoxide, limonene diepoxide, and the like. Additional useful epoxides include, for example, vinyl cyclohexane dioxide, bis(3,4-epoxycyclohexl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane carboxylate, and 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane. Additionally, acrylic copolymers containing copolymerized glycidyl acrylate or meythacrylate units may be used. These acrylic copolymers can be prepared by the reaction of C 1 -C 18 , more preferably C 1 -C 12 , esters of alpha,beta-ethylenically unsaturated carboxylic acids with either glycidyl acrylate or methacrylate. These monomers can be copolymerized optionally in the presence of other copolymerizable monomers such as vinyl aromatic compounds, acrylonitrile or methacrylonitrile and the like. These acrylic copolymers are prepared by conventional techniques known in the art whereby the monomers are polymerized in solution or dispersed form in the presence of initiators such as benzoyl peroxide or azo-bis-isobutyronitrile, or the like. Such pre-formed glycidyl-containing materials, such as the glycidyl-containing acrylates; the alicyclic epoxides; bis-phenol-epichlorohydrin adducts; or the epoxidized fatty materials, are subsequently reacted with a hydroxybenzoic acid to form the adduct of the present invention. Representative preferred epoxy compounds suitable for use in formation of the adduct of the present invention include, for example, propylene oxide, ethylene oxide, and like oxides. Cardura E ester (a glycidyl ester of Versatic 911 acid which is a mixture of aliphatic, mostly tertiary, acids with 9-11 carbon atoms, Cardura and Versatic being trademarks of Shell Chemical Company, New York, N.Y.); mono-epoxides of C 8 -C 22 mono-olefins and especially α-olefins; and the like and even mixtures thereof may be used also. The adduct is formed by reacting the hydroxybenzoic acid and the epoxy compound, optionally in a solvent therefor, at a temperature ranging from about 90° to about 120° C. to initiate such reaction. Once the reaction is initiated, such reaction is exothermic, and the reaction temperature can rise to a temperature of about 150° to 175° C. usually without application of external heat. The reaction temperature then is maintained at about 150° to 170° C. (and always less than about 200° C.) until the reaction has been determined to be substantially complete. The resulting adduct then can be used in formation of polymers ideally suited for VPC systems though it must be understood that the adduct can find wide use in formation of polyester polymers (by reaction of the adduct with polyester-forming ingredients such as polyols, polycarboxylic acids, and their equivalents) suitable for use in a wide variety of applications including, for example, adhesives, molding compounds, coating compositions curable by heat or like techniques, and a wide variety of other uses. Of importance, though, is that the resulting ester-alcohol adduct now is stable for use in standard polyesterification reactions where temperatures exceeding 200° C. often are required. A wide variety of acids and alcohols desirably can be used in synthesizing polyesters for capping by the adduct disclosed herein. Suitable carboxylic acids for this purpose include, for example, C 2 -C 12 linear aliphatic dibasic acids; aromatic dicarboxylic acids such as isophthalic, orthophthalic, terephthalic acids and their anhydrides, where the formation of the anhydride is possible; trimellitic anhydride and the like; monocarboxylic acids such as, for example, benzoic acid, para-tertiary-butyl benzoic acid, 2-ethyl hexoic acid, fatty acids derived from naturally occurring oils such as tall oil, glyceride oils, and the like; and the like and mixtures thereof. Suitable alcohols usefulin polyester synthesis include, for example, glycols such as ethylene glycol, propylene glycol and the like; polyhydric alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, hexane diol, butane diol, glycerine, hexane triol, and the like in mixtures thereof; sterically hindered diols such as neopentyl glycol, cyclohexane dimethanol, and the like and mixtures thereof. Moreover, additional ingredients include propylene oxide, ethylene oxide, and the like; epoxide-containing materials such as epoxidized fatty compounds; acrylic copolymers containing copolymerized glycidyl acrylate and methacrylate units; and the like and mixtures thereof. It will be appreciated that the foregoing list is merely representative of the wide variety of ingredients (even containing different functionality for reaction with the adduct, e.g. isocyanate) which can be used in the present invention. Prime uses of the ester-alcohol adduct of the present invention include VPC coatings technology, as noted above. One preferred VPC coating's use is in the formation of a phenol-functional polymer which contains ethylenic unsaturation and wherein the phenol functionality is derived from the adduct of the present invention. Such unsaturated polymer is admixed with an ethylenically unsaturated diluent which is addition polymerizable with the ethylenic unsaturation of the polymer and optionally fugitive organic solvent. Such ingredients are admixed with a multi-isocyanate curing agent and can be cured by exposure to a vaporous tertiary amine catalyst wherein additional catalysts, e.g., peroxides, in the composition catalyze the addition polymerization reaction. Additionally, the adduct may be useful in forming a phenol-functional ethylenically unsaturated polymer which is cured with the multi-isocyanate curing agent in the presence of a vaporous tertiary amine, wherein the ethylenic unsaturation in the polymer is self-cross-linking. Further, the adduct may be useful in forming phenol-functional polymers which in admixture with multi-isocyanate curing agents dispersed in a fugitive organic solvent or an aqueous solvent have been determined to be extremely valuable in coating surface-porous substrates, as disclosed in commonly assigned application of Blegen et al., U.S. Ser. No. 270,896, filed on June 5, 1981 the disclosure of which is expressly incorporated herein by reference. Such coatings system solves a problem which plagues this commerical art in that conventional heat-cured coatings suffer from extreme surface imperfections which trap air and/or solvent in such porosity of the coated substrate. Heat curing of the coating causes these entrapped components to be expelled during such heat-curing operations, thus causing a coated surface replete in pits and other surface imperfections. The rapid room temperature cure achieved via VPC techniques produces a coating which does not suffer from such pinholing surface imperfections. Additionally, such disclosure additionally notes that adhesion, for example, can be improved by the addition of inert fillers to the coating composition. Yet another use for the adduct of the present invention is in the formation of VPC polyester coating compositions specially formulated for flexible substrates as disclosed by Blegen in commonly assigned U.S. Ser. No. 216,323 filed on Dec. 15, 1980, the disclosure of which is expressly incorporated herein by reference. Such disclosure provides a particularly adapted polyester resin which in combination with the multi-isocyanate curing agent and a unique mar-resisting agent of an organic compound physically incompatible in the coating composition and having an effective chain length of at least about 12 carbon atoms, provides an unusually mar-resistant and flexible coating ideally intended for flexible substrates such as flexible vinyl substrates. With appropriate modification, the adduct of the present invention also can be useful in forming coating compositions as disclosed in U.S. Pat. Nos. 3,789,044, 3,822,226, and 3,836,491. Such patents disclose vapor permeation curable coating compositions wherein the phenol functionality is derived from a hydroxybenzoic acid. Thus, the basic resins disclosed therein are hydroxy-functional prior to theaddition of the hydroxybenzoic capping agent. Accordingly, such resins only need be rendered carboxyl-functional either by separate addition of a dicarboxylic acid or the like to the resin mix or increasing the proportion of such acid in the mix in order to provide a carboxyl-functional resin suitable for capping with the adduct of the present invention. Implementation of this clearly is readily apparent to those skilled in this art. A variety of additional uses can be contemplated for the adduct of the present invention as those skilled in this art will fully appreciate. Of importance in resin design in the present invention is that the phenol-functional compound be substantially free of reactive aliphatic hydroxyl groups. Aliphatic hydroxyl groups diminish the pot life of the coating composition as well as are slower to cure with the isocyanate curing agent in the presence of the catalyst. Thus, any aliphatic hydroxyl groups on the phenol-functional compound should be sufficiently shielded (sterically hindered) so that they are substantially unreactive or non-participatory in the isocyanate curing reaction. Multi-isocyanate cross-linking agents cross link with the aromatic hydroxyl groups of the resulting adduct-capped polymer under the influence of a vaporous tertiary amine to form urethane linkages and to cure the coating. Aromatic isocyanates are necessary in order to obtain the desired rapid reaction in the presence of the vaporous tertiary amine catalysts at room temperature. For high performance coatings, initial color as well as the discoloration due to sunlight can be minimized by including at least a moderate level of aliphatic isocyanate content in the curing agent. Of course, polymeric isocyanates are employed in order to reduce toxic vapors of isocyanate monomers. Further, alcohol-modified and other modified isocyanate compositions find utility in the invention. Multi-isocynates preferably will have from about 2-4 isocyanate groups for use in the coating composition of the present invention. Suitable multi-isocyanates for use in the present invention include, for example, hexamethylene diisocyanate, 4,4'-toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethyl polyphenyl isocyanate (Polymeric MDI or PAPI), m- and p- phenylene diisocyanates, bitolylene diisocyanate, triphenylmethane triisocyanate, tris-(4-isocyanatophenyl) thiophosphate, cyclohexane diisocyanate (CHDI), bis-(isocyanatomethyl) cyclohexane (H 6 XDI), dicyclohexylmethane diisocyanate (H 12 MDI), trimethylhexane diisocyanate, dimer acid diisocyanate (DDI), dicyclohexylmethane diisocyanate, and dimethyl derivatives thereof, trimethyl hexamethylene diisocyanate, lysine diisocyanate and its methyl ester, isophorone diisocyanate, methyl cyclohexane diisocyanate, 1,5-napthalene diisocyanate, triphenyl methane triisocyanate, xylylene and xylene diisocyanate and methyl derivatives thereof, polymethylene polyphenyl isocyanates, chlorophenylene-2,4-diisocyanate, and the like and mixtures thereof. Aromatic and aliphatic poly-isocyanate dimers, trimers, oligomers, polymers (including biuret and isocyanurate derivatives), and isocyanate functional prepolymers often are available as preformed packages and such packages are suitable for use in the present invention also. The ratio of aromatic hydroxyl equivalents from the phenol-funtional compound to the isocyanate equivalents of the multi-isocyanate cross-linking agent should be greater than 1:1 and can range on up to about 1:2. The precise intended application of the coating composition often will dictate this ratio or isocyanate index. At high cross-linking densities or isocyanate equivalents, harder but relatively inflexible films are produced while at lower cross-linking densities or isocyanate equivalents flexibility of the films increases. Optimizing the particular property or combination of properties desired can be determined as those skilled in this art will appreciate. Usually a solvent or vehicle for the coating composition will be required and advantageously such solvent is a volatile organic solvent. Typical solvents include, for example, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethylene glycol monoethyl ether acetate, xylene, toluene, and the like, and often mixtures thereof. The proportion of solvent, and hence the non-volatile solids content of the coating composition, depends upon factors including method of application, desired application viscosity, and the like factors. A variety of additives can be included in the coating composition. The coating composition can contain opacifying pigments and inert extenders such as, for example, titanium dioxide, zinc oxide, clays such as kaolinite clays, silica, talc, and the like. Additionally, the coating composition can contain corrosion inhibiting pigments, plasticizers, flow leveling agents, surfactants, tinctorial pigments, and a wide variety of conventional coating additives. The finally compounded coating composition (phenol-functional resin, curing agent, solvent, and optional additives) possesses an excellent pot life of at least 4 hours in an open pot and often on up to 8-18 hours or longer. The coating composition of the present invention can be cured in the presence of a tertiary amine such as, for example, triethyl amine, dimethyl ethyl amine, cyclohexyl dimethyl amine, methyl diethyl amine, and the like, by exposure thereto for times ranging from as short as 5 seconds on up to 30 seconds or longer (e.g. about 2 minutes). The coating composition thus cured may be immediately handled without fear of deleterious tackiness or blocking of the cured film. In practicing the present invention, the coating composition is applied to the substrate by direct roll coat or curtain coating with or without knife, reverse roller coat, atomized application, or like conventional technique. Use of a two-head spray equipment is unnecesary since the coating composition of the present invention possesses such an excellent pot life. After the film is applied to the substrate, the coated substrate is passed through a zone or region which contains the vaporous tertiary amine. Representative vapor curing chambers for vapor curing the coating include those shown in U.S. Pat. Nos. 3,851,402 and 3,931,684, the disclosures of which are expressly incorporated herein by reference. The vaporous tertiary amine often is admixed with a carrier gas, such as an inert gas like nitrogen or carbon dioxide, in order to facilitate its dispersion in the curing chamber as well as for minimizing the chance of explosion. The saturated atmosphere in the curing chamber normally will contain the vaporous tertiary amine in a proportion of between about 2% and 12% with catalyst concentrations somewhere in the range of 4-8% being preferred. Room temperature may be maintained during the entire sequence of operations from coating, to curing of the coated substrate. An advantage of room temperature curing of the coating is that application to thermoplastic subtrates which are sensitive to heat can be practiced. In this regard, substrates suitable for being coated by the coating composition of the present invention includes, for example, metal, thermoplastic, hardboard or fiberboard, and the like. The following examples show how the present invention can be practiced but should not be construed as limiting. In this application, all units are in the metric system unless otherwise expressly indicated. Also, all references cited herein are expressly incorporated herein by reference. EXAMPLE 1 The adduct was formed from para-hydroxybenzoic acid and Cardura E epoxy-ester (a glycidyl ester of Versatic 911 acid; Versatic 911 acid is a mixture of aliphatic, mostly tertiary, acids with 9-11 carbon atoms; Shell Chemical Company, New York, N.Y.). These ingredients (1:1 molar ratio) were heated in a reaction vessel to about 115° C. at which time an exothermic reaction increased the reaction temperature to 180° C. in about 2 minutes. The reaction mixture then cleared. Within one hour following the exotherm, the acid value of the reaction mixture dropped to 32. The reaction was maintained until the acid number of the resulting ester-alcohol adduct was less than 10. EXAMPLE 2 In order to demonstrate the degradation of hydroxybenzoic acid when directly reacted with a polyol for formation of a polyester, one mole of glycerine was reacted with two moles of para-hydroxybenzoic acid. The reaction mixture was heated for a period of one week at gradually increasing temperatures ranging from 170° C. to 225° C. After seven days of reaction, the acid value of the reaction mixture had dropped to 52.2. The temperature of the reaction mixture then was raised gradually to 235° C. in the presence of azeotroping solvents added to the reaction mixture; however, the reaction mass gelled. These results demonstrate that direct reaction of hydroxybenzoic acid with a polyol for synthesis of a polyester is impractical since degradation of the hydroxybenzoic acid is prevalent. Based upon the results reported in Example 1 and in the remaining examples, it is clear that formation of the epoxy-ester adduct does permit the hydroxybenzoic acid to be incorporated successfully into a polyester. EXAMPLE 3 Two different reaction schemes were developed for the reaction of the epoxide with the hydroxybenzoic acid for formation of the ester-alcohol adduct, depending on whether the epoxide was a liquid or a gas at the reaction temperature (ca. 160° C.) Both methods result in the substantially complete conversion of the hydroxybenzoic acid into the desired ester-alcohol adduct which is formed prior to addition of other ingredients for forming a polyester. The reaction scheme for formation of the adduct from an epoxide which is liquid at reaction temperatures can be illustrated by the following reaction. Two moles of salicylic acid were reacted with two moles of Cardura E epoxide according to the reaction scheme set forth in Example 1. The resulting adduct then was reacted with maleic anhydride at 210° C. reaction temperature to produce a difunctional polyester containing unsaturation in the backbone. This polyester was a moderate viscosity material at room temperature with a hydroxyl number of 146 and an acid value of 7. The reaction scheme for formation of the adduct from an epoxide which is a gas at reaction temperature can be illustrated by the following reaction. Two moles of salicylic acid were reacted with two moles of propylene oxide by first melting the salicyclic acid in a reaction vessel and maintaining the molten acid at its melting point of about 160°-165° C. The propylene oxide then was added to the molten acid dropwise. Unreacted vaporized propylene oxide was returned to he reaction vessel by use of a reflux condenser which was attached to such vessel. When the acid value of the reaction mixture was determined to be less than 5, the reaction vessel was cooled and one mole of maleic anhydride added thereto. After flushing the headspace of the reaction vessel with nitrogen gas, the reaction vessel was heated to 210° C. and held at this temperature until the acid value of the resulting resin was determined to be under 10. The resulting resin was vacuum stripped and cooled to room temperature. This polyester was determined to have a hydroxyl number of 168 and an acid value of 5.6. In neither of the adduct formation reactions detailed above nor in the subsequent polyester formation therefrom was any degradation of the hydroxybenzoic acid apparent. Again, the novelty of the adduct and its use in formation of polyol-polyesters is demonstrated. EXAMPLE 4 Several polyol (polyester) polymers were prepared from the ester-alcohol adduct of this invention. The adduct was formed according to one of the reaction schemes set forth in Example 3. ______________________________________POLYOL 3511-160Reactant Mole Ratio______________________________________p-Hydroxybenzoic Acid 2.0Cardura E epoxy 2.0Neopentyl Glycol 2.0Adipic Acid 2.0Isophthalic Acid 1.0______________________________________ Hydroxyl Value = 80 Acid Value = 4.5 (80% by weight of the polyol in Cellosolve acetate solvent) POLYOL 3511-181BReactant* Mole Ratio______________________________________Salicylic Acid 2.0Cardura E ester 1.0Propylene Oxide 1.0Adipic Acid 2.0Neopentyl Glycol 2.0Isophthalic Acid 1.0______________________________________ Hydroxy Value = 83 (no solvent) Acid Value = 9.5 *The salicylic acidpropylene oxide adduct (preformed at a 1:1 molar ratio was charged to the reaction followed by the salicylic acidCardura E epoxy adduct (preformed at a 1:1 molar ratio) and the other reactants. POLYOL 3511-183Reactant* Mole Ratio______________________________________Salicylic Acid 2.0Propylene Oxide 1.0Cardura E ester 1.0Adipic Acid 2.0Neopentyl Glycol 1.0Isophthalic Acid 1.03,4-bis(p-hydroxyphenyl)-3,4-hexanediol 1.0______________________________________ Hydroxy Value = 110 Acid Value = 27.2 (no solvent) *Prepared in the manner of Polyol 3511181B. POLYOL 3895-27Reactant Mole Ratio______________________________________Salicylic Acid 2.0Propylene Oxide 2.0Fumaric Acid 1.0______________________________________ Hydroxy Value = 187 Acid Value = 17 (no solvent) POLYOL 3895-29Reactant Mole Ratio______________________________________Salicyclic Acid 2.0Ethylene Oxide 2.0Fumaric Acid 1.0______________________________________ Hydroxyl Value = 147 Acid Value = 18.1 (no solvent) POLYOL 3895-59Reactant Mole Ratio______________________________________Salicylic Acid 2.0Cardura E ester 2.0Fumaric Acid 1.0Propylene Glycol 6.1Adipic Acid 6.0______________________________________ Hydroxy Value = 41.4 Acid Value = 10.96 (no solvent) In none of the above reactions was any degradation of the hydroxybenzoic acid evident. EXAMPLE 5 Three of the polyols of Example 4 were compounded into coatings formulations in order to establish vaporous tertiary amine catalyzed curability of such polyols. The formulations are given below: ______________________________________COATING (gms)Ingredient 3511-160 3511-181B 3511-182.sup.(3)______________________________________Polyol 70.1 61.0 51.0Curing Agent.sup.(1) 40.2 40.2 40.2Cellosolve Acetate.sup.(2) 45.0 30.0 35.0______________________________________ .sup.(1) Mixture of Mondur HC isocyanate and Desmodur L2291A isocyanate (160:26 parts by weight ratio respectively); Mondur HC isocyanate is the tetrafunctional reaction product of hexamethylene diisocyanate and toluen diisocyanate (11.5% NCO content, equivalent weight of 365, 60% solids in Cellosolve acetate/xylene), Mobay Chemical Company, Pittsburgh, Pa. Desmodur L2291A isocyanate is an aliphatic polyfunctional isocyanate of the hexamethylene diisocyanate biuret type, Mobay Chemical Company, Pittsburgh, Pa. .sup.(2) Cellosolve acetate (urethane grade) is ethylene glycol monoethyl ether acetate, Union Carbide Corporation, New York, New York. .sup.(3) Polyol 3511183 was cut to 90% by weight in Cellosolve acetate before incorporation in the coating. The coating compositions were coated on glass plates with a Meyer bar to give a 0.1-0.5 mil dry film and cured by exposure to vaporous triethylamine catalyst carried by N 2 or CO 2 carrier gas (about 7% catalyst by volume) in a gas curing chamber. Viscosity measurements of the coating compositions were recorded as well as results of survey performance tests. __________________________________________________________________________ Cure SwardViscosity (cps) Time Hardness.sup.(1) MEK Rub.sup.(2)Coating Initial 4 hr. 24 hr. (sec) RT.sup.(3) HT.sup.(4) RT HT__________________________________________________________________________3511-160 119 150 12 190 90 34 36 27 733511-181B 220 271.5 450 120.sup.+ 22 10 10 73511-183 148 -- 197.5 120.sup.+ 38 46 13 23__________________________________________________________________________ .sup.(1) Plate glass is defined as 100 for Sward Hardness. .sup.(2) Methyl ethyl ketone (MEK) wetted rag rubbed over one area of cured film with moderate thumb pressure until glass substrate is visible. .sup.(3) RT is room temperature. .sup.(4) HT: Samples held at 160° C. for 5 minutes after vaporous amine catalyst exposure, then allowed to cool for 3 days at room temperature prior to testing. Several observations can be made from the above-tabulated data. The stability of the coating compositions is established by the viscosity measurements reported. Several factors impact the marginal performance of the coating samples. First, the polymers were synthesized in a survey test evaluation program intended to establish operability of the vapor cure systems and to establish further fruitful areas of research. No optimization of polymer design, curing agent design, or the like was attempted. Second, an apparent likely explanation (one of several explanations possible) as to the low performance results resides in use of a di-functional polymer for cross-linking. Increasing the number of cross-linking sites on the polymer should improve the performance of the coating compositions. Still, these results establish the usefulness of the adduct formation of the present invention.
The present invention is an improvement in a method for making a phenol-functional polyester polymer wherein a hydroxybenzoic acid, a polyol, and a dicarboxylic acid are subjected to a polyesterification reaction under polyesterification conditions to make said polymer. The improvement comprises conducting the reaction in two stages, the first stage comprising the formation of an ester-alcohol adduct between said hydroxybenzoic acid and an epoxy compound wherein the ratio of carboxyl groups from said hydroxybenzoic acid to said oxirane groups of said epoxy compound is about 1:1. The second stage of the improvement comprises conducting the polyesterification reaction with said adduct.
2
BACKGROUND OF THE INVENTION The present invention relates to a wire electrode supplying device for use in a wire cut electric discharge machining apparatus. FIG. 1 shows a conventional wire electrode supplying device disclosed, for instance, by Published Examined Japanese Patent Application No. 11111/1985. In such a device, while being restrained with a jet stream of machining solution (hereinafter referred to as "a jet stream", when applicable) a wire electrode is conveyed by a wire electrode feeding unit (not shown) from a wire guide member on the wire electrode supplying side to a wire guide member on the wire electrode receiving side which are provided on both sides of a workpiece to be machined. In FIG. 1, reference numeral 1 designates a workpiece; 2, a machining start hole; 3, a wire electrode; 4, a wire guide on the wire electrode supplying side; 5, a wire guide on the wire electrode receiving side, 6, a jet nozzle; and 7, a jet stream. In automatically supplying the wire electrode with the wire electrode supplying device thus constructed, the jet stream 7 is jetted from the wire guide 4 on the wire electrode supplying side, and under this condition, the wire electrode is passed through the machining start hole 2 and the wire guide 5 on the wire electrode receiving side by means of a wire electrode supplying mechanism (not shown) while being restrained by the jet stream, and is then taken up by a wire take-up mechanism (not shown) or received in a predetermined container Thus, the wire cut electric discharge machining operation can be started. The conventional wire electrode supplying device in a wire cut electric discharge machining apparatus machine is designed as described above. Therefore, when the wire electrode comes out of the jet stream without being restrained, it becomes impossible to supply the wire electrode. FIGS. 2(a) and 2(b) are explanatory FIGURES for describing the difficulty that the wire electrode comes out of the jet stream during the wire electrode supplying operation. In FIGS. 2(a) and 2(b), those components which have been previously described with reference to FIG. 1 are therefore similarly numbered. FIG. 2(a) shows the case when the end portion of the wire electrodes comes out of the jet stream before reaching the wire guide 5 on the wire electrode receiving side. In this case, the wire electrode is not inserted into the wire guide 5, and therefore the wire electrode supplying operation must be stopped This difficulty is liable to occur especially when the wire electrode remains greatly curled. In general, a wire electrode is wound on a wire electrode supplying bobbin before use, and therefore it remains curled to some extent. In addition, the wire electrode is curled when drawn. Furthermore, usually in the wire cut electric discharge machining apparatus pulleys and rollers are provided along the wire electrode laying path from the wire electrode supplying bobbin to the wire guide on the wire electrode receiving side, and therefore the wire electrode is additionally curled while being conveyed along the wire electrode laying path. That is, there are many causes to curl the wire electrode. Thus, the curvature and direction of curl of the wire electrode are variously changed while it is conveyed along the wire electrode supplying path. On the other hand, the jet stream acts to make the curled wire electrode straight, and to restrain it so that it is positioned along, the central, axis of the jet stream. This restraining force is attributed to the shearing force of the fluid. The velocity of the jet stream is higher than the wire electrode supplying speed. Therefore, a fluid shearing force acts uniformly on the minute parts of the wire electrode in the wire supplying direction, and, on a point of the wire electrode, a force proportional to the distance between the point and the end of the wire electrode is exerted, thus pulling the wire electrode on the wire electrode supplying side. As a result, the curled wire electrode is made straight, and it is held at the center of the jet stream. However, it goes without saying that the restraining force of the jet stream exerted on the wire electrode is limited. According to the experiment of the present inventor, in the case where a 0.3 mm diameter brass wire is conveyed with a jet stream 1.5 mm in diameter and 5 kg f/cm 2 in pressure, the wire electrode curled with a curvature radius (p) of at least 200 mm as shown in FIG. 3 is positively restrained by the jet stream, but a wire electrode curled with a curvature radius of less than 200 mm is not restrained by the jet stream, thus coming out of the latter. In the case of FIG. 2(a), after the end portion of the wire electrode has passed through the wire guide on the wire electrode receiving side, a load is developed at the wire guide to obstruct the insertion of the wire electrode, so that the wire electrode being supplied has no way to go, thus coming out of the jet stream. In this case also, the conveyance of the wire electrode must be suspended. That is, in the conventional wire electrode supplying device, when the wire electrode is greatly curled, or when a load to obstruct the insertion of the wire electrode is developed at the wire guide on the wire electrode receiving side, the wire electrode is not restrained by the jet stream, thus coming out of the latter, as a result of which the wire electrode supplying operation must be suspended. SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to eliminate drawbacks accompanying the prior art device, and the object is accomplished by the provision of a wire electrode supplying device for use in a wire cut electric discharge machining apparatus comprising means for detecting when the wire electrode is released from the jet stream of machining solution, to come out of it. BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings: FIG. 1 is an explanatory diagram showing a conventional wire electrode supplying device; FIGS. 2(a) and 2(b) are explanatory diagrams for a description of difficulties accompanying the conventional wire electrode supplying device; FIG. 3 an explanatory diagram for a description of the curl of a wire electrode; FIG. 4 is an explanatory diagram showing the arrangement of one example of a wire electrode supplying device for use in a wire cut electric discharge machining apparatus according to the present invention; FIG. 5 is a circuit diagram showing a contact detecting circuit in the wire electrode supplying device in FIG. 4; and FIGS. 6(a) and 6(b) are explanatory diagrams showing other examples of the wire electrode supplying device according to the invention. DESCRIPTION OF PREFERRED EMBODIMENTS Preferred embodiments of this invention will be described with reference to the accompanying drawings. In FIG. 4, parts corresponding functionally to those already described with reference to FIG. 1 are therefore designated by the same reference numerals or characters. Further in FIG. 4, reference numeral 8 designates a capstan roller; 9, a pinch roller; 10, a wire electrode supplying motor coupled to the capstan roller; 11, a cutter; 12, a cutter board, both 11 and 12 being mounted on a conventional wire electrode cutting mechanism which has been disclosed, for instance, in Published Unexamined Japanese Patent Application (OPI) No 80528/1985; 13, a guide die for guiding a wire electrode 3 to a wire guide 4 on the wire electrode supplying side (hereinafter referred to as "an upper wire guide 4", when applicable); and 14, a die guide for supporting the wire electrode, the die guide 14 being brazed to the upper wire guide 4. The upper wire guide 4 is cylindrical, and an electrical feeder 15 is built therein. The wire electrode 3 is supported along the central axis of the upper wire guide 4 on both sides of the electrical feeder 15 by the guide die 13 and the die guide 14, so that it is caused to rub the cut of the electrical feeder 15. Further in FIG. 4, reference numeral 16 designates a fluid inlet formed in a jet nozzle 6; and 17, a numerical control device. The numerical control device 17, as shown in FIG. 5, includes a contact detecting circuit 20. One terminal of the circuit 20 is connected to the workpiece 1, and the other terminal is connected through the upper wire guide 4 and the electrical feeder 15 to the wire electrode 3. In the circuit, a comparator 23 compares an interelectrode voltage Eo from a DC source 21 which is applied across the workpiece 1 and the wire electrode 3 with a comparison voltage Ec from a comparison voltage source 22. When the wire electrode 3 is brought into contact with the workpiece so that the interelectrode voltage Eo becomes lower than the comparison voltage Ec, the comparator 23 outputs a contact detection signal, which is applied to the CPU in the numerical control device 17. The operation of the embodiment shown in FIG. 4 will be described. It is assumed that before the wire electrode supplying operation starts, the cutter 11 has moved to the cutter board 12 by the wire electrode cutting mechanism (not shown); that is, the wire electrode has been cut with the cutter. Upon start of the wire electrode supplying operation, in response to a signal from the numerical control device 17 the wire supplying motor 10 is operated to rotate the capstan roller 8 and the pinch roller 9 to thereby feed the wire electrode 3. The wire electrode 3 is inserted into the guide die 13 and the wire guide 4, and then passed through the die guide 14 to the jet nozzle 6. The stream of machining solution 7 is jetted as follows: Simultaneously when the wire electrode supplying motor is operated, or in a delay time set by the numerical control device 17, a machining solution is supplied into the jet nozzle 6 through the fluid inlet 16 by a machining solution supplying device (not shown), thus forming the aforementioned jet stream. Thus, the wire electrode 3 is conveyed towards the lower wire guide 5 while being restrained by the jet stream. Now, the operation carried out when the wire electrode is released from the jet stream, thus coming out of the latter will be described. Even if the wire electrode comes out of the jet stream, the wire electrode supplying motor is kept rotated. Therefore, the wire electrode is caused to go outside the lower wire guide 5, or it is bent in the machining start hole, thus contacting the workpiece. This contact is transmitted, as a signal, to the numerical control device 17, as a result of which the numerical control device suspends the rotation of the wire electrode supplying motor 10. Thereafter, the wire electrode 3 is cut by moving the cutter 11 to the cutter board 12 with the wire cutting mechanism, and its end portion thus cut off is removed. Thereafter, the wire electrode supplying operation is carried out all over again. Thus, the curled portion of the wire electrode which causes the failure in the wire electrode supplying operation has been removed; that is, the recovery operation has been accomplished. Under this condition, the remaining wire electrode is supplied so that the wire electrode supplying operation is continued. The insertion of the wire electrode into the lower wire guide 5 is obstructed in the case where, when the wire electrode 3 is inserted, its slide resistance is increased with the curvature of the curled portion of the wire electrode, or the slide resistance is increased as the angle of approach of the wire electrode, having a degree of freedom, increases in probability. Therefore, in these cases also, the above-described recovery operation is carried out to continue the wire electrode supplying operation. In the above-described wire electrode supplying device, means for detecting when the wire electrode comes out of the jet stream may be designed as shown in FIGS. 6(a) and 6(b). In the case of FIG. 6(a), a detecting electrode 18 is provided on the part of the lower wire guide 5 which is confronted with the workpiece, so as to detect the contact of the wire electrode with at least a part of a member of the lower wire guide 5. In the case of FIG. 6(b), sensors 19 such as optical sensors or proximity sensors are fixedly or movably provided near the jet stream, to detect when the wire electrode comes out of it. As was described above, the wire electrode supplying device of the invention is so designed as to detect when the wire electrode is released from the jet stream of machining solution, to come out of it. Therefore, whenever the wire electrode comes out of the jet stream, the wire electrode supplying operation is suspended, and the recovery operation is carried out. Thus, the wire electrode supplying operation is positively carried out, and the unmanned operation of the wire cut electric discharge machine can be carried out with higher reliability.
A detecting unit for detecting when the wire electrode is released from a jet stream of a machining solution during the feeding of the wire electrode. Upon detection of the release of the wire electrode, the feeding of the wire electrode is suspended automatically to remove the deformed wire electrode.
1
TECHNICAL FIELD OF THE INVENTION [0001] The present invention relates to “flush cutting,” or “milling” using a guide attached to a router. More specifically, the present invention is a router base, which is manually operated by a user as a guide when attached to an offset router, to mill wood, using a portion of the existing wooden workpiece surface to control the guide. With the present invention, a user may “flush cut” projections from a wooden surface, finish (smooth) areas of a wooden surface, or remove a volume of wood to custom shape a wooden workpiece for special applications. BACKGROUND ART OF THE INVENTION [0002] Removing projections or imperfections from a wooden surface is a common task when working with wood. For instance, in assembling wooden boat decking, holes are drilled in the decking material to create wells which will accept wooden plugs. Decking screws are then typically counter-sunk at the bottom of such wells, and the wooden plugs are then driven into the wells, and glued in place, to seal the screws underneath from moisture and weather. The top ends of the wooden plugs, along with residual glue, projecting above the level of the top surface of the deck so constructed, remain to be removed after the plugs are driven into the wells. Removal of the ends of the plugs and residual glue as they project above the planks of the deck is necessary to achieve the smooth surface required for finished decking. [0003] Other tasks when working with wood are difficult to achieve without special tools. One such task is the creation of a custom piece, such a wooden threshold. When such a piece must be wider than standard sizes, shaping a threshold to fit a required shape using hand or power tools found in most woodworking shops is difficult and time consuming, and the resulting custom piece often uneven and unacceptable. Other tasks easily accomplished using the present invention include removing excess dried glue at the joinder of two pieces of wood, and planing a surface to smooth it where the wood grain has been raised by water or weathering. [0004] Currently there is no simple tool or process to perform some of these woodworking tasks. Where a tool is available to perform some part of these tasks, the tool often is not suitable to complete the entire task, or it is expensive, or using the tool is time consuming or difficult. Wood workers have therefore found it necessary to use a variety of tools, or apply exceptional skill, to accomplish even simple tasks. To take only one example, boat makers fabricating wooden boat decks have up until now sawed off the tops plugs inserted in decks by hand, or chiseled them off, a laborious and time consuming job, and then planed or sanded the surface of the deck to achieve a smooth surface. Even when such methods are used, however, these tools are not optimal to achieve a smooth surface, as a saw, chisel, or plane may each mar the surface of the deck, or take too much of the plug as it splits with its grain. Using both a saw or chisel in conjunction with a plane or sand paper also requires time for each operation or application of a tool, thereby increasing labor costs. To take another example, contractors and wood workers often must fabricate custom pieces to fit a job requiring cutting for unusual dimensions using standard-sized wood stock, or fabricate suitable pieces from combinations of pre-existing standard-sized wood stock, or order a custom piece. As a result, either much time is spent custom fabricating such pieces (if the pieces may be fabricated at all in this way), or the cost of an installation is large, when projects involve unusual dimensions are encountered (such as thresholds). [0005] Apparatus and methods for working a wooden surface, including saws, routers, planes, and similar tools, are common in the related art. Routers, for instance, are used to remove material from surfaces for decorative and functional purposes. Routers typically have a base, and a motor disposed in a housing. The motor drives a rotatable shaft which extends downward beyond the lower end of the housing and base when the router is sitting flat on a surface, with the shaft adapted to secure a router bit thereto. The router bit extends through a central opening in the base to cut a workpiece. Existing routers, because of their relatively small size and rotary cutting action, come perhaps closest to providing the kind of facility and flexibility necessary to overcome the difficulties set forth above. However, existing routers, because of the way the router bit is oriented toward the workpiece, are not set up for, or adaptable to, removal of irregularities in a wooden surface, or cutting portions of a larger piece to modify its shape to create a threshold, or other custom piece. [0006] Existing standard routers use a cast base, typically formed of aluminum and having one side, the underside or bottom side, machined to create a planer guide face through which the shaft and bit protrude. When cutting (the edge of) a workpiece, a user slides the bottom of the router base across the workpiece along its edge. Generally, a second guide, often a bearing attached to the end of the bit, but sometimes some other form of “edgeguide” which may be clamped to the workpiece, is used to assure a smooth cut along the edge of the workpiece. The cutting bit of a router has a shank which is held in place on the shaft by appropriate holding mechanism, including an adjustable, generally hexagonal, set screw. In some routers, the cutting bit may be moved in small increments parallel to the motor shaft, toward or away from the motor, by a fine adjustment mechanism. However, standard routers are all designed so the bit extends below the router base, as standard routers are all designed to smooth edges or drill holes in the workpiece. Standard routers may have “sub-bases,” “spacing blocks,” or “sub-base plates,” which may be attached to the underside surface of a router base to facilitate specific router applications, none of which accomplish the functions of the present invention so far as this inventor is aware. [0007] Other routers are “offset.” That is, the axis of rotation of the motor and attached shaft is parallel to, but displaced from, the axis of rotation of the collet and shaft which supports the router bit or cutting head. In offset routers, the router bit generally extends through an opening in the router base which is offset from the axis of the motor and shaft. Such a configuration allows a user to view the bit, and the area of the workpiece around the bit, as the user operates the router. This ability to view the cutting bit, available only when the cutting bit is offset (or placed before or in front of the router), is important for the present invention, as only by placing the cutter in front of the router can a user in the present invention flush cut to the same surface upon which the router is sitting. As more fully explained below, the ability to view the cutting operation, when incorporated into the present invention, allows a user to mill uneven surfaces in front of the router, in the path of the router. Using the present invention, the same surface upon which the router sub-base sits acts as a guide as the cutting bit approaches and then cuts through an irregularity on that surface. [0008] No apparatus or method for working a wooden surface in the related art of which the inventor is aware, including all routers known in the related art, specifically address the difficulty and uneven results inherent in smoothing a wooden surface having a projecting plug or other irregularity, and no apparatus or method allows a user to form a custom threshold or door jam, or other similar custom piece using only a simple, commonly found, powered hand tool and at least one flat surface as a guide. In attempting to achieve smooth surfaces in wood, and form custom pieces, others have created various cutting, smoothing, planing, and forming apparatus, and methods associated therewith. Such apparatus and methods within the related art include: U.S. Pat. No. 1,574,740 to Raynor, which discloses a cutting device for smoothing a surface. U.S. Pat. No. 4,132,254 to Shockovsky, which discloses portable planing machine, with runners as guides, for use with a power cutter. U.S. Pat. No. 4,324,514 to Craven, which discloses an apparatus for guiding a small router head, for cutting sheet metal printing plates to desired outlines. U.S. Pat. No. 4,529,343 to Adams, which discloses an apparatus for making a custom edge using a router and guide. U.S. Pat. No. 4,551,047 to Price, which discloses a router having a rotatable cutter for paint removal and other smoothing operations. U.S. Pat. No. 4,718,468 to Cowman, which discloses a router guide comprising a base plate, for securing to the underside of the router, and a guide coupled to the base plate. U.S. Pat. No. 5,013,196 to Friegang, which discloses a scribing accessory for an offset router, for trimming a counter top. U.S. Pat. No. 5,048,580 to Smith, which discloses an attachable workpiece guide for a portable power router, and a planar router base. U.S. Pat. No. 5,445,198 to McCurry, which discloses a router sub-base with edge-guide. U.S. Pat. No. 5,452,721 to Engler, III, et al., which discloses a router base-plate for accomplishing a variety of woodworking tasks. U.S. Pat. No. 5,685,675 to Beekman, which discloses an offset router guide assembly for guiding the movement of a router around an outer edge. U.S. Pat. No. 6,068,036 to Cassidy, which discloses a large panel surface planer. U.S. Pat. No. 6,145,556 to Wood, which discloses a router guide comprising a base plate for cutting groove of varying widths. U.S. Pat. No. 6,148,880 to Dehde et. al., which discloses a planer-type face milling machine, with disk-shaped cutting head running parallel to the workpiece surface. [0023] While the inventions disclosed in these related patents fulfill their respective objectives, these prior patents do not describe or suggest an apparatus or method for working a wooden surface to remove a projecting wooden plug, or any other irregularity using a router, nor does anything in related art describe or suggest an apparatus or method which allows a user to form a custom threshold or door jam, or other similar custom piece using only a simple, commonly found, powered hand tool, such as a router. Nothing in the prior art describes or suggests using any powered hand tool to smooth a surface of irregularities using the existing flat surface as a guide, or remove material using such surface as a guide to produce a custom piece which cannot otherwise be formed using a simple powered hand tool. Nothing in the prior art describes or suggest accomplishing any of these tasks using a powered hand tool “free hand,” i.e., without a guide other than the surface upon which the hand tool sits. [0024] The present invention overcomes the drawbacks of prior inventions. A router is used for its small size and versatility. The router is “offset,” so that a user may see the workpiece, and wood shavings are easily removed. The offset router (versus the conventional router) also has the distinct advantage of cutting outside the area occupied by the base when the router is in use, thereby allowing the user to cut away material at the margin of a flat surface, or trim wooden plugs from an otherwise smooth surface, using that same flat surface as a guide. This is accomplished by placing the cutting bit in “front” of the router (in front of the router sub-base, really), in the best position to see the work, and the only position from which a user may flush cut to the same surface upon which the router is sitting. By utilizing these features, and other features set forth below, one can, with the offset router base addition, or “sub-base,” of the present invention, conveniently trim irregularities on the surface of a wooden workpiece and, with the same sub-base, remove material from a wooden workpiece to create a non-standard threshold, or other custom piece. DISCLOSURE OF INVENTION [0000] Summary of the Invention [0025] In its simplest form, this invention is a router sub-base, essentially a pad of material of known and established thickness attached to the bottom side of a pre-existing base of an offset router. This pad of material may be known as a “sub-base,” a “spacing block,” or a “sub-base plate,” but in this application we shall generally refer to this material, and this invention when formed into embodiments of the present invention, as the “sub-base.” In describing the sub-base in this application, we shall generally describe its dimensions when it is properly positioned on an offset router, and that router is sitting on a flat surface with its base down. The sub-base is of uniform thickness, with substantially vertical sides at the edges of the sub-base. The sub-base is also flat and smooth along its top side, planar face, for attachment to the base of the router, and flat and smooth along its bottom side, planar face, so that it may slide easily over the surface of the workpiece. [0026] The sub-base may be of almost any size horizontally, however a convenient size for most sub-bases is large enough to cover the entire lower surface of the offset router to which the sub-base is fastened, except the area of the router base at and near the collet and shaft which supports the router bit. This size is most convenient because the sub-base in this configuration does not extend beyond the router base, to thereby make the router more unwieldy. On the other hand the sub-base should generally extend to the edge of the router base to gain the full mechanical advantage associated with a larger area when using the router on a flat surface, a process which will be explained more fully below. Of course, in any single application, a sub-base larger than the router base may be advantageous for the greater stability such a sub-base provides on a flat surface, and a sub-base smaller than the router base may be advantageous for the ability such a sub-base may provide to fit into tighter spaces. The sub-base may be of almost any shape so long as the top side face and the bottom side face are substantially parallel (and planar). Thus, the vertical edges may be discrete, individual sides, or the vertical edges may bend into a single “edge” which circumvents the entire sub-base (much as the edge of a coin circumvents the entire coin). However, a generally optimum shape is the same shape as the router base to which the sub-base is attached. All such modifications to sub-bases intended for use on offset routers are encompassed within the present invention. [0027] As noted above, the sub-base of the present invention, when attached to the router base, does not extend into the area under the router base near the collet and router bit. Instead a clearance is provided between the sub-base and the router bit to allow the router bit to rotate as it is intended to rotate when the router is in operation and cutting. The clearance between the sub-base and router bit is also sufficient to allow wood shavings and dust to easily clear the bit as it rotates when in operation and cutting. However, the most important benefit derived from the clearance between the bit and the sub-base is that a user may guide the bit across a projection such as a wooden plug, by moving the nose of the router forward toward the plug and over it, or by moving the nose of the router from one side to the other side, without interference from either the sub-base, or the safety guide which is usually supplied at the nose of the router to prevent injury from the bit. [0028] The vertical shape of the edge of the sub-base nearest the router bit may be flat or curved, however a flat, vertical edge facing the router bit has been found to be effective at clearing wood shavings and dust. The distance between that vertical edge and the router bit may vary, and may be quite close, however one-eighth inch appears to be generally adequate for this purpose. As with the overall size of the sub-base, the distance between the vertical edge of the sub-base and the router bit is, in some sense, a compromise between the added stability afforded by a larger sub-base (with vertical edge closer to the bit) on the one hand, and the ease of use more effective clearing of shavings (with vertical edge further from the bit) on the other hand. [0029] Continuing with the shape and size of the sub-base, the sub-base is, in the preferred embodiment of the invention, about ten one-thousandths ({fraction (10/1,000)}) of an inch thicker than the distance between the underside of the base of the router and the distal end of the router bit. This spacing is generally accomplished by setting the base of the router on a flat surface with its adjustment screw loose, with a feeler gauge under the cutting bit. Such a thickness provides for cutting of projections (such as newly installed plugs) which extend from a flat surface (such as a boat deck, or other workpiece) to a height of about ten one-thousandths of an inch above the level of the flat surface. This is close to an optimal distance for a plug to extend from a boat deck during construction, a small remaining projection being desirable to avoid marring the surface of the deck, and the ease of sanding off the end of a plug extending this distance from the surface of the deck. [0030] It may be appreciated that, since most routers, including offset routers, allow for adjustment of the cutting bit in a direction parallel to the motor and shaft, i.e. vertically when the router base is placed flat on a horizontal surface, the thickness of the sub-base may vary, and may therefore be of any reasonable thickness. However, the sub-base will generally be approximately as thick as the distance from the tip of the router bit to the bottom of the base of the router and, for routers generally available, the thickness of the sub-base will be within a range around such dimension equal to the range of adjustment for the cutting bit of which the router is capable. From the user's perspective, he or she may simply purchase a sub-base with thickness equal to the distance between the underside of the base of the router and the distal end of the router bit when the bit is set to about the midpoint within its range of adjustability. In many application, including removing the tops of standard sized plugs in boat deck building, a sub-base of 0.80 inches thick is preferred. As standard bases are often about 0.20 inches thick, the thickness of the base and sub-base together is often about a combined 1.00 inch thick. [0031] After the sub-base is attached to the router as set forth herein, the user may then adjust the bit so that its distal end is about ten one-thousandths ({fraction (10/1,000)}) of one inch closer to the lower surface of the router base than the lower surface of the sub-base is to the lower surface of the router base. Put another way, the end of the cutting bit should be “recessed” from the lower surface of the sub-base, such that when the router is fitted with the sub-base, and the lower surface of the sub-base is placed on a flat, horizontal surface, the end of the bit sits vertically above the flat, horizontal surface about {fraction (10/1,000)} of one inch. As noted above, this spacing is generally easily accomplished by setting the base of the router on a flat surface with its adjustment screw loose, with a feeler gauge under the cutting bit, or by inserting such a gauge under the cutting bit while the router sits on a flat surface with its adjustment screw loose (or by loosening the adjustment screw). [0032] The sub-base of the present invention may be fabricated from a variety of materials, including wood, steel, aluminum, and plastic, so long as the material is hard enough to resist wear as it slides across a wooden surface when in use. While materials harder than wood may mar such a surface, such materials are generally preferred because a sub-base made from such materials may be used for a longer time than a sub-base made from softer materials, and a the risk of damage to the workpiece is slight when the user has gained proficiency with the router and sub-base. [0033] The sub-base of the present invention may generally be fastened to the base of a standard offset router as it comes from the manufacturer. The bases of most offset routers are fastened to the main body of the router with screws or bolts (generally four in number), which screws or bolts may be removed, and replaced with longer screws or bolts having the same diameter, pitch, and head size and shape. The length of the new replacement screws is approximately the length of the old factory-installed screws, plus the thickness of the sub-base. As the sub-base is supplied with holes oriented to allow insertion of the new replacement screws through the sub-base and into the screw holes of the main body of the router, a user may remove the old factory screws or bolts of the router base, place the sub-base against the bottom surface of the base of the router, insert the new replacement screws or bolts, and drive the new screws into place (or secure the ends of the new bolts with suitable nuts). The sub-base must be formed so as to provide wells or counter sinks in its lower face, to allow the new replacement screws or bolts to recede from the lower face, thereby allowing the lower face to slide across a wooden surface without marring it. Thus, for routers of standard size, having a base of about 0.20 inches thick, the addition of a preferred size sub-base of about 0.80 inches requires extended screws which are about 0.80 inches longer than the screws originally supplied with the router. [0034] The sub-base may also be installed as a replacement of the router base, rather than under the existing router base. Such installation on the router is desirable in the event the user wishes to work in a tight spot, such as very close to a wall. In such case, the safety guard on the nose of most offset routers is then absent, and the router may then be moved closer to walls and into tight corners. In such installation, the router base is removed, rather than retained in place as in the usual installation of the present invention, and a thicker sub-base (in essence, a replacement router base) is installed in its place. The thicker sub-base is thicker by the amount of the router base which is removed, but may in all other respects have the dimensions of the usual sub-base as set forth above. Of course, with an installation of the sub-base without the router base, shorter new replacement screws or bolts is desirable, so that they do not extend above the screw holes of the main body of the router. [0035] It may be noted that use of the sub-base without the original router base is generally not recommended or desirable, except in the special circumstances where the user wishes to work in a tight place or very close to a wall or other object. The router base generally has a “nose” which surrounds the bit, thereby providing a “stop” which keeps the cutting edges of the bit away from objects which should not be cut. Use of the sub-base without the router base increases the risk of inadvertently placing the spinning bit against some object, such as a wall or the hand of the user. [0036] In one preferred embodiment of the present invention, the sub-base is formed with a channel or groove in the lower surface of the sub-base. The channel should be at least as wide as any plug used to secure decking to its supporting under structure (joists), and at least ten one-thousandths ({fraction (10/1,000)}) of an inch deep. At this depth, the channel is at least as deep as the distance the cutting bit will remain above the surface of such a deck when a router having the sub-base of the present invention is in operation in a preferred mode. Accordingly, the channel allows one to cut off material to a height above the lower surface of the sub-base as it sits on the flat surface of the workpiece (and therefore above the flat surface of the workpiece itself). [0037] The channel should extend entirely across the lower surface of the sub-base, preferably from its “front” edge, nearest the cutting bit, to its back edge, away from the cutting bit. With such a channel, the router with sub-base may travel over any part of any plugs still projecting, or over any other projections remaining, after cutting, without restriction, as the router is moved “forward” (cutting bit leading). This allows an additional direction of movement as the router cuts a plug or other projection, in addition to movement of the router side to side. As noted above, plugs and other projections are preferably cut close to, but not flush with, the flat surface from which they extend, thereby avoiding damage to such surface. Portions of plugs and other projections remaining such a distance above the surface of the deck or other workpiece may be easily removed by sanding, which is usually required to finish the surface in any case. The channel may also be considerably wider and/or deeper than the dimensions set forth above, and in most cases a wider and deeper channel is preferred, better results being achieved when the channel is at least twice as wide as the diameter of any plug being cut, and at least double the {fraction (10/1,000)} clearance between router bit and workpiece surface mentioned above. [0038] For the task of removing the tops of boat decking plugs of standard size, a router bit having a diameter of approximately three-fourths of one inch (¾″), extending through hole in the router base of about seven-eighths of one inch (⅞″) or thirteen-sixteenths of one inch ({fraction (13/16)}″) is preferred. With such dimensions, sufficient clearance is provided so that the cutting bit never contacts the router base as the bit is adjusted, regardless of the thickness of the sub-base of the present invention. The cutting bit may with such dimension be even retracted into the base if necessary or desirable. Since router bases are typically supplied with holes of less than three-fourths of one inch (¾″), a manufacturer or user must increase the size of the standard router base hole by re-drilling the original router base hole if a user wishes to utilize the present invention for removal of decking plugs in this preferred embodiment. For removing the tops of decking plugs, a sub-base of about 0.80 inches thick is preferred, with a channel depth of 0.125 inches, and width of 0.90 inches. For other tasks, such as milling a threshold, a larger bit is preferred, generally a bit equal to or greater than one inch (1″). Again, for these tasks, re-drilling the original hole in the router base is preferred to avoid contact between the bit and router base (or the inside of the original hole in the router base). [0039] It should be noted that the sub-base of the present invention may be somewhat modified in dimensions to fit a regular, centered-bit, router, and a user using such router may accomplish the removal of plugs, glue and irregularities from flat wooden surfaces. While use of the sub-base of the present invention on standard routers is less convenient, the channel of the sub-base may be widened to allow a user to cut across a plug easily. For other tasks, such as forming a custom threshold from standard wood stock, the sub-base may be modified to support at least some of the base of a standard router. While such a configuration is not optimal, as forming a custom piece cannot be reasonably be accomplished to the standards of professional wood workers in this configuration, all such modifications intended for standard, centered-bit, routers are encompassed within the present invention. [0040] When in use, the apparatus of the present invention allows a user to work with wood using at least two new processes. These processes include: (1) removing the tops of plugs used to fasten decking boards to underlying substrate, or removing other projections on a flat surface such as a deck, and (2) creation of custom, generally oversize, wooden pieces for special applications such as custom thresholds. In addition, milling a small section of an existing piece to remove irregularities and foreign objects (such as glue) is made possible using a standard offset router. The new processes mentioned above may be more specifically described as follows: 1. Removing the tops of plugs—Using the router base of the present invention on an offset router or a regular, centered-bit, router, a user may remove the tops of plugs (and attendant dried glue) which have been used to fasten decking boards to underlying substrate by: A. Attaching the sub-base of the present invention to a router using suitable means, B. Attaching a suitable cutting bit to the collet of the router, C. Setting the router on a flat surface having plugs or other projections, D. Adjusting the cutting bit of the router using the adjustments provided on the router so that the distal end of the bit is recessed back from (above when the router is sitting on a horizontal surface) the lower surface of the sub-base about {fraction (10/1,000)} on one inch, E. Turning on the router, F. Moving the router across the flat surface, keeping the bottom of the sub-base against the flat surface, so that the bit of the router moves to and through a plug or other projection, thereby cutting the plug or other projection so that it extends about {fraction (10/1,000)} of one inch from the flat surface after cutting, and G. Moving the main part of the router over the cut plug or other projection, so that the remainder of the plug or other projection, extending from the flat surface after the plug or projection is cut, moves through the channel formed in the lower surface of the sub-base, or moving the main part of the router from one side to the other, so that the bit of the router moves away from the cut plug. 2. Creation of custom wooden pieces for special applications—Using the router base of the present invention on an offset router, a user may remove material from a piece of wood using a precut or pre-existing flat surface on that piece of wood as a guide by: A. Attaching the sub-base of the present invention to an offset router using suitable means, B. Attaching a suitable cutting bit to the collet of the router, C. Setting the router on a flat surface of a workpiece, D. Adjusting the cutting bit of the router using the adjustments provided on the router so that the distal end of the bit is approximately equal to the lower surface of the sub-base (for instance, resting on the flat surface), E. Turning on the router, F. Moving the router freehand so that the bit moves, side to side and forward (generally in a series of arcs), to and through a portion of the workpiece remaining at or near the edge of the flat surface of the workpiece, using the flat surface as a guide by placing the lower surface of the sub-base on the flat surface as the user moves the router through such series of arcs, thereby removing stock from the workpiece at or near the edge of the flat surface, G. Repeating the previous step until sufficient material has been removed from the workpiece, at the desired locations, perhaps limited by one or more stops against which the router nosepiece may bear, to fabricate or machine the desired custom piece. [0057] It may be noted that, if a piece of wood has no pre-existing flat surface to use as a guide when creating a custom piece, a wood worker may cut a into a workpiece with a table saw or other standard equipment, so that the cut is formed. One of the flat surfaces created at the sides of such a cut could be formed into a guiding surface, as a flat surface is formed at the side of the cut toward the main body of the workpiece. Such flat surface may then extend in the direction a flat surface would extend if it already existed on the chosen workpiece. That portion of the workpiece remaining on the other side of the cut (the “overhang” remaining on the opposite side of the cut away from the main body), if any, may be removed by cutting away before the present invention is applied to the workpiece. [0058] The more important features of the invention have thus been outlined, rather broadly, so that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. Additional features of specific embodiments of the invention will be described below. However, before explaining preferred embodiments of the invention in detail, it may be noted briefly that the present invention substantially departs from pre-existing apparatus and methods of the prior art, and in so doing provides the user with the highly desirable ability to flush cut to the same surface the cutting tool is sitting on, using an existing flat surface as a guide. This facility is enhanced, when the present invention is used with an offset router. When the cutting bit is placed in front of the base in such offset router, a user may cut projections above a surface to any desired height while viewing the cutting process. Using an offset router, a user may also conveniently cut away wood at the edge of any flat surface of a workpiece to create custom pieces, such as threshold, using such flat surfaces of the workpiece as a guide for further cutting. OBJECTS OF THE INVENTION [0059] A principal object of the present invention is to provide an apparatus for smoothing a wooden surface using a router. [0060] A further principle object of the present invention is to provide an apparatus for cutting off the tops of plugs and other projections, and dried glue associated therewith, when such plugs are used in building decks on boats and buildings, using a router. [0061] A further principal object of the present invention is to provide an apparatus for removing portions of a workpiece, using an existing flat surface on that workpiece as a guide, to create custom pieces, using an offset router. [0062] A further object of the present invention is to provide a method for smoothing a wooden surface using a router. [0063] A further object of the present invention is to provide a method for cutting off the tops of plugs and other projections, and glue associated therewith, when such plugs are used in building decks on boats and buildings, using a router. [0064] A further object of the present invention is to provide a method for removing portions of a workpiece, using an existing flat surface on that workpiece as a guide, to create custom pieces, using an offset router. BRIEF DESCRIPTION OF DRAWINGS [0065] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate one preferred embodiment of the present invention, and such drawings, together with the description set forth herein, serve to explain the principles of the invention. [0066] FIG. 1 is a side view drawing of one preferred embodiment of the present invention, showing a router in overall arrangement, its offset attachment, its original base, and the sub-base of the present intention. [0067] FIG. 2 is a front view drawing of some of the router shown in FIG. 1 (from the side), in which the channel of the sub-base and other details from the front are more apparent. [0068] FIG. 3 is top down drawing of the router shown in FIG. 1 and FIG. 2 , in which the channel is specifically located. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS [0000] Apparatus of the Invention [0069] Referring initially to FIG. 1 , a first embodiment of the present invention is shown in side view. In FIG. 1 a router, with motor housing 1 , within which a motor resides, is also equipped with a power cord 2 , and switch 3 . The router 1 has attached to it an offset attachment 4 using attachment means 5 . The offset attachment 4 transmits the rotary motion of the motor to a holding mechanism, such as a collet 6 having an adjustable, generally hexagonal, set screw 7 . The offset attachment 4 also has attached to it a base 8 , with a lower surface 9 , which is employed by a user to guide the router across the top surface of a workpiece (not shown). The base 8 is attached to the offset attachment 4 by holding means (usually screws). In FIG. 1 , the sub-base of the present invention 10 is also shown, and the holding means normally used for the base 9 of the router has been replaced with new extended screws 11 , which screws are longer than the screws originally supplied with the router. In FIG. 1 , the upper face 12 of the sub-base 10 is attached to the router by extended screws 11 , and bears against the lower surface 9 of the base 8 of offset attachment 4 . The lower face 13 of sub-base 10 has formed in it a channel 15 , which extends the length of the sub-base 10 , from the front edge 18 of the sub-base 10 to the back edge 19 of the sub-base 10 . In this preferred embodiment, the floor 16 of the channel 15 extends fore and aft, 0.125 inches deep, from the front face 18 of the sub-base 10 to the back edge 19 of the sub-base 10 , and the channel 15 is 0.90 inches wide. In this preferred embodiments, the sub-base 10 is 0.80 inches thick. As the base 8 is in this embodiment 0.20 inches thick, the thickness of the base 8 and sub-base 10 together is in this embodiment 1.00 inches thick. As a result, the extended screws 11 are in this embodiment 0.80 inches longer than the screws originally supplied with the router to hold the base 9 to the offset attachment 4 . Before the router may be used, a cutting bit 20 , with shaft 21 is inserted into collet 6 . Shaft 21 is then adjusted vertically into the correct position (noted below) in collet 6 , and set screw 7 is tightened to secure shaft 21 to collet 6 , thereby correctly and securely positioning bit 20 for use. [0070] FIG. 2 is a front view of the apparatus of the present invention, showing motor housing 1 , offset attachment 4 , with collet 6 and set and set screw 7 . The base 8 of the router, with lower surface 9 , is again attached to the offset attachment 4 , and again sub-base 10 is shown secured to base 8 with new extended screws 11 . Again the upper face 12 of the sub-base 10 is thereby attached to the router by extended screws 11 , and bears against the lower surface 9 of the base 8 of offset attachment 4 . Again cutting bit 20 , with shaft 21 is shown inserted into collet 6 , and shaft 21 is adjusted vertically into the correct position in collet 6 , and set screw 7 is tightened to secure shaft 21 to collet 6 . The correct position for bit 20 is, generally, about ten one-thousandths of one inch ({fraction (10/1,000)}″) above the surface upon which the router sits 25 . Accordingly, shaft 21 with attached bit 20 is adjusted in collet 6 (often with fine adjustments) until there appears a clearance of about {fraction (10/1,000)}″ between the bit 20 and such surface 25 . This can often be accomplished, with experience, “by eye” when viewing the light between the bit 20 and such surface 25 , however a user may also simply insert a gauge of appropriate thickness between the bit 20 and such surface 25 while, at substantially the same time, tightening the set screw 7 in collet 6 . [0071] Also appearing in FIG. 2 is channel 15 , in this preferred embodiment extending fore and aft, 0.125 inches deep, from the front edge of the sub-base 10 to the back edge of the sub-base 10 . The channel is further defined by right channel side 14 and left channel side 17 , which are 0.90 inches from each other in this embodiment, thereby providing a channel 15 0.90 inches wide and 0.125 inches deep, front to back along the lower surface 13 of sub-base 10 . Finally, in FIG. 2 there appears the front face of front edge 18 of the sub-base 10 , which is formed in sub-base 10 at the time of manufacture to provide a space between bit 20 and the sub-base 10 . Thus, front edge 18 is defined by ridges in the outside edge of sub-base 10 , i.e., ridge 27 on the right side of the router, and ridge 28 on the left side of the router. Between ridge 27 and ridge 28 , the front edge 18 presents a flat face toward the front of the router and the bit 20 . [0072] FIG. 3 is a top down view of the apparatus of the present invention, showing motor housing 1 , power cord 2 , switch 3 , offset attachment 4 , and base 8 of the router. FIG. 3 also shows the top of threaded holes into which extended screws 11 are screwed (at 23 ). Channel 15 is again shown in FIG. 3 , however because channel 15 is at the bottom of the router, it is shown by dotted lines which correspond to right channel side 14 and left channel side 17 (which are 0.90 inches from each other in this embodiment, thereby creating a 0.90 inch wide channel). [0073] Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope of the invention being indicated by the following claims and equivalents.
A router sub-base and method is disclosed, utilizing a pad of material attached to a router base, to flush cut projections from a wooden surface, smooth areas of a wooden surface, or remove a volume of wood to custom shape a wooden workpiece for special applications, in which a user may manually operate the router to mill wood, using a portion of the existing wooden workpiece surface as a guide to control cutting.
1
FIELD OF INVENTION [0001] The present invention generally concerns devices, systems and methods for transportation; and more particularly, in various representative and exemplary embodiments, to the towing and maneuvering of trailers, for example. BACKGROUND [0002] Trailers are vehicles that may be towed by another vehicle, such as for example, a small open cart or a platform used for transporting a boat. The tow engagement portion of a trailer may often be generally supported by a trailer tongue jack when the trailer is parked or otherwise disengaged with the towing vehicle. [0003] Conventional trailer tongue jacks may be secured to a trailer tongue extension and may be configured with a baseplate at the lower end of the jack to distribute load weight over the ground. Trailer jacks are typically configured in the form of elongated shafts that have an upper portion secured to the trailer tongue extension and a lower portion that may be collapsible. A crank arm that may be rotated about the axis of the jack shaft, or in some cases about a different axis, may be employed to extend or collapse the shaft. Consequently, the elevation of the trailer tongue extension can be varied over a particular range for specific applications. [0004] When a vehicle is re-positioned for engagement with a trailer hitch disposed on the forward end of a tongue extension, careful maneuvering for proper alignment is generally required. For example, a towing vehicle may need to back up numerous times in order to achieve suitable alignment with the trailer hitch and trailer tongue extension. [0005] Typical trailer jacks have a 6″ hard wheel and a manual jack screw. The wheel is generally intended to allow the operator to roll the trailer manually. Due to the design of the wheels, varying transportation surfaces, and high loads on the wheel, it may often be difficult to maneuver a trailer with a conventional trailer jack. For example, backing a vehicle to a trailer and aligning the ball post of the vehicle to the trailer hitch can be quite time consuming. The wheel of conventional trailer jacks is often a poor mechanism for positioning the trailer. Moreover, wheels of existing trailer jacks generally have few features incorporated into their design for steering the jack wheel, inasmuch as most trailer jacks employ a “free castering” element. [0006] Accordingly, a need exists inter alia to provide an improved system by which a trailer tongue extension may be maneuvered so that a trailer hitch may be suitably positioned and aligned for proper engagement with, for example, a ball post of a towing vehicle. SUMMARY OF THE INVENTION [0007] In various representative aspects, the present invention provides an apparatus and method for maneuvering and transporting trailers. Exemplary features are generally disclosed as including a mounting bracket adapted for attachment to a trailer; a jack shaft adapted for attachment to the mounting bracket; a wheel supported by a wheel assembly at one end of the jack shaft, wherein the wheel assembly provides rotation about the vertical axis of the shaft; a right-angle gear motor configured to provide rotary propulsion of the wheel; and a steering extension adapted to permit rotation of the wheel assembly in order to maneuver the trailer. [0008] Additional advantages of the present invention will be set forth in the Detailed Description which follows and may be obvious from the Detailed Description or may be learned by practice of exemplary embodiments of the invention. Still other advantages of the invention may be realized by means of any of the instrumentalities, methods or combinations particularly pointed out in the claims. BRIEF DESCRIPTION OF THE DRAWINGS [0009] Representative elements, operational features, applications and/or advantages of the present invention reside in the details of construction and operation as more fully hereafter depicted, described and claimed—reference being made to the accompanying drawings forming a part hereof, wherein like numerals refer to like parts throughout. Other elements, operational features, applications and/or advantages may become apparent in light of certain exemplary embodiments recited in the Detailed Description, wherein: [0010] FIG. 1 representatively illustrates a three-quarter, perspective view of a tug device in accordance with an exemplary embodiment of the present invention; [0011] FIG. 2 representatively illustrates a front view of a portion of the device generally depicted in FIG. 1 in accordance with another exemplary embodiment of the present invention; [0012] FIG. 3 representatively illustrates a side view of the device generally depicted in FIG. 1 in accordance with another exemplary embodiment of the present invention; [0013] FIG. 4 representatively illustrates a top view of the device generally depicted in FIG. 1 in accordance with another exemplary embodiment of the present invention; [0014] FIG. 5 representatively illustrates a top view of the device generally depicted in FIG. 1 in accordance with yet another exemplary embodiment of the present invention; [0015] FIG. 6 representatively illustrates a side view of the device generally depicted in FIG. 1 in an at least partially retracted position in accordance with another exemplary embodiment of the present invention; [0016] FIG. 7 representatively illustrates a side view of the device generally depicted in FIG. 1 in a stowed position in accordance with another exemplary embodiment of the present invention; and [0017] FIG. 8 representatively illustrates a three-quarter, perspective view of an alternative positioning of the tiller arm of the device generally depicted in FIG. 1 in accordance with yet another exemplary embodiment of the present invention. [0018] Elements in the Figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the Figures may be exaggerated relative to other elements to help improve understanding of various embodiments of the present invention. Furthermore, the terms “first”, “second”, and the like herein, if any, are generally used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. Moreover, the terms “front”, “back”, “top”, “bottom”, “over”, “under”, and the like, if any, are generally employed for descriptive purposes and not necessarily for comprehensively describing exclusive relative position or order. Any of the preceding terms so used may be interchanged under appropriate circumstances such that various embodiments of the invention described herein, for example, are capable of operation in orientations and environments other than those explicitly illustrated or otherwise described. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS [0019] The following descriptions are of exemplary embodiments of the invention and the inventor's conception of the best mode and are not intended to limit the scope, applicability or configuration of the invention in any way. Rather, the following Description is intended to provide convenient illustrations for implementing various embodiments of the invention. As will become apparent, changes may be made in the function and/or arrangement of any of the elements described in the disclosed exemplary embodiments without departing from the spirit and scope of the invention. [0020] A detailed description of an exemplary application, namely an apparatus and method for towing and maneuvering trailers, is provided as a specific enabling disclosure that may be readily generalized to any application of the disclosed device, system and method for transporting load articles. [0021] In accordance with various representative and exemplary embodiments, the present invention provides a trailer tug jack ( FIG. 1 ) for a trailer tongue extension 320 and hitch 325 configured for attachment with a ball post 315 affixed to a towing vehicle 300 . The disclosed trailer jack device ( FIG. 1 ) comprises a mounting bracket 120 that may be attached to a trailer. A jack shaft ( 150 , 130 ) is affixed to the bracket with the shaft ( 150 , 130 ) and/or mounting bracket components pivotal between at least two of a first position for operational towing of a load (see FIG. 3 ), a second position that comprises at least partial retraction of at least a portion of the jack shaft (see FIG. 6 ), and a third position corresponding to stowage of the jack shaft (see FIG. 7 ). In certain exemplary applications, the first position may be pivotally substantially equivalent to the second position and/or the second position may be pivotally substantially equivalent to the third position. In general, however, the first position is that for which the disclosed trailer jack may be used when the trailer is a rest and/or when the trailer tug is used to align and engage the trailer hitch 325 to a ball post 315 of a towing vehicle 300 . [0022] The jack shaft may be configured with an upper portion 150 and an at least partially telescoping lower portion 130 . The jack shaft may also be configured to comprise a hand crank ( 160 , 165 ) at the upper end of the jack shaft 150 that may be used to articulate telescopic extension or retraction of the lower portion of the jack shaft 130 with respect to the upper portion 150 . Accordingly, the elevation of the trailer tongue extension 320 may be altered in order to assist with engagement of the trailer hitch 325 with the receiving ball post 315 of the towing vehicle 300 . The lower portion of the jack shaft 130 may be suitably adapted to provide for rotation of a wheel 140 and/or wheel assembly about the principle (i.e., vertical) axis of the jack shaft ( 150 , 130 ). Alternatively, conjunctively and/or sequentially, the upper portion of the jack shaft 150 may be rotatably connected with the mounting bracket 120 about the principal axis (e.g., vertical axis) of the jack shaft. Configured as such an embodiment, jack shaft 130 may be made to disallow rotation about the primary axis relative to the upper portion 150 and the lower portion 130 may telescope relative to the upper portion 150 by means previously described. In general, the wheel assembly is distally disposed at the lower end of the jack shaft 130 . A right-angle gear motor 100 , for example, may be attached directly to the wheel 140 or to a drive gear. In the case of a drive gear, the gear may be mechanically connected with the wheel 140 . In an alternative exemplary embodiment, a chain or drive belt may be configured for attachment with the drive gear and/or the wheel 140 . In another representative embodiment, the drive gear may be connected with, for example, an axle gear. This may be accomplished, for example, by the drive gear directly meshing with another gear driven thereon, or alternatively, with an intermediate gear that may be employed so as to provide a mechanical advantage between the drive gear and the gear driven thereon. [0023] High loading of wheel 140 and various surface topologies, combined with extremely high torque input and shearing action of steering, were observed to separate the wheel from the hub in several preliminary embodiments. Numerous tests were performed to determine an appropriate combination of materials to provide acceptable performance over a broad range of practical conditions. Accordingly, wheel 140 may be comprised of a machined or cast metal (e.g., aluminum, steel, etc.) hub with a relatively high tensile strength liquid cast polyurethane wheel tread on the outer portion, wherein the thickness of the polyurethane maybe up to approximately 15% to about more than 22% of the total diameter of the wheel and providing a shore hardness in the range of up to approximately 80 to about more than 95 Durometer. Alternatively, conjunctively or sequentially, the hub may be cast from any polymeric material that is suitably adapted to provide sufficient support that may be desirable for loading, torsion and adhesion. Additionally, the polymeric material may be suitably configured to comprise UV inhibitors, thereby providing another exemplary embodiment suitably adapted for outdoor use, for example. In a representative and exemplary application in accordance with one embodiment of the present invention, wheel 140 may comprise a high grade liquid cast polyurethane having a hardness in the approximate range of about 90 to about 95 Durometer (Shore A) with an elongation at break of approximately 430%, a tensile strength in the approximate range of about 7000 to about 7400 psi, a tear strength of about 700 pli. (DIE C), and an abrasion resistance on the order of about 5 to about 10 times that of standard urethane. [0024] In accordance with an exemplary and representative embodiment of the present invention, FIG. 1 illustrates a powered trailer tug device comprising a jack and powered wheel. The tug generally allows a trailer to be maneuvered substantially independently of the tow vehicle; for example, permitting the trailer to be driven to the towing vehicle ball post. The disclosed tug also generally allows the trailer and load to be easily maneuvered into tight spaces without the requirement of a tow vehicle. [0025] The wheel 140 is driven by a very high-torque, right-angle drive electric gear motor 100 . The jack may be either manual or electric. In an exemplary embodiment, gear motor 100 may comprise a reversible electric gear motor. The wheel axle centerline 145 is centered to the vertical axis of the jack shaft 150 , 130 . The axle is keyed to both the wheel 140 and the gear motor 100 and driven directly from the gear motor 100 . Alternatively, the gear motor 100 could be offset from the drive wheel and engaged to the wheel 140 via a chain, belt, sprocket and/or gear assembly. The axle rotation and loading may be transferred to the jack through axle bearings maintained in, for example, an integrated axle and gear motor support assembly 143 . [0026] Electric gear motor 100 may also be configured with a power cord 110 for delivery of electric current to gear motor 100 from a garage AC wall outlet, a battery, a power outlet of the towing vehicle, a power outlet integrated into the trailer, a power outlet integrated into a vehicle supported by the trailer and being towed by the towing vehicle, and/or the like. [0027] The lower portion of jack shaft 130 may be configured to be at least partially collapsible with respect to the upper portion of jack shaft 150 . Collar 155 general provides axial rotation of jack shaft 150 relative to mounting plate 120 , alignment and containment of jack shaft ( 150 , 130 ), as well as a point of attachment for mounting plate 120 . Mounting plate 120 may comprise a quick-release element 125 for attachment/disengagement as well as to permit/lock pivoting of jack shaft ( 150 , 130 ) about an axis substantially normal to mounting plate 120 , for example. [0028] An integrated tiller-extension/crank-arm 160 may be provided to allow for steering as well as for retracting and/or extending jack shaft 130 . Configured as such an embodiment, lower jack shaft portion 130 may be made to disallow rotation about the primary axis relative to jack shaft upper portion 150 and lower portion 130 may telescope relative to upper portion 150 by means previously described. A tiller/crank handle 165 may be attached to a portion of the steering extension 160 so as to provide a steering arm (e.g., tiller) to maneuver the drive wheel 140 . This may be accomplished, for example, with a center bored hole through the internal jack screw with the tiller shaft through the bore hole and affixed to the integral axle and gear motor support assembly. Alternatively the entire assembly may be rotated by affixing the tiller handle to the outer casing or assembly thereto attached and the outer casing attached to the trailer frame mount via a sleeve and bearing bracket arrangement 155 , for example. The tiller may comprise drive wheel motor controls as well. [0029] In accordance with another exemplary embodiment, as generally depicted in FIG. 2 for example, a sleeve and bearing bracket arrangement may comprise an upper bearing assembly 257 and lower bearing assembly 253 affixed to jack shaft 150 and entrapping shaft collar and bracket assembly 155 . Bearing assemblies 257 and 253 generally provide jack shaft ( 150 , 130 ) alignment as well as support of normal bearing load (e.g., weight) of tongue 320 and reduction of rotational friction corresponding to rotation of jack shaft ( 150 , 130 ) within collar 155 for steering of the wheel assembly. Additionally, FIG. 2 shows a bracket pivot element 223 for mounting bracket 120 . Bracket pivot 223 generally allows the jack assembly to rotate into storage and usage positions. In various representative applications of the present invention, bracket pivot 223 may be supplied as standard equipment with the trailer tug device, or may alternatively be supplied as an OEM product. [0030] As generally depicted in FIGS. 3, 4 and 5 , the trailer tug device disclosed herein as an exemplary embodiment of the present inventions may be used for alignment of a trailer hitch 325 with a ball post 315 supported by a tongue extension 305 affixed to towing vehicle 300 . Trailers of the type typically towed by vehicles may include mobile homes, boat trailers, livestock trailers, construction trailers, gardening trailers, and/or the like. A vehicle trailer hitch typically includes a fixed portion that may be secured to the rear end of the towing vehicle 300 with a removable telescoping portion 305 configured with a trailer hitch ball post 315 secured, for example, by a nut. The upper segment of trailer hitch ball post 315 is typically a volumetrically spherical section. Telescoping portion 305 , in addition to other parts of the trailer hitch that may be attached to it, can be remove from the fixed towing vehicle portion 300 when the trailer hitch is not in use. [0031] The towing vehicle 300 trailer hitch ( 305 , 315 ) is representatively illustrated to show a particular operating environment in which the invention may be utilized. A conventional trailer has a horizontally extending trailer tongue 320 with a trailer hitch 325 at the forward end that includes a ball post receiving well 330 for engagement with towing vehicle 300 ball post 315 . Alignment problems may occur with conventional trailer jacks when attempting to connect a trailer to a vehicle; especially when the trailer hitch 325 is to be aligned above ball post 315 before the trailer may be coupled to the towing vehicle 300 . Various representative and exemplary embodiments of the present invention provide improved means for interconnecting a towing vehicle 300 with a trailer hitch 325 . [0032] FIGS. 3 and 4 show wheel assembly and wheel 140 aligned with respect to tongue extension 320 such that if gear motor 100 is engaged to rotationally propel wheel 140 , the trailer would move in a direction co-parallel with the principle axis of tongue extension 320 . To align ball receiving well 330 of trailer hitch 325 with ball post 315 , the trailer tongue extension 320 must be moved not only forward, but also non-orthogonally in the direction indicated 500 , for example, as generally depicted in FIG. 5 . By steering jack shaft ( 150 , 130 ) in the indicated alignment and engaging right-angle motor 100 , wheel 140 will move the trailer and trailer hitch 325 so that the ball post receiving well 330 can be moved substantially over ball post 315 . Thereafter, the lower portion of jack shaft 130 may be at least partially retracted so as to reduce the elevation of trailer tongue extension 320 , so that the ball post receiving well 330 comes to settle over and engage ball post 315 . Conventional trailer hitches typically have mechanisms for securing the hitch to the towing vehicle ball post (not illustrated in the Figures). In general, the disclosed tug device (see FIG. 1 ) may be affixed by means of mounting plate 120 to a trailer tongue extension 320 such that ball post receiving well 330 of trailer hitch 325 may be aligned 500 and subsequently engaged with the towing vehicle 300 ball post 315 . [0033] FIG. 6 generally depicts the tug device representatively illustrated for example in FIG. 1 in a partially retracted position of the lower portion of jack shaft 130 in accordance with an exemplary embodiment of the present invention. FIG. 7 generally depicts the tug device representatively illustrated in FIG. 6 in a jack shaft stowage position in accordance with another exemplary embodiment of the present invention. [0034] FIG. 8 representatively illustrates an exemplary embodiment, in accordance with the present invention, wherein steering extension 160 (e.g., “tiller arm”) may be configured with a pivoting attachment 800 with respect to jack shaft 150 such that steering extension 160 may also function as a hand crank for articulating extension/retraction of the lower portion of jack shaft 130 . Accordingly, crank handle 165 may be revolved about an axis substantially perpendicular to the principle axis of jack shaft ( 150 , 130 ) in order to extend or retract drive wheel 140 from engagement with the ground. Extension or retraction may be obtained by a gearing configuration between crank arm 160 and, for example, a threaded member within upper jack shaft 150 and via a connecting shaft 800 (not illustrated in the Figures). [0035] In the foregoing specification, the invention has been described with reference to specific exemplary embodiments; however, it will be appreciated that various modifications and changes may be made without departing from the scope of the present invention as set forth in the claims below. The specification and Figures are to be regarded in an illustrative manner, rather than a restrictive one and all such modifications are intended to be included within the scope of the present invention. Accordingly, the scope of the invention should be determined by the claims appended hereto and their legal equivalents rather than by merely the examples described above. For example, the steps recited in any method or process claims may be executed in any order and are not limited to the specific order presented in the claims. Additionally, the components and/or elements recited in any device claims may be assembled or otherwise operationally configured in a variety of permutations to produce substantially the same result as the present invention and are accordingly not limited to the specific configuration recited in the claims. [0036] Benefits, other advantages and solutions to problems have been described above with regard to particular embodiments; however, any benefit, advantage, solution to problems or any element that may cause any particular benefit, advantage or solution to occur or to become more pronounced are not to be construed as critical, required or essential features or components of any or all the claims. [0037] As used herein, the terms “comprises”, “comprising”, or any variation thereof, are intended to reference a non-exclusive inclusion, such that a process, method, article, composition or apparatus that comprises a list of elements does not include only those elements recited, but may also include other elements not expressly listed or inherent to such process, method, article, composition or apparatus. Other combinations and/or modifications of the above-described structures, arrangements, applications, proportions, elements, materials or components used in the practice of the present invention, in addition to those not specifically recited, may be varied or otherwise particularly adapted by those skilled in the art to specific environments, manufacturing specifications, design parameters or other operating requirements without departing from the general principles of the same.
An exemplary apparatus, system and method for towing and transporting articles is disclosed as comprising inter alia: a mounting bracket ( 120 ) adapted for attachment to a load; a jack shaft ( 150, 130 ) adapted for attachment to the mounting bracket ( 120 ); a wheel ( 140 ) supported by a wheel assembly at one end of the jack shaft ( 130 ), wherein the wheel assembly is configured for rotation about the vertical axis of the shaft ( 130 ); a right-angle gear motor ( 100 ) configured to provide rotary propulsion of the wheel ( 140 ); and a steering extension ( 160 ) adapted to permit rotation of the wheel assembly in order to guide the direction of movement for towing. Disclosed features and specifications may be variously controlled, adapted or otherwise optionally modified to improve towing, transportation and/or positioning of load articles for any application or operating environment. Exemplary embodiments of the present invention generally provide for towing and transportation of trailers, such as, for example, vehicle trailers.
1
[0001] This is a divisional of application Ser. No. 11/070,413, filed Mar. 2, 2005 which claims the benefit of U.S. Provisional Application No. 60/548,945, filed Mar. 2, 2004, both of which are incorporated herein by reference. BACKGROUND OF THE INVENTION A. GOVERNMENT INTERESTS [0002] None B. RELATED APPLICATIONS [0003] The present application claims priority under 35 U.S.C. § 119 to U.S. Provisional Patent Application Ser. No. 60/548,945, filed Mar. 2, 2004. The entire contents of the aforementioned application are specifically incorporated herein by reference in its entirety. C. FIELD OF THE INVENTION [0004] This invention relates to an improved method of preparing an implantable paste for placement between injured bones or placement in bony voids to induce regeneration, and the compositions produced thereby. Specifically, mineral, ceramic, or processed bone particles, so-called bioactive particles (BP), are coated with a matrix material (MM) capable of forming a viscous gel when reconstituted with water, saline, autologous blood, sera, or other medically acceptable solution. This MM may be a natural or synthetic polymeric material, producing a wettable paste upon exposure to water, saline, or another aqueous solution. In storage, the composition will be granular and dry, but easily wetted during reconstitution. To prepare the composition for administration, the material is reconstituted to a viscous malleable paste by the simple addition of water or other medically acceptable solution without the need for aggressive mixing. The paste may be delivered by syringe or manually deposited yet will be resistant to lavage or to displacement by gravity induced flow. D. DESCRIPTION OF RELATED ART [0005] Bone pastes, such as REGENAFIL™ or OSTEOFIL™ produced by Regeneration Technologies, Inc., comprise particles of allograft demineralized bone matrix (DBM) and gelatin (U.S. Patent Applications 20020098222, 20020018796, and 20020076429). As taught by Scheicher (U.S. Pat. No. 4,191,747), suspending osteoinductive and/or osteoconductive materials in gelatin solutions provides an implantable composition with temperature dependant flow properties. Above the gel transition temperature, the composition is free flowing while below that temperature, i.e. when at body temperature, it forms a stable mass resistant to deformation and dissolution. [0006] However, there are some drawbacks to such compositions. If provided as a pre-mixed suspension of DBM and hydrated gelatin, the product must be stored frozen to prevent degradation of the osteoinductive capability of the DBM. Prior to use, frozen material must not only be thawed but raised above the gel transition temperature in order to yield a free-flowing paste. [0007] Regeneration Technologies, Inc. produces a version of OSTEOFIL™ that can be stored at room temperature. This version is comprised of a mixture of DBM particles and gelatin particles. The drawback of this paste composition and method of preparation is that heated liquid and/or aggressive mixing is required to produce a uniform and free-flowing suspension (U.S. Patent Applications 20010016703, 20010037091, 20030180262). [0008] It is conventional to store drugs, vaccines, medicaments, and solutions in a sealed vial or other container for later use. Drugs, vaccines, medicaments, and solutions may be stored in a dry or powdered form to increase the shelf life and reduce inventory space. Such dry or powdered materials are typically stored in a conventional sealed vial having a puncturable closure, such as an elastomeric stopper, and reconstituted in liquid form for later use, such as administration to a patient, by adding a diluent or solvent. [0009] Dry materials available for reconstitution may also be stored directly in a syringe. For example, as described in U.S. Pat. No. 6,773,714 (Dunn, 2004), leuprolide acetate, a peptide drug, is lyophilized directly in a syringe prior to use. A biodegradable polymer and solvent solution is filled into another syringe. The two syringes are coupled together and the contents are drawn back and forth between the two syringes until the polymer/solvent solution and the leuprolide acetate are effectively mixed together, forming a flowable composition. The flowable composition is drawn into one syringe and the two syringes then disconnected. A needle is inserted onto the syringe containing the flowable composition and then injected through the needle into the body. Other flowable compositions are described in U.S. Pat. Nos. 5,324,519; 4,938,763; 5,702,716; 5,744,153; and 5,990,194. None of these techniques, though, anticipate the preparation of an easily dispersible bioactive particle composition, prepared from the precipitation of a high molecular-weight polymer onto the bioactive particle, with the described characteristics in the present invention. SUMMARY OF THE INVENTION [0000] A. Features and Advantages of the Invention [0010] The present invention overcomes these and other inherent deficiencies in the, prior art by providing novel bioactive particles and preparation methods for use in preparing improved therapeutic products. The described processes involve forming bioactive particles in a solution and/or microencapsulating particles, and compositions produced thereby. The process utilizes alcohol precipitation under mechanical stirring at controlled temperatures, which provides the proper forces during precipitation to control the particle growth and mixing properties. Preferential precipitation of the higher molecular weight fraction of the matrix material produces desirable final compositions with high surface area, controllable gelation, and shelf-life stability. Bioactive particles may be (1) formed in a solution to obtain a particle suspension and then (2) dried in an oven or fluid bed to control the structure of the particle or particle surface. In general, the process can be used to microencapsulate bioactive particles by suspending the drug particles in a solution including a coating material (such as a biodegradable polymer) and adding alcohol to the solution under controlled process conditions. The bioactive particle compositions produced thereby possess improved properties including, but not limited to, improved flow and syringability, controlled adhesion, stability, and/or resistance to moisture. This process, and the compositions produced, also provide significant advantages in the manufacture of bioactive particulate formulations, as well as biomedical particulate compositions, where sensitive macromolecules, such as proteins or DNA, are involved that would be degraded using more rigorous processing conditions or temperatures. [0000] B. Summary of the Invention [0011] The present invention provides compositions for repairing bone that comprise: bioactive particles; and a coating on the bioactive particles comprising at least one high molecular weight polymer, wherein the composition is in a form capable of repairing bone. The bioactive particles may be chosen from mineral particles, ceramic particles and processed bone particles. The processed bone particles may be derived from human, bovine, ovine or porcine sources. The processed bone particles may be derived from a demineralized bone matrix and range in size from about 100 to about 800 microns. Alternatively, the processed bone particles may comprise ground cortical and cancellous bone chips ranging in size from about 1.0 to about 3.0 millimeters. In some embodiments, one or more compositions described herein are in paste form. The paste may be prepared by contacting the bioactive particles coated with at least one high molecular weight polymer with a solution. The high molecular weight polymer may be a naturally occurring high molecular weight polymer. The high molecular weight polymer may be a synthetic polymer. The high molecular weight polymer may be chosen from gelatin, pectin, hydrogel polymers, polycarbophils, polyanhydrides, polyacrylic acids, alginates, and gums. The composition may further comprise a drug. The composition for repairing bone may comprise: bloactive particles; and a coating on the bioactive particles that may comprise at least one at least one high molecular weight polymer, wherein the composition may be in a form capable of repairing bone; wherein the bioactive particles may be derived from a demineralized bone matrix and range in size from about 100 to about 800 microns; wherein the high molecular weight polymer may be gelatin. [0012] The present invention provides a method of preparing a composition for repairing bone comprising: providing a solution comprising at least one high molecular weight polymer; adding bioactive particles to the solution; and precipitating the at least one high molecular weight polymer, thereby forming bioactive particles coated with the at least one high molecular weight polymer. The high molecular weight polymer may be precipitated using a solvent chosen from 1-propanol, 2-propanol, ethanol, hexanol, and acetone. The method may involve drying the bioactive particles coated with the at least one high molecular weight polymer, thereby producing a granular preparation suitable for reconstitution. The bioactive particles may be dried in a convection oven, a vacuum oven, or a fluidized bed apparatus. The bioactive particles may be processed bone particles and the polymer may be gelatin ranging in amounts from about 1:2 to about 10:1 weight fraction. The present invention provides a composition for repairing bone prepared according to this method. [0013] The present invention provides a method of repairing bone comprising: providing a dry composition comprising bioactive particles coated with at least one high molecular weight polymer; contacting the dry composition with a solution, thereby to convert the dry composition into a wet composition; and placing the wet composition in contact with a bone defect on an internal or external bone surface, wherein the wet composition may be capable of repairing bone. BRIEF DESCRIPTION OF THE DRAWINGS [0014] The drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein. [0015] FIG. 1 is a schematic of the mixing process. A vessel, 13, which may be heated or cooled, 3, has a cover, 21, through which components of the composition may be added, 23, and through which end products and byproducts may be removed, 25. The composition may be stirred with an impeller, 31. [0016] FIG. 2A is a scanning electron micrograph of Bioglass® 45S5 bioactive glass particles coated with porcine gelatin at 500 times magnification. [0017] FIG. 2B is a scanning electron micrograph of Bioglass® 45S5 bioactive glass particles coated with porcine gelatin at 50 times magnification. [0018] FIG. 3A is a scanning electron micrograph of processed bovine cortical bone chips coated with porcine gelatin at 50 times magnification. [0019] FIG. 3B is a scanning electron micrograph of demineralized bone matrix coated with porcine gelatin at 50 times magnification. [0020] FIG. 4 is an example of size exclusion chromatography spectra for the porcine gelatin at different stages of the process. The top trace (A) shows the initial autoclaved porcine gelatin solution before coating. The top middle trace (B) is from gelatin found on the coated particles from Example 4. The bottom middle trace (C) is from gelatin found on the coated particles from Example 3. The bottom trace (D) is for the molecular weight standards used to calibrate the runs. The shifting to the left of the dominant peaks seen in the two middle traces relative to the top and bottom traces indicate the coating process excludes lower molecular weight fractions of the gelatin. [0021] FIG. 5A is an x-ray radiograph, taken at day 28, of coated bovine bone chips implanted in the mouse. The bright area indicates mineralization is still present. [0022] FIG. 5B is an x-ray radiograph, taken at day 28, of coated bioactive glass particles implanted in the mouse. The bright area indicates mineralization is still present. DETAILED DESCRIPTION OF THE INVENTION [0023] The invention is directed to methods of forming microencapsulated bioactive particles and wettable pastes, and the compositions produced thereby. “Bioactive particles” to be produced in accordance with this invention are typically, but not limited to, those 750 micrometers to 1.5 millimeters in size particles. Such bioactive particles and wetted paste compositions include, but are not limited to, allograft bone, xenograft bone, processed bone, natural bone substitutes, calcium salts, bioactive glasses, for human or animal use, cosmetics, as well as inert particles for which a biogels or pastes for bone void-filling or regeneration, as well as hard and soft tissue augmentation. The possibilities and combinations are numerous. [0000] A. COMPOSITIONS OF COATED BIOACTIVE PARTICLES [0024] The present invention relates to compositions of implantable pastes and methods for incorporating (1) mineral, ceramic, or processed bone particles as the BP and additionally (2) binders, bulking agents, excipients, and/or surface modifiers as the MM into easily wetting granular product that provides the same or improved shelf-life stability of current dry compositions but much simpler reconstitution. This is achieved by coating the component or components selected from group (1) with one or more of the components from group (2) to yield a dry, granular composition that wets easily to form a cohesive yet malleable paste. [0025] For example, demineralized bone matrix (DBM) particles might be coated with a thin layer of gelatin and subsequently dried. The resulting dry granular composition will easily wet when an aqueous solution such as physiologic saline is added. The thin gelatin layer around each particle of DBM will absorb water from the saline and become adhesive. The coated particles will form a cohesive and malleable paste even though a) the gelatin coating may not be completely rehydrated and b) the paste may not be at a temperature above the gel transition temperature. [0026] For use in so-called bone pastes, a variety of matrix materials have been tested including hydrogel polymers, polycarbophils, polyanhydrides, polyacrylic acids, alginates, gelatins, gums, and pectin. Adhesion may be affected by physical or mechanical bonds; secondary chemical bonds; and/or primary, ionic or covalent bonds, which can improve the adhesion of delivery system or viscosity. The disclosed method may be used to coat mineral, ceramic, and/or processed bone particles with such materials to produce an implantable composition with good shelf-life stability, ease of storage, and ease of reconstitution. Those coating materials that do not possess a gel transition temperature may lack the resistance to lavage that a gelatin based composition would possess. However, such compositions would still possess the ease and rapidity of reconstitution afforded by this method. [0027] When delivering a non-soluble particulate material or composition to a site in the body for the purposes of promoting acceleration, delay, or enhancement of the healing process, it is desirable to use a paste. Pastes are desirable because these are easily formed to fill irregular voids or volumes, yet tend to remain where they are placed. [0028] When the implanted material is organic or tissue-derived, long-term storage of the material becomes an issue. In the case of so-called bone pastes, the DBM in these pastes is subject to hydrolytic degradation if stored hydrated at room temperature. Frozen pastes require low-temperature freezers for transportation and storage, as well as time to thaw prior to use. Current dry compositions of pastes require aggressive mixing and warm liquids to reconstitute and, in the case of gelatin based pastes, must be maintained at a temperature above body temperature to be easily flowable. [0000] B. METHODS FOR FORMING COATED BIOACTIVE PARTICLES [0029] In the current invention, the inventors found that it is possible to produce porous compositions that wet easily and reconstitute to an implantable paste without the need of aggressive mixing. It is the object of this invention to produce such paste compositions consisting of bioactive particles of minerals, ceramics, and/or processed bone, and coating these bioactive particles with a wettable material or materials capable of forming a viscous gel upon exposure to water, such as gelatin, pectin, hydrogel polymers, polycarbophils, polyanhydrides, polyacrylic acids, alginates, and gums; with or without the inclusion of drugs, binders, wetting agents, and/or bulking agents. [0030] One particular embodiment of this invention is to produce a dry granular composition comprised of DBM coated with gelatin in the approximate mass ratio of 8 parts DBM to 3 parts gelatin. Such a composition is reconstituted to a malleable paste by exposing a densely packed plug of the composition to water in the approximate mass ratio of 7 parts dry composition to 4 parts water and allowing the mixture to sit for approximately 30 seconds, or such time sufficient for the gelatin coating on the DBM particles to rehydrate. Other aqueous solutions, such as saline, sera, or whole blood, could be substituted for water. [0031] To produce this dry composition, damp DBM particles taken at the end of the demineralization process would be assayed for water content. Once the dry mass of DBM particles is calculated by known methods, these damp DBM particles would be added to a sufficient quantity of 3% m/m gelatin solution in deionized water to produce an approximate mass ratio of 2 parts DBM to 1 part gelatin. The excess of gelatin is required because some of the gelatin will be lost during the coating process through incomplete precipitation. The gelatin/DBM suspension starts out above its gelation temperature. The suspension is agitated or rapidly stirred while a quantity of isopropanol, ethanol, and/or acetone, for example, is added slowly to the mix. A simple schematic of a mixing apparatus is depicted in FIG. 1. Low-frequency sonication may be used in addition to stirring, as described in PCT application WO 03/090717. The isopropanol, ethanol, and/or acetone acts as a non solvent for the gelatin in solution. Similarly, a metal ion complexing agent, such as zinc, or pH shift may be used to precipitated the gelatin. The quantity of nonsolvent needed to drive gelatin out of solution depends on the non-solvent chosen, its temperature, and the concentration of gelatin in solution. [0032] It can be observed by those skilled in the art that the cloudiness of the supernatant during the coating process is a result of less than all of the gelatin coming out of the solution at once. The least soluble (generally higher molecular weight) traction of gelatin will be precipitated first. Thus, this process and composition differs from that taught by Scheicher (U.S. Pat. No. 4,191,747) and others in so far as not only are the particles pre-coated with gelatin prior to creating an implantable paste, but the resulting intermediate composition is comprised of DBM suspended in gelatin of higher average molecular weight than other methods, because of how the gelatin was attached onto the surface of the DBM particles. The resulting compositon is easily dried and demonstrates improved stability and wettability compared to other compositions. [0033] Once sufficient gelatin has been deposited onto the DBM particles the mixer can be stopped and the supernatant decanted. In the case of isopropanol used as the non-solvent, a volume is chilled to 15 degrees Celsius and approximately 5 parts added to 1 part initial gelatin solution as a volume ratio and agitated for about 3 minutes. The remaining material is filtered through a 270 mesh seive and washed again in isopropanol with agitation for about 2 minutes. The resulting particulate mass is then dried overnight in an oven at 35 degrees Celsius, yielding a granular powder that wets easily to form a cohesive, malleable paste. [0034] This granular composition can be loaded into appropriate containers and sterilized via ionizing radiation (X-ray, e-beam, or gamma). It will be recognized by one skilled in the art that the amount of material required for the desired effect on administration will, of course, vary with the composition and the nature and severity of the condition and size of the person or animal undergoing treatment, and is ultimately at the discretion of the physician. [0035] While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not limitation. The present invention is not limited to the described compositions and methods, nor is it limited to a particular composition or material, nor is the present invention limited to a particular scale or batch size of production. Thus, the breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents. [0000] C. USES FOR COATED BIOACTIVE PARTIALS [0036] Bioactive particles coated with matrix material or matrix materials may be used to produce easily reconstituted and malleable pastes. Such compositions may be placed in contact with an internal or external bone surface for the purposes including, but not limited to, void filling, e.g. inducing or conducting the regrowth of bony tissue in a surgically or traumatically induced void in boney tissue. Such pastes may also be used to form drug depots, e.g. bioactive particles with chemotherapy agents may be injected into a surgically induced void from which cancerous tissue was removed. D. EXAMPLES [0037] The following examples are included to demonstrate example embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute relevant examples for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. Example 1 [0038] A solution of porcine gelatin (12 g) in water (388 g) was stirred in a polypropylene pitcher using a Lightnin Mixer with a two-blade impeller. To this was added bovine tendon collagen (15.8 g). To this was added a total of 1900 ml of isopropyl alcohol. After precipitate formed, the stirring was stopped and the particles were allowed to settle. Supernatant was decanted and the particulate material was rinsed with 300 ml of isopropyl alcohol. Decanting and rinsing were repeated again. After final decant, the curd-like particles were dried at room temperature under vacuum overnight. A total of 22.1 g of finely divided dry curd-like particles were collected. Moisture content, as determined by loss on heating, was 7.8% mass/mass. Approximately 1.4 g was placed in a 10 ml syringe and wetted with 1 ml saline, easily syringable after reconstitution. Example 2 [0039] A solution of porcine gelatin (6 g) in water (194 g) was stirred in a polypropylene pitcher using a Lightnin Mixer with a two-blade impeller. To this was added calcium sulfate dihydrate particles (12.35 g; sieved to 1-3 mm size range). To this was added a total of 900 ml of isopropyl alcohol. After precipitate formed, the stirring was stopped and the particles were allowed to settle. Supernatant was decanted and the particulate material was rinsed with 200 ml of isopropyl alcohol. Decanting and rinsing were repeated again. After final decant, the curd-like particles were dried at room temperature under vacuum for 5.5 hours. A total of 22.1 g of finely divided dry curd-like particles were collected. Moisture content, as determined by loss on heating, was 15.8% mass/mass. Example 3 [0040] A solution of porcine gelatin (3 g) in water (100 g) was stirred in a 600 ml pyrex beaker using a magnetic stir bar. To this was added Bioglass® 45S5 bioactive glass particles (6.0 g; sieved to 90 to 710 micron size range). To this was added a total of 350 ml of isopropyl alcohol. After precipitate formed, the stirring was stopped and the particles were allowed to settle. Supernatant was decanted and the particulate material was rinsed with 150 ml of isopropyl alcohol. Decanting and rinsing were repeated again. After final decant, the curd-like particles were dried at room temperature under vacuum overnight. A total of 8.3 g of finely divided dry curd-like particles were collected. Moisture content, as determined by loss on heating, was 6.1% mass/mass. [0041] The particles are shown in FIG. 2A and B and appeared several hundred microns in size, with regions of incomplete gelatin coating attached to the surface. The particles mixed easily in a plastic weighboat to form a sticky clump of putty-like material. Approximately 1.7 g was placed in a 10 ml syringe and wetted with 1 ml saline, easily syringable after reconstitution. Samples were placed into leg muscle ectopic sites of athymic mice and 28 day radiographs are shown in FIG. 5A, demonstrating sites of mineral deposits. Additional samples were packed into syringes and sterilized by gamma-irradiation. Further, reconstituted samples were injected into critical-size drilled defects in rabbits and demonstrated osteoconductive responses by radiography. Example 4 [0042] A solution of porcine gelatin (34.5 g) in water (1,115 g) was stirred in a polypropylene pitcher using a Lightnin Mixer with a two-blade impeller. To this was added demineralized bovine bone (bovine DBM) suspension (35 g) taken right after the acid neutralization step (i.e. 53.5 g moist demineralized bone). To this was added a total of 3000 ml of isopropyl alcohol. After precipitate formed, the stirring was stopped and the particles were allowed to settle. Supernatant was decanted and the particulate material was rinsed with ca. 400 ml of isopropyl alcohol. Decanting and rinsing were repeated two more times. After final decant, the particulate curds were dried at room temperature under vacuum for 17 hours. After sieving, 96.5 g of spongy dry curd-like particles were obtained with approximately 35% moisture content. The particles are shown in FIG. 3A and appeared several hundred microns in size with a roughened surface indicating a gelatin coating. Approximately 1.3 g was placed in a 10 ml syringe and wetted with 0.8 ml saline and 1 ml rat blood, both samples easily syringable after reconstitution. [0043] In addition, the molecular weight of (A) autoclaved gelatin starting solution (1% in water) was compared to (B) gelatin diluted (1%) from the above Example as well as (C) Example 3. Size Exclusion Chromotography (SEC) chromatograms, including the molecular weight marker (D) shows thyroglobulin (bovine, MW670,000) at 6.919 minutes, g-globulin (bovine, MW=158,000) at 8.101 minutes, ovalbumin (chicken, MW44,000) at 9.108 minutes, myoglobin (horse, MW=17,000) at 11.212 minutes, and vitamin B12 (MW1,350) at 14.440 minutes. These SEC profiles display clearly that the described method selectively coats the bioactive particles with the high molecular weight fraction of the polymer, in this case gelatin, and the low molecular weight fraction stays in solution and is decanted off before drying. Example 5 [0044] A solution of porcine gelatin (25 g) in water (808 g) was stirred in a polypropylene pitcher using a Lightnin Mixer with a two-blade impeller. To this was added ground bovine cortical bone particles (50 g; cleaned; moist; sieved to 150-1,000 micron size range). To this was added a total of 2400 ml of isopropyl alcohol. After precipitate formed, the stirring was stopped and the particles were allowed to settle. Supernatant was decanted and the particulate material was rinsed with 600 ml of isopropyl alcohol. Decanting and rinsing were repeated two more times. After final decant, the curd-like particles were dried at room temperature under vacuum overnight. A total of 71 g of dry curd-like particles were collected. The particles are shown in FIG. 3B and appeared several hundred microns in size and gelled upon mixing with saline. Example 6 [0045] A solution of hyaluronic acid (4.5 g) in water (300 g) was stirred in a polypropylene pitcher using a Lightnin Mixer with a two-blade impeller. To this was added demineralized bovine cortical bone (11.2 g). To this was added a total of 600 ml of isopropyl alcohol. After precipitate formed, the stirring was stopped and the particles were allowed to settle. Supernatant was decanted and the particulate material was rinsed with 300 ml of isopropyl alcohol. Decanting and rinsing were repeated again. After final decant, the curd-like particles were dried at room temperature under vacuum overnight. Large clumped curd-like particles were produced; some clear indicating hyaluronic acid was not thoroughly dissolved. Example 7 [0046] A solution of 100,000 molecular weight polyethylene oxide (ca 2.5 g) in water (50 ml) was stirred for 30 seconds after the addition of Bioglass® bioactive glass (2.5 g; sieved to 90-710 micron size range). To this was added a solution of isopropyl alcohol and hexanol (120 ml, 1:5 ratio) while stirring for another minute. Solution was placed in the freezer (−5 degrees C.) under stirring where precipitate formed after 1 hour. Supernatant was decanted and the particulate material was rinsed with 100% hexanol. Decanting and rinsing were repeated again. After final decant, the curd-like particles were dried at room temperature under vacuum overnight. Example 8 [0047] A solution of porcine gelatin (3 g) and polyhexamethylene biguanide (PHMB, a biguanide antimicrobial, 100 mg) in water (100 g) was stirred in a 600 ml pyrex beaker using a magnetic stir bar. To this was added Bioglass® 45S5 bioactive glass particles (6.0 g; sieved to 90 to 710 micron size range). To this was added a total of 350 ml of isopropyl alcohol. After precipitate formed, the stirring was stopped and the particles were allowed to settle. Supernatant was decanted and the particulate material was rinsed with 150 ml of isopropyl alcohol. Decanting and rinsing were repeated again. After final decant, the curd-like particles were dried at room temperature under vacuum overnight. A total of approximately 8 g of finely divided dry curd-like particles were collected. Moisture content, as determined by loss on heating, was similar to Example 3 above and PHMB content, analyzed by HPLC, was approximately 1%. After reconstitution, the antimicrobial slow-releasing paste could be used to prevent infection for several days following placement in the wound. Similar drug-releasing systems incorporating drugs and/or bioactive proteins could be prepared in a similar fashion by mixing during the precipitation step or after the particles are dried. Finally, a drug or bioactive protein could also be introduced in the reconstitution fluid to produce a homogenous mixture. Example 9 [0048] A solution of porcine gelatin (87 g) in water (2,813 g) was stirred in a stainless steel bowl using a air-powered stirrer with a two-blade impeller. To this was added Bioglass® 45S5 bioactive glass particles (174 g). To this was added a total of 9,000 ml of isopropyl alcohol. After precipitate formed, the stirring was stopped and the particles were allowed to settle. Supernatant was decanted and the particulate material was rinsed with ca. 3,000 ml of isopropyl alcohol. Decanting and rinsing were repeated two more times. After final decant, the particulate curds were dried in a Glatt Uni-Glatt fluid bed dryer at 35° C. for 1 hour. After sieving, 230 g of dense dry curd-like particles were obtained. Approximately 2.6 g was placed in a 10 ml syringe and wetted with 2.0 ml saline, both samples easily syringable after reconstitution. VI. CITED DOCUMENTS [0000] 1. Wironen, J. F. and Grooms, J. M., “Bone paste”, U.S. Pat. Applic. 20020098222, submitted Mar. 13, 1997. 2. Wironen, J. F., “Thermally sterilized bone paste”, U.S. Pat. Applic. 20020018796, submitted Jan. 28, 1998. 3. Wironen, J., Felton, P., and Jaw, R. “Bone paste subjected to irradiative and thermal Treatment”, U.S. Pat. Applic. 20020076429, submitted Sep. 16, 1998. 4. Scheicher, H., “Corrective agent for the covering and/or filling of bone defects, method for the preparation of same and method of using the same”, U.S. Pat. No. 4,191,747, issued Mar. 4, 1980. 5. Wironen, J., Kao, P., and Bernhardt, A., “System for reconstituting pastes and methods of using same”, U.S. Pat. Applic. 20010016703, submitted Dec. 29, 2000. 6. Wironen, J., and Walpole, M., “System for reconstituting pastes and methods of using same”, U.S. Pat. Applic. 20010037091, submitted Nov. 1, 2001 7. Wironen, J., Kao, P., and Bernhardt, A., “System for reconstituting pastes and methods of using same”, U.S. Pat. Applic. 20030180262, submitted Oct. 11, 2001. 8. Talton, J. and McConville, C, “Process for forming and modifying particles and compositions produced thereby”, PCT application WO 03/090717, filed Apr. 23, 2002.
This invention relates to an improved method of preparing an implantable gel or paste for placement between injured bones or placement in bony voids to induce regeneration, and the compositions produced thereby. Specifically, mineral, ceramic, or processed bone particles are coated with a high molecular weight polymer capable of forming a viscous gel when reconstituted with water, saline, autologous blood, sera, or other medically acceptable solution. This high molecular weight polymer coating material may be a natural or synthetic polymeric material, producing a wettable gel upon exposure to water, saline, or another solution. In storage, the composition will be granular and dry but easily wetted. In use, the material is reconstituted to a viscous malleable paste by the simple addition of water or other medically acceptable solution without the need for aggressive mixing. The paste may be delivered by syringe or manually deposited yet will be resistant to lavage or to displacement by gravity induced flow.
0
FIELD OF THE INVENTION [0001] This invention relates to a safety device for a load carrying vehicle. BACKGROUND OF THE INVENTION [0002] The laws of most (if not all), provinces and states require that if a vehicle is carrying a load which overhangs beyond the rear, front or sides of the vehicle, then a safety device has to be attached to the protruding end of the load. This is usually a flag and/or a lamp. For lack of anything ‘purpose made’, people transporting lumber, piping and other such materials that overhang the vehicle, typically fasten a red ‘rag’ or strip of red plastic to the material in a makeshift fashion. [0003] The problem with the make-shift strip of red cloth or plastic tape is that in the majority of cases, the state and provincial legislation requires an open flag at the end of the load (the flag size required tends to vary between 12 to 18 inches square, depending on the state or province) and, during twilight and evening, a red or amber light visible from the rear and sides of the load. [0004] This presents a problem for anyone transporting overhanging loads, and most makeshift solutions, either taped or tacked to the load, do not meet the legislated requirements, not to mention the risk of potential accident or injury as a result of a poorly marked overhanging load. SUMMARY OF THE INVENTION [0005] It is an object of the present invention to provide an improved safety device for a load-carrying vehicle which is convenient to use and is capable of providing warning of a protruding load to a cyclist, pedestrian, or driver of a following vehicle. [0006] According to the present invention, there is provided a safety device for use with a load-carrying vehicle comprising; a supporting member having means for attaching to a load, said supporting member having a lamp casing fastened thereon, and a flag-supporting arrangement for the mounting of a flag. The flag may be brightly coloured. [0007] The term “flag” as used herein, is to be understood as applying to a piece of cloth or other material, brightly coloured, for use as a warning device. BRIEF DESCRIPTION OF THE DRAWINGS [0008] An embodiment of the invention will now be described, by way of example, with references to the accompany drawings in which: [0009] FIG. 1 is a perspective view of the safety device, [0010] FIG. 2 is a side view of the safety device of FIG. 1 , [0011] FIG. 3 is a bottom view of the safety device of FIGS. 1 and 2 , [0012] FIG. 4 is a side view of the safety device in silhouette format, [0013] FIG. 5 is a plan view in silhouette format, and [0014] FIG. 6 is a front view of the safety device in silhouette format in the direction IV in FIG. 5 . [0015] The same reference numerals are applied in the figures to like parts. DETAILED DESCRIPTION OF THE INVENTION [0016] Referring to FIG. 1 the safety device comprises a supporting member comprising two elongate parts 2 and 4 hingedly connected in a base unit 6 with a spring mechanism 8 . An LED flashing unit 10 with a reflector lens is provided on the base unit 6 whilst a switch 12 is provided for control of the flashing unit 10 . [0017] The upper elongate part 2 is formed with a serrated inner lower surface 3 to facilitate the gripping of a load. [0018] Longitudinal grooves 14 and 16 are formed respectively in the elongate parts 2 and 4 . A transverse groove 18 is provided in the upper surface of elongate part 2 to facilitate the use of bungee cords (not shown) or other means to fasten the safety device onto a load etc. [0019] A pair of apertures 20 and 22 is drilled through the upper elongate part 2 with corresponding apertures 24 and 26 in the lower elongate part 4 . Two screws 28 and 29 are shown in FIG. 2 and, in use, these are passed through the holes or apertures 20 and 22 and screwed onto the load 42 ( FIG. 2 ) to fasten the safety device onto the load 42 in addition to, or instead of, a bungee cord. [0020] FIG. 2 also shows a piece of the load 43 under the clamp. The holes in the clamp (apertures 20 , 24 , and 22 , 26 ) are aligned such that a screw can pass through 20 , 24 and 22 , 26 when the clamp is fully closed (i.e. there is no piece of wood within the jaws). Thus, the user can screw the clamp down onto a load 43 . [0021] When the load 30 is metallic, magnetic members 32 may be provided to hold the safety device on the load and/or the vehicle. [0022] Referring to FIG. 1 it will be seen that a flag 34 , or similar warning device, is fastened to, or hung from, the safety device in those jurisdictions where this is required. It is often stated that this should be a red flag. Three indents such as 36 and 38 ( FIGS. 4 and 5 ) are provided on opposite sides of the base unit 6 to facilitate the use of square rods (not shown) for hanging flag 34 downwards from base unit 6 . Screws (not shown) can be used to fasten the rods in place. [0023] In FIG. 1 a blunt-ended depression 40 of circular cross-section is provided in the base unit 6 for receiving the end of a load 42 , which may be tubing. For receiving loads of different diameter or thickness, internal indentations are shown in FIGS. 2 and 4 . The depression 40 is identified in FIG. 4 and another depression 44 of small diameter is also identified in FIG. 4 . Thus loads of different diameter or size can be accommodated by the base unit 6 . [0024] It will be seen that the embodiment incorporates a brightly coloured safety flag and an LED flashing signal integrated into a clamp for attaching to overhanging loads during transport. The clamp can be attached to the load material in several manners. [0025] The clamp provides notches for three-quarter-inch material, and for one-inch material, as well as a one-inch diameter notch for tubing or pipe. In addition to fastening the clamp using the pressure exerted by the jaws, it can optionally be fastened to material using the screw holes in the clamp, or by using the notches in the clamp to secure it to material with a bungee-cord. In addition, the clamp can be attached to metal material by using magnets in the base of the clamp. [0026] The clamp advantageously includes an 18×18 inch flag of bright red material, which can be attached to the bottom rear of the clamp, or to either side of the clamp. The back of the clamp houses a red LED light that is visible from the sides as well as the rear. The battery-powered LED light has switch that cycles through on-flashing-off. In some cases, a steady light can be used. [0027] There is an unfulfilled need in the market for a versatile, easily attachable (and removable) reusable clamp that meets virtually all of the highway safety codes by incorporating both an open red flag and a flashing red light. The flag and light may, of course, be amber if required. [0028] It will be seen that the embodiment incorporates a brightly coloured safety flag and an LED flashing signal integrated into a clamp for attaching to overhanging loads during transport. The clamp can be attached to the load material in several manners. [0029] In another modification spring mechanism 8 could include a corresponding arm at approximately 45° to enable to user to better open the elongate parts 2 and 4 . In a further modification a pair of pivoting arms, extendable to 90°, could be positioned under the elongate parts 2 and 4 and able to hold the flag in postion. [0030] While the invention has been described with reference to specific embodiments, modifications and variations of the invention may be constructed without departing from the scope of the invention, which is defined in the following claims.
A safety device for use with a load-carrying vehicle, which includes a lamp and a flag to warn vehicles of overhanging or extended loads.
1
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This patent application claims priority from U.S. provisional patent application 60/524,776 filed Nov. 25, 2003. BACKGROUND OF THE INVENTION [0002] The present patent application is directed to a pizza oven specifically intended to bake frozen pizzas of two different types. A trend in modern food preparation equipment is toward specialized appliances for specific applications. One type of specialized appliance is the pizza over, a specialized small electric oven optimized for the baking of frozen pizzas, but also used for other types of food articles. A number of designs and types of pizza ovens are currently sold in commerce. [0003] A limitation on the used of pizza ovens arises from the changing technology of frozen pizza. Originally, all frozen pizzas were very similar in terms of their cooking requirements, but the frozen pizzas are commonly sold in today's marketplace are of two different types requiring two different baking procedures. For many years, all frozen pizzas had pre-baked crust which only needed to be heated thoroughly, and the cheese and toppings heated, before being ready for serving. In recent years, a new type of frozen pizza has become popular, a frozen pizza in which the dough is intended to rise during the baking process. To properly bake a pizza with a self-rising crust, the pizza must be baked at a lower temperature for a longer period of time, to give the crust time to heat up and then rise. Many pizza ovens are not capable of properly baking a frozen pizza with a self-rising crust to take full advantage of the product as it was intended. BRIEF SUMMARY OF THE INVENTION [0004] The pizza oven as described here is intended to be the simplest possible appliance which still is capable of baking both styles of pizza with the simplest possible interface for the user. In summary, the pizza oven has two simple controls, one intended to initiate a pizza baking operation for a frozen pizza with a pre-baked crust and the other intended to initiate a pizza baking operation for a frozen pizza with a self-rising crust. These two different user control cause the pizza oven to bake the inserted pizzas in very different ways, while maintaining the absolute simplest possible user interface. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS [0005] FIG. 1 is a perspective view of a pizza oven constructed in accordance with the present invention. [0006] FIG. 2 is plan view of the user controls for the pizza oven of FIG. 1 . DETAILED DESCRIPTION OF THE INVENTION [0007] Shown in FIG. 1 is the pizza oven constructed in accordance with the present invention. This pizza oven is designed to have the simplest possible controls for operation while still permitting the optimal baking of the two main types of frozen pizzas. [0008] The oven 10 is a rectangular oven with interior electric heating elements to supply the heating energy. The oven includes a removable tray 12 onto which the item to be baked is placed for insertion into the oven. One difference from the conventional pizza oven is that the oven is provided with a taller front opening, approximately 3 inches. This wider opening is to accommodate the larger size of pizzas with rising crust. User operable controls and a display are located on the front of the oven. [0009] The control display 14 on the front of the oven is shown in greater detail in FIG. 2 . The control display include a four digit numeric display to display time of cooking and time left to cook. The control part of the control display has only five user operable inputs, in the form of five buttons. One button is simply a power button, on or off. Two of the buttons are for setting or adjusting the cooking interval, one button being up and one button being down. The other two buttons are alternately for high temperature and low temperature cooking, and these two buttons are linked so that only one setting can be selected at any one time. [0010] In its interior, not shown, the oven includes upper and lower electric heating elements and a temperature sensor. The heating element are under electronic digital control, which also is connected to sense the output of the temperature sensor, to be able to maintain constant temperature, in a manner well known in the art. The front removable tray includes a front panel to seal the front opening in the oven when the tray is inserted if the oven. [0011] In its operation, the oven is controlled so as to default to perform only one of two different processes, depending on which of the two cooking temperature buttons is pressed. If the low temperature button is pressed, the oven will default to cook at around 350° F., and the normal default time period presented to the user will be between twenty and thirty minutes, typically twenty five minutes. The default time period will be presented to the user on the four digit display. If the user presses the power button, cooking of the food begins for the default time period. If the user presses the high temperature cooking option, the oven cooks at around 450° F., and the default time range is set to between twelve to fifteen minutes. The two buttons for controlling the time period of cooking can be used, if needed, to alter the default cooking time period to shorten or lengthen the cooking time period, as experience requires. This option may also be appropriate in the event the oven is used for foods other than pizzas. Note that the cooking temperature is fixed at the choice of the two temperatures appropriate for frozen pizzas. [0012] In way the oven has a pre-set set of conditions for self-rising pizzas and a pre-set set of conditions for pre-baked pizzas all in the same oven with minimal interfaces or effort required by the user. The user has only to pick one of two buttons, one associated with pre-baked crust pizzas, or one associated with self-rising crust pizzas, to operate the oven. While the user has the option to vary cooking time, this is normally not necessary when cooking pizzas, and the unit requires absolutely minimal control by the user.
A dual temperature pizza oven ( 10 ) is arranged to cook at two different temperatures depending on whether a pre-backed or self-rising crust pizza is to be cooked.
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BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to barriers for equestrian competition, training, and exhibitions. More specifically, the invention is an equestrian standard and jump cup that is easily and accurately adjustable along the standard. 2. Description of the Related Art One aspect of equestrian competition and exhibition is jumping in which a horse and rider jump over an obstacle, often referred to as a "barrier". Often the barrier is constituted of a pair of upright stands, known as "standards", a pair of blocks, known as "jump cups", movably mounted on the standards, and a pole extending horizontally between the jump cups. The rider directs the horse to jump over the pole. In competition, scoring is based on the number of poles cleared by the horse, and the height at which the various poles are set. The height of the poles is frequently changed based on the different riders, different horses, and the particular competition or exhibition. To provide flexibility, an equestrian barrier known as a "caveletti" has been developed. A caveletti can be oriented in different manners and stacked upon other cavelettis to present barriers of different heights. However, stacking can provide a very unstable arrangement. Also, when using cavelettis, several pieces must be transported to the site of the competition in order to provide a wide range of barrier heights. There have been several attempts to provide an equestrian barrier that is easy to setup and adjust. For example, U.S. Pat. No. 4,414,920 discloses a rectangular block which can be stacked with other similar blocks to provide barrier supports of varying heights. However, this device inherently has the same limitations as a caveletti, i.e. low stability and many pieces. U.S. Pat. No. 2,989,309 discloses an equestrian standard having a supporting block that can be positioned and fixed at intervals along the standard to provide a barrier having variable height. The supporting block has a pivoting lever attached thereto which engagements with one of plural notches formed on an outer surface of the support while a flat surface of the block abuts a flat inner surface of the support. The lever has a release mechanism which permits movement of the block downward in the event that the horse fails to clear the barrier and falls downward on the bar. The release mechanism is incorporated in the lever and the block is free to move along the support absent the retaining function of the lever. For this reason, the adjustment of the jump cup is not always precise. SUMMARY OF THE INVENTION It is an object of the invention to overcome limitations of conventional equestrian barriers. It is another object of the invention to permit a jump cup to be easily positioned and retained at various heights along and upright standard. It is still a further object of the invention to position a jump cup at various positions along a standard in a reliable and precise manner. It is yet another object of the invention to permit a standard and jump cup to be easily formed from recycled plastic. To achieve these objects, a first aspect of the invention includes a standard having a post supported by a base. An inner side of the post has notches formed therein at predetermined intervals. The notches are defined by an upper notch surface that is substantially flat and by a lower notch surface that is arcuate, is concave upward, and has a substantially constant radius of curvature. A jump cup has a first end defined by upper and lower surfaces that correspond substantially to the upper and lower notch surfaces respectively. A second and of the jump cup has a support surface adapted to support a pole or the like. The first end of the jump cup is inserted into a desired one of the notches to be retained at a desired height along the standard. A second aspect of the invention includes a standard having a post supported by a base. An outer side of the post has grooves formed therein at predetermined intervals. An inner side of the post has notches formed therein at predetermined intervals. The notches are defined by an upper notch surface that is substantially flat and by a lower notch surface that is arcuate, is concave upward, and has a substantially constant radius of curvature. A jump cup has a first end defined by upper and lower surfaces that correspond substantially to the upper and lower notch surfaces respectively. A second end of the jump cup has a support surface adapted to support a pole or the like. A bracket is pivotally mounted to the jump cup. The first and of the jump cup is inserted into a desired one of the notches to be retained at a desired height along the standard. The standard passes through an opening in the bracket and a portion of the bracket is received in one of the grooves to provide additional stability. BRIEF DESCRIPTION OF THE DRAWING The invention will be described through preferred embodiments illustrated in the drawing in which: FIG. 1 is a perspective view of a standard and jump cup according to the invention; FIG. 2 is a side view of a barrier constituted of a pair of standards and jump cups of FIG. 1; FIG. 3 is a perspective view of another standard and jump cup according to the invention; FIG. 4 is a side view of a barrier constituted of a pair of standards and jump cups of FIG. 3; and FIG. 5 is a side view of the jump cup of FIGS. 3 and 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 1 illustrates standard 20 and jump cup 30 in accordance with the invention. Standard 20 includes base 24 and upwardly extending post 22. Base 24 is constituted of a plurality, four in FIG. 1, of triangular blocks defining opening 25 in a top portion of base 24. Post 22 is received in opening 25 and secured therein through a pressure fit or by being seated on cross braces 21 (see FIG. 2) extending between the triangular blocks. Base 24 can be molded as a single piece, or as multiple pieces secured together with adhesive or the like, out of a resinous material made from recycled plastic or other materials. Further, post 22 can be made of similar materials and be formed integrally or separately from base 24. A first surface, or inside surface, of post 22 has notches 26 (only one of which is indicated) formed therein at regular intervals. Notches 26 each are defined by upper surface 27 and lower surface 29. Upper surface 27 is substantially flat and preferably substantially perpendicular to a longitudinal, i.e. vertical, axis of post 22. Lower surface 29 is arcuate, extends from upper surface 27 to the inside surface, and preferably has a constant radius of curvature. The preferred dimensions of notches 26 are discussed in greater detail below. Jump cup 30 is essentially a block having first end 32 and second end 34. First end 32 has a curved lower surface which corresponds substantially with lower surface 29 of notches 26. Second end 34 has support area 36 defined thereon by an indentation, recess, or other configuration capable of supporting an end of bar 40 (see FIG. 2). First end 32 can be loosely fitted into any one of notches 26 to provide support for bar 40 as illustrated in FIG. 2. First end 32 is retained in notch 26 due to a torsional component of force due to gravity as indicated by arrow x. The configuration of notch 26 and first end 32 permits first end 32 to be easily inserted in notch 26, with virtually no frictional or other resistance, and retained in notch 26 by the torsional component of gravity which tends to cause the curved lower surface of first end 32 to slide upward along curved lower surface 29 of notch 26 thereby pressing a flat upper portion of first end 32 against upper surface 27 of notch 26. FIG. 2 illustrates a barrier constituted of a pair of standards 20 and a corresponding pair of jump cups 30. As illustrated, standards 20 are placed in opposition to one another with the first surfaces, or inside surfaces, facing towards one another. In this position, jump cups 30 can be inserted into appropriate notches 26 depending on the desired height of the barrier. For example, notches 26 can be spaced apart by 6 inches to permit the barrier height to be adjusted in 6 inch intervals. Once jump cups 30 are inserted into notches 26, jump cups 30 are retained on standards 20 in the manner describe above. Bar 40 is then placed on jump cups 30 with respective ends of bar 40 resting on support areas 36 of jump cups 30. It is apparent that the barrier can be easily set up and adjusted to a broad range of desired heights. Further, because jump cups 30 are pressed against upper surface 27 of notch 26, the height of jump cups 30, and thus the height of the barrier, is accurately maintained. Of course, plural pairs of standards 20 and jump cups 30 can be placed in series to support plural bars 40 to constitute a barrier having increased depth. Applicant has found that particular dimensions of standard 20 and jump cup 30 yield optimal results. As illustrated in FIG. 1, the interval b between notches 26 is preferably 6 inches to permit the barrier height to be adjusted at 6 inch intervals. The radius of curvature of lower surface 29 of notch 26 is preferably between 11/2 and 21/2 inches and most preferably 2 inches. The height of each notch 26 relative to the bottom of base 24 is adjusted to yield barrier heights at even half foot intervals based on the depth of the recess defining support area 36, the thickness of bar 40, and other known variables. The distance a between upper surface 27 and lower surface 29, at the inside surface of post 22, is preferably 2 inches. The length c and width b of a cross section of post 22 are both preferably 4 inches. The width e of each triangular portion of base 24 is preferably 4 inches. The height f of each triangular portion of base 24 is preferably 16 inches. The height g of standard 20 in its entirety is typically about 66 inches. The length and width h of a bottom of base 24 is preferably 24 inches. The dimensions of first end 32 of jump cup 30 correspond substantially to the dimensions of notch 26, with adequate tolerance to permit easy insertion and removal of first end 32 into and from notch 26. FIGS. 3 and 4 illustrate another standard 20' and jump cup 30' according to the invention. Many aspects of standard 20' and jump cup 30' are similar to standard 20 and jump cup 30 of FIGS. 1 and 2 and similar elements are labeled with the same reference numerals. A second surface, or outside surface, of post 22 has grooves 50 (only one of which is indicated) formed therein at regular intervals. The preferred configuration of grooves 50 is described in detail below. Grooves 50 are defined in post 22 by upper and lower angled surfaces which each define about a 45° angle with respect to the other surface of post 22. Of course, this angle can be adjusted based on the dimensions of other elements described below. Bracket 40 is pivotally coupled to jump cup 30' at pivot point 48 (see FIG. 5). Bracket 40 is constituted of levers 42 which extend substantially in parallel to one another and cross member 44 connecting free ends of levers 42 to define an opening in bracket 40. Abutment surface 46 is defined on cross member 44 and extends at about a 45 degree angle with respect to longitudinal axes of levers 42. FIG. 4 illustrates a barrier constituted of a pair of standards 20' and jump cups 30' having brackets 40. Each bracket 40 extends around post 22 with post 22 extending through the opening defined in bracket 40. Jump cup 30' can be pivoted upward to lie essentially parallel to post 22 to permit jump cup 30' and bracket 40 to be moved up or down along post 22. Jump cup 30' can then be pivoted to the position illustrated in FIG. 4 to be seated in an appropriate one of notches 26 while cross member 46 is seated in a groove 50 immediately above the notch 26. Bracket 40 provides additional stability to jump cup 30'. Preferably grooves 50 are formed at interval k which is about 6 inches. Of course, interval k can be adjusted to correspond to the distance between notches 26. Preferably, the height j of grooves 50 is about 2 inches. The length n of levers 42 is preferably 9 inches and the length r of jump cup 30' is 7 inches. The height q of cross member 24 is preferably 2 inches. Of course, cross member 24 should be sized to be received in slot 50 with adequate tolerance. The particular dimensions disclosed above are exemplary. However, these dimensions can be adjusted as desired and thus are not to be construed as limiting the scope of the invention. The invention can be formed of any suitable materials, such as recycled plastic, wood, metal, or the like. Further, multiple posts can be supported by a single base and can be fixed to the base or removable from the base. The invention has been described through examples that are not intended to limit the scope of the invention as defined by the appended claims.
An equestrian barrier having a standard, a jump cup that can be adjusted to various positions along the standard, and a pole supported by the jump cup. The standard has notches formed at intervals therein. Each notch is defined by a lower arcuate surface. An end of the jump cup has a corresponding curved surface. When the end of the jump cup is received in one of the notches, the pair of curved surfaces oppose each other and the torsional component of gravity tends to seat an upper surface of the jump cup against an upper surface of the notch. A bracket can be provided to increase stability by engaging a groove formed on an opposite side of the standard.
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CROSS REFERENCE TO RELATED APPLICATIONS This application is the U.S. National Stage of International Application No. PCT/BEO1/00094 filed 28 May, 2001, and claims the priority of European Application No. 00201815.8 filed 24 May 2000. The entirety of each of those applications is incorporated herein by reference. BACKGROUND OF THE INVENTION The present invention relates to a process for forming a vitreous layer on a refractory surface, in which a vitrifying agent is projected by means of an apparatus against the said surface with an oxygen-containing carrier gas and simultaneously with a combustible gas, the latter generating a combustion flame. High-temperature furnaces used for various industrial applications may be subjected to a certain amount of degradation over time. It is found that dust or by-products coming from the raw materials and/or from their reaction products accumulate on the various refractory surfaces of the furnace. This-phenomenon is particularly important in coke ovens where the combustion of coal generates the formation of graphite carbon on the refractory surfaces and into the thickness of the refractories, where it may cause cracking. This carbon builds up particularly in the region of the feeding ports, the roof, the flue of the oven and the space between the door and the jambs. Not only does this build-up embrittle the refractory materials but it also decreases the level of charging of the oven. In addition, the cracking is a source of pollution. It is also observed that the mechanical extraction of the coke is made more difficult because of the friction existing between the coke and the graphite carbon deposited on the refractory surfaces. The build-up of graphite carbon in the charging ports also slows down the rate of charging of the oven. Currently, in order to remove the graphite carbon it is necessary to stop the oven and burn off the graphite carbon to generate CO 2 . This process, given its slowness, results in the loss of productivity and, moreover, can create local overheating in the refractory bricks, something which may in course of time damage the oven. In the feeding ports, mechanical cleaning is sometimes necessary in order to remove the graphite carbon, which most particularly damages them. Patent Application EP 908 428 A1 (Kawasaki Steel Corporation) proposes the application in the carbonizing chamber of the oven of a vitrifying agent containing predominantly silica and/or Na 2 O and to prevent the graphite carbon from adhering to the exposed surfaces. The process involves spraying an aqueous solution or a suspension in water of this agent onto a surface while maintaining the temperature of the latter at 900° C. or more for at least 30 minutes. Patent Application EP 773 203 A1 (Asahi Chemical Company) describes a similar process for forming a layer of metal oxides on the walls of a coke oven. The process consists in the hot application, using conventional methods, of an aquceous solution or a suspension in water of metal oxide precursors. In both these methods, the water which comes into contact with the hot refractory surface causes a thermal shock which embrittles the refractory bricks. Silica, of which the refractory bricks are composed, contains a small amount of lime (CaO) which, in the presence of water, is converted into hydrated lime (Ca(OH) 2 ) This hydration causes these bricks to crumble. The vitreous layers formed according to these processes are generally very thin and tend to wear away rapidly. Patent Application JP 58-33189 (Kurosaki & Nippon Steel) describes the formation of a vitreous coating for repairing the walls of coke ovens by flame-spraying a mixture of vitrifiable oxides. The layer thus formed tends to crystallize over time, which causes it to crack. To remedy this drawback, Patent Application DE 38 03 047 A1 (Kurosaki & Nippon Steel) describes the formation of a vitreous coating having a high silica content which contains, during its formation, at least 60% of a crystalline phase. SUMMARY OF THE INVENTION One of the objects of the present invention is to solve the various problems mentioned. The present invention relates to a process for forming a vitreous layer on a refractory surface, in which a vitrifying agent is projected by means of an apparatus against the said surface with an oxygen-containing carrier gas and simultaneously with a combustible gas, the latter generating a combustion flame, characterized in that the vitrifying agent comprises particles of cullet and in that the flame generated provides, at least partially, the heat needed to form the vitreous layer on the surface. With respect to the spraying of a mixture of vitrifiable oxides, the present process has the advantage of requiring less energy to melt the raw material particles, and consequently provides a higher rate of application. It also allows the addition of oxide particles which keep their individuality in the layer, which thus benefits from a higher mechanical strength. The advantage of such a process is also that the vitrifying agent does not need to be dissolved or put into suspension in water. Furthermore, the heat released by the flame generated by the combustion of the combustible gas makes it possible to obtain a vitreous layer without necessarily working on a hot surface. This heat also makes it possible to obtain a layer which is molten at the temperature of the flame, but is mechanically resistant at the operating temperature of the oven. Preferably, the vitrifying agent is projected by means of an apparatus comprising a tubular lance having a central duct, via which the vitrifying agent and the oxygen-containing gas are delivered, and one or more peripheral ducts via which the combustible gas is delivered. The combustible gas burns in contact with an oxygen-containing gas. The combustible gas can generate the flame when it comes into contact at the outlet of the lance with the oxygen-containing carrier gas which serves to project the vitrifying agent. Oxygen-containing gas may also be, and preferably, is introduced into and mixed with the combustible gas in the peripheral duct or ducts so as to generate a flame at the outlet of the lance. Preferably, the carrier gas is oxygen, that is to say pure oxygen of industrial quality, while the combustible gas is propane, acetylene or tetrene®, which is a propylene-based gas. These various combustible gases, and particularly acetylene or tetrene®, make it possible to obtain a high flame temperature, possibly above 2 000° C. The apparatus used to project the vitrifying agent preferably comprises a single tubular lance, which makes it easier to apply the vitreous layer locally to the regions most exposed to graphite carbon deposition. The apparatus is preferably the lance described in Patent Application WO 98/46 367 A1 (Glaverbel) by means of which the vitrifying agent is sprayed simultaneously with flame generation. BRIEF DESCRIPTION OF THE DRAWINGS In the drawings, FIG. I is a vertical section through a convergent/divergent nozzle and FIG. II is a cross-section of a convergent/divergent nozzle. DETAILED DESCRIPTION The tubular lance used to project the vitrifying agent may be fitted with a duck-bill nozzle or with a convergent/divergent nozzle. FIG. I is a vertical section through a convergent/divergent nozzle and FIG. II is a cross section through this nozzle. This nozzle has a central diameter 1 , an outlet diameter 2 and an external diameter 3 . The central diameter is, for example, at least 8 mm and at most 12 mm ( 1 , FIGS. I and II). Using such a nozzle makes it possible to deposit a vitreous layer over a larger refractory surface than that involving the use of cylindrical nozzles, while still maintaining identical the other projection parameters. If, by way of example, the vitrifying agent is projeted from a lance placed at a distance of 60 mm from the refractory surface, the surface covered by a convergent/divergent nozzle having a central diameter of 12 mm is at least 10 times larger than that covered by a cylindrical nozzle having a central diameter of 12 mm. The duck-bill nozzle terminates in a slot and allows strips of vitreous material to be deposited, for example strips having a width of about 200 mm using a lance whose central tube has a diameter of 16 mm, when the nozzle is located at 60 mm from the substrate. The lance will be placed at a maximum distance of 100 mm and preferably at a distance of 60 mm from the surface onto which the vitrifying agent is projected. The vitrifying agent comprises cullet, such as borosilicate cullet, and/or soda-lime cullet. The latter has the advantage of being easily available, inexpensive and easy to melt. The cullet will preferably contain, by weight, 55%-75% SiO 2 , 0%-10% Al 2 O 3 , 0%-15% B 2 O 3 , 0%-16% CaO, 0%-10% MgO, 0%-20% Na 2 O, 0%-10% K 2 O, 0%-10% BaO, 0%-10% SrO, 0%-5% ZrO 2 . The soda-lime cullet will preferably contain, by weight, 55%-75% SiO 2 , 0%-7% Al 2 O 3 , 0%-5% B 2 O 3 , 0%-16% CaO, 0%-10% MgO, 10%-20% Na 2 O, 0%-10% K 2 O, 0%-10% BaO, 0%-10% SrO, 0%-5% ZrO 2 and, optionally, colouring agents. The borosilicate cullet will preferably contain, by weight, 55%-75% SiO 2 , 0%-10% Al 2 O 3 , 0%-10% CaO, 0%-10% Na 2 O, 0%-5% K 2 O, 5%-15% B 2 O 3 and, optionally, minor constituents such as TiO 2 , BaO, ZnO and Fe 2 O 3 . The cullet particles generally have a diameter of less than 2 000 μm and preferably less than 600 μm. It is in fact important for the cullet particles not to be too large so as to form a homogeneous vitreous layer and so as to melt easily. The vitrifying agent may also contain, in addition to the cullet, certain additives such as metal oxides and/or metals. These additives make it possible to obtain a vitreous layer having a higher melting point than when they are not present. Moreover, if the metal or metals present burn, the heat released by their combustion combined with the heat of the flame generated by combustion of the combustible gas makes it possible to cover surfaces whose temperature is lower than when one works without these metals. Prefarably, the vitrifying agent contains at least 40% by weight of cullet, allowing a low permeability of the formed layer. The metal oxide particles have a diameter of less than or equal to 2 000 μm and the metal particles have a diameter of less than or equal to 50 μm. These particle sizes favour the formation of a homogeneous vitreous layer. Furthermore, the smaller the diameter of the metal particles the greater their reactivity. Moreover, since the thickness of the vitreous layer formed is proportional to the size of the oxide particles, it is preferable for this not to be too great so as not to modify in the course of time; the rate of charging of the oven. The thickness of the vitreous layer will preferably vary from a minimum of 0.1 mm to a maximum of 5 mm. The vitrifying agent may contain various metal oxides among which zirconium oxide (ZrO 2 ), alumina (Al 2 O 3 ) or titanium oxide (TiO 2 ), or oxide mixtures such as AZS (a refractory product containing Al 2 O 3 , ZrO 2 and SiO 2 ), will be preferred. AZS is supplied in the form of the ground refractory product. ZrO 2 is reputed to be a “neutral” element and therefore does not carry the risk of giving rise to reactions other than those intended for forming the vitreous layer on the refractory surface. Furthermore, the presence of ZrO 2 improves the thermal properties of the vitreous layer at high temperature. ZrO 2 may be provided in the form of particles of refractory material such as AZS. AZS contains a vitreous phase which will enrich, with zirconia and alumina, the vitreous layer formed and will improve its thermomechanical properties. Al 2 O 3 has the properties of being very wear-resistant and abrasion-resistant. Alumina can also diffuse into the glass, thereby increasing its thermal resistance. It has also been noted that the vitreous layers formed using a vitrifying agent comprising cullet and alumina are in general less porous. The alumina can be supplied in the form of kaolin. TiO 2 can act as a catalyst for the oxidation of carbon. In this way, it will be even more difficult for carbon to build up on the refractory surface of the oven. The vitrifying agent may contain various metals preferably chosen from aluminium and silicon. Although silicon is generally classed as a semi-metal, it will be regarded here as a metal since within the content of the present invention it behaves like the other metals. The presence of metal tends to facilitate the penetration of the metal oxide into the vitreous layer, making it smoother and more resistant at high temperature. The unburned metal particles oxidize during operation of the oven and thereby increase the temperature and facilitate the oxidation of carbon. Silicon or aluminium oxidizing in the vitreous layer increase its viscosity. Aluminium has the particular feature of oxidizing easily, releasing a large amount of heat, which makes it even easier to form the vitreous layer. The vitrifying agent is projected onto a surface having a temperature of between 20° C. and 1 400° C. Above 1 400° C., the vitreous layer starts to melt and no longer adheres to the surface onto which it is projected. In one particular application of the process, the vitrifying agent is sprayed onto a surface having a temperature of between 800° C. and 1 100° C. This temperature range is usually encountered in the field of coke ovens in which the problem of graphite carbon deposition on the internal surfaces is most frequent. It is possible to treat an oven locally, for example at the feeding ports, but also over the entire internal surface of the oven. The vitreous layer obtained according to the present invention has a degree of permeability. The higher the permeability, the more porous the vitreous layer. The lower the permeability, the greater the sealing provided by the vitreous layer. If the permeability is high, graphite carbon can infiltrate the pores of the vitreous layer and little by little will build up on the refractory layer. The permeability of a material, defined according to the standard III.13 (PRE/R 16) 78, p. 1 communicated to the ISO/TC33, is the property that refractory materials have of being penetrated by a gas due to the effect of a pressure difference. It is represented by μ, contained in the following formula, which expresses the volume of gas passing through a given material in a given time: V/t =μ·(1/η)·( S/L )·( p 1 −p 2 )·( p 1 +p 2 )/2 p where V=volume of gas at an absolute pressure p passing through the material in a time t; S=flow cross section of the material; L=thickness of the material penetrated; P 1 =absolute pressure at the gas inlet; P 2 =absolute pressure at the gas outlet; p=pressure at which the gas that has flowed is measured; η=dynamic viscosity of the gas at the test temperature. In the rest of the text, the permeability will be expressed in nanoperms (nP). One nanoperm is equal to 10 −13 m 2 . The permeability will preferably have a value of less than that of the permeability of the refractory surface, the latter generally having a permeability value of between 5 nanoperms and 15 nanoperms. The present invention will be illustrated in greater detail with the aid of the examples which follow. EXAMPLE 1 A lance fitted with a convergent/divergent nozzle was used to project the vitrifying agent composed, by weight, of 40% cullet, containing, by weight, 70.5%-71.5% SiO 2 , 9.5%-9.6% CaO, 13.8%-14.0% Na 2 O, 0.58%-0.63% Al 2 O 3 and 0.7%-0.9% Fe 2 O 3 , and 60% tabular alumina (98.3% of the alumina particles had a diameter of between 180 μm and 600 μm). The substrate consisted of silica bricks. The lance used in this example is identical, except for the shape of the nozzle, to that described in Patent Application WO 98/46 367 A1 (Glaverbel) and had a central duct and several peripheral ducts. The vitrifying agent was projected by means of the central duct, in the presence of oxygen, at the same time as propane and oxygen were projected separately by means of the peripheral ducts. The vitrifying agent was projected with a mass flow rate of 27 kg/h. The oxygen serving as carrier gas had a flow rate of 24 m 3 /h. The oxygen and propane pressures in the peripheral ducts were 4 bar and 2 bar, respectively. The combustion of the propane with oxygen, which took place at the outlets of these peripheral ducts, generated a flame. The refractory surface was swept by the lance, keeping a distance of 60 mm from it, and at an angle of 90° to this surface. The mixture was projected with a velocity of about 150 km/h and the projection time was 10 s/dm 2 of refractory surface. The latter had a temperature of 1 100° C. Two measurements of the permeability of the surface after it had cooled were taken. One measurement was taken right after application of the vitreous layer and the other after 48 hours had elapsed at a temperature of 1 100° C. The latter measurement made it possible to check; the flow of the vitreous layer over the wall. Should the vitreous layer flow, the permeability becomes higher. The permeability of the surface covered with the vitreous layer was measured immediately after this layer was applied and cooled and it had a value of 0.24 nanoperms. The permeability of this same surface after 48 h of ageing at 1 100° C., followed by its cooling, was 0.4 nanoperms. As a variant, the silica bricks were replaced with chamotte bricks. A similar result was obtained. EXAMPLES 2 to 15 We now illustrate in Table 1 other embodiments of the invention. In Examples 2 to 14, the carrier gas was pure oxygen of industrial quality and the combustible gas was propane. In Example 15, the oxygen-containing carrier gas was dry air. In Examples 2 to 7, the oxygen-containing, carrier gas had a flow rate of 22 m 3 /h and in Examples 8 to 15 it was 24 m 3 /h. The alumina used in Examples 8, 9 and 14 was the same as that used in Example 1, whereas that used in Example 15 was electrocast alumina P120 (the diameter of the alumina particles was less than 150 μm). The zirconium oxide used in Examples 6, 7 and 10-13 may have a maximum content of 6% by weight of CaO serving as stabilizing agent. Unless otherwise specified in Table 1, the other parameters were identical to those in Example 1. For a refractory surface at the same temperature, it may be seen that the vitreous layer resulting from projecting a vitrifying agent containing cullet and an additive (Examples 4-12) is less permeable than the vitreous layer resulting from projecting a vitrifying agent containing 100 cullet (Examples 2 and 3). It may be noted that lower permeability values are obtained when the cullet content is at least 40% by weight (Examples 2 to 12). EXAMPLE 16 A lance similar to that described in Example 1 was used to project a mixture of particles containing, by weight 55% soda-lime cullet similar to that in Example 1, 29% alumina, 10% ground AZS refractory and 6% aluminium. The maximum size of the cullet particles was 1 mm. The maximum size of the alumina particles was 600 μm. The maximum size of the AZS particles was 500 μm. The size of the aluminium particles did not exceed 45 μm. The mixture was projected onto chamotte bricks placed in the inner wall of a coke oven at a point where the wall temperature is 1 250° C. The mixture was sprayed at a rate of 42 kg/h into oxygen having a flow rate of 19 Nm 3 /h. The oxygen pressure and the propane pressure in the peripheral ducts were 3.2 bar and 1.6bar, respectively. The vitreous layer formed at a rate of about 0.05 m 2 /minute. The permeability of the surface covered with the vitreous layer was 0.35 nanoperm after 7 days at 1 250° C. EXAMPLES 17 to 22 Table 2 illustrates further examples using other particle mixtures, in which the projection parameters and the particle sizes were those of Example 16. The silicon particles had a size of less than 45 μm. The zircon particles had a maxium size of 1 mm. Examples 19 to 22 used a borosilicate cullet the maximum particle size of which was 1 mm. This cullet was mainly composed, by weight, of 65.8% SiO 2 5.1% Al 2 O 3 , 7.2% Na 2 O, 2.1% K 2 O, 1.5% TiO 2 , 14.3% B 2 O 3 and 1.4% BaO. The surface on which the vitreous layer was formed was at 1 200° C. in Example 17 and at 1 250° C. in Examples 18 to 22. The substrate consisted of chamotte bricks but a similar result was found when the substrate consisted of silica bricks. TABLE 1 Examples Conditions 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Percentage 100 100 95 95 90 90 80 60 80 60 40 20 38 50 of cullet Diameter of <355 <355 <355 <355 <355 <355 <355 <355 <355 <355 <355 <355 <425 <425 the cullet particles (μm) Metal oxide / / TiO 2 TiO 2 ZrO 2 ZrO 2 Al a O 3 Al 2 O 3 ZrO 2 ZrO 2 ZrO 2 ZrO 2 Al 2 O 3 Al 2 O 3 Percentage / / 5 5 10 10 20 40 20 40 60 80 50 50 of metal oxide Metal / / / / / / / / / / / / Si/Al / Percentage / / / / / / / / / / / / 7/5 / of metal Temperature 1 100 800 1 100 800 1 100 800 1 100 1 100 1 100 1 100 1 100 1 100 1 100 1 100 of the refractory surface (° C.) Permeability 1.00 0.32 0.11 0.05 0.27 0.05 0.10 0.83 0.38 0.17 0.21 1.57 2.78 2.39 Permeability 2.96 1.69 2.69 1.74 1.23 2.69 0.56 2.74 2.17 1.10 2.19 26.77 / / after 48 h at 1 100° C. Permeability / / / / / / / / / / / / 3.46 5.06 after 24 h at 1 100° C. TABLE 2 Examples Conditions 17 18 19 20 21 22 Percentage of 60 55 28 soda-lime cullet Percentage of / / 27 55 55 55 borosilicate cullet Metal oxide Al 2 O 3 Al 2 O 3 Al 2 O 3 Al 2 O 3 Al 2 O 3 Al 2 O 3 Metal oxide AZS ZrO 2 . SiO 2 Percentage of 34 25 35 25 29/10 24/15 metal oxides Metal Al Al Al Al Al Al Metal Si Percentage of 6 6/14 10 20 6 6 metal Temperature 1 200 1 250 1 250 1 250 1 250 1 250 of the refractory surface (° C.) Permeability 0.77 0.77 0.93 1.48 1.03 0.9 after 7 days at 1 250° C.
A process for forming a vitreous layer on a refractory surface, in which a vitrifying agent is projected by means of an apparatus against the surface with an oxygen-containing carrier gas and simultaneously with a combustible gas, the latter generating a combustion flame, characterized in that the vitrifying agent comprises particles of cullet and in that the flame generated provides, at least partially, the heat needed to form the vitreous layer on the surface. The vitreous layer thus formed makes it possible to prevent the build-up, on the refractory walls of high-temperature ovens, of dust or by-products coming from the raw materials and/or their reaction products.
2
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority based on U.S. Provisional Application No. 61/494,019, filed Jun. 7, 2012. The contents of each of which is incorporated by reference in its entirety. TECHNICAL FIELD OF THE INVENTION [0002] The present invention relates in general to the field of sterilization, specifically to an apparatus and method of making and using vacuum and steam for the disinfection of natural products including plant materials and powders in need of sterilization before they can be used by manufacturers and/or consumers. STATEMENT OF FEDERALLY FUNDED RESEARCH [0003] None. INCORPORATION-BY-REFERENCE OF MATERIALS FILED ON COMPACT DISC [0004] None. BACKGROUND OF THE INVENTION [0005] Without limiting the scope of the invention, its background is described in connection with a sterilization apparatus and method of sterilization of powders. [0006] For example, U.S. Pat. No. 7,895,938 discloses an apparatus and method for steam disinfection of a liquid dispensing machine and a method of using the apparatus. This is achieved by injecting steam into a drained dispenser machine equipped with a cover having a safety valve that matches the top of the dispenser to provide sealing. The steam is generated by a steam generator physically integrated with the new liquid dispenser machine. The steam circulates through the fluid compartment of the liquid dispenser and continues through its conduits and exits at the taps which are held open by a stepped boss. The sanitizing period can be adjusted and controlled. [0007] For example, U.S. Pat. No. 7,892,483 discloses a sterilization process for steroid compositions, in which the steroid is heat treated in the form of a wet mass comprising the steroid, water and an excipient. [0008] For example, U.S. Pat. No. 7,858,028 discloses a pasteurizing or sterilizing process and relates to a method for preparing a product having a low content of microorganisms by using steam. The method can be used to pasteurize or sterilize a product, while retaining the activity of one or more active substances that may be present in the product, and relates to a method wherein a product is dried with air. BRIEF SUMMARY OF THE INVENTION [0009] The present invention provides a process for sterilization of natural products without negatively effecting the properties of the final product by providing one or more samples comprising one or more natural products for sterilization before they can be used by manufacturers and/or consumers; placing the one or more samples in a steam permeable container; placing the steam permeable container in a sterilization chamber; heating the sterilization chamber to a predetermined temperature; controlling the predetermined temperature; pressurizing the sterilization chamber to a predetermined pressure; controlling the predetermined pressure; supplying an amount of steam to the sterilization chamber; and controlling an application time for the heating, the pressurizing and the supplying the amount of steam to achieve at least partial sterilization of the one or more samples. [0010] The present invention provides dry steam sterilized natural product produced by providing one or more samples comprising one or more natural products for sterilization before they can be used by manufacturers and/or consumers; placing the one or more samples in a steam permeable container; placing the steam permeable container in a sterilization chamber; heating the sterilization chamber to a predetermined temperature; controlling the predetermined temperature; pressurizing the sterilization chamber to a predetermined pressure; controlling the predetermined pressure; supplying an amount of steam to the sterilization chamber; and controlling an application time for the heating, the pressurizing and the supplying the amount of steam to achieve at least partial sterilization of the one or more samples. [0011] The present invention provides a system for the sterilization of natural products without negatively effecting the properties of the system having a sterilization chamber; a sample area within the sterilization chamber to hold one or more steam permeable containers; a heater source connected to the sterilization chamber for heating the sterilization chamber to a predetermined temperature; a heater control unit connected to the heater source for controlling the predetermined temperature; a pressure source connected to the sterilization chamber for pressurizing the sterilization chamber to a predetermined pressure; a pressure control unit connected to the pressure source for controlling the predetermined pressure; a steam aperture for supplying steam to the sterilization chamber; a steam control unit connected to the temperature and duration of the steam; and an interface connected to the heater control unit, pressure control unit, and steam control unit. BRIEF DESCRIPTION OF THE DRAWINGS [0012] For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which: [0013] FIGS. 1 a and 1 b are graphs that illustrate the plate count testing as a function of time. [0014] FIG. 2 illustrates a graph of the vacuum and temperature profile for the steam sterilization cycle. [0015] FIG. 3 is an image and location of numerous samples distributed on six shelves on two racks. [0016] FIG. 4 is a table of the weights of the samples. [0017] FIGS. 5 , 6 and 7 are graphs of the temperature as a function of time for the samples. [0018] FIGS. 8 a and 8 b are tables of the results from the sterilization of the samples. [0019] FIGS. 9 and 10 are graphs of the results from the sterilization of the samples. [0020] FIG. 11 is an image of numerous samples distributed on six shelves on two racks. [0021] FIG. 12 is a table of the weights of the samples. [0022] FIGS. 13 and 14 are graphs of the temperature as a function of time for the samples. [0023] FIGS. 15 a and 16 a are tables of the results from the sterilization of the samples and FIGS. 15 b and 16 b are graphs of the results from the sterilization of the samples. [0024] FIG. 17 is an image of numerous samples distributed on six shelves on two racks. [0025] FIGS. 18-19 are tables of the weights of the samples. [0026] FIGS. 20 , 21 and 22 are graphs of the temperature as a function of time for the samples. [0027] FIGS. 23 and 24 are graphs of the APC Micro test results showing cfu/g as a function of samples location. [0028] FIGS. 25 a and 26 a are tables of the weights of the samples and FIGS. 25 b and 26 b are graphs of the APC Micro test results showing cfu/g as a function of samples location. DETAILED DESCRIPTION OF THE INVENTION [0029] While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention. [0030] To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims. [0031] The present invention may be used to process many natural products including plant materials and powders in need of sterilization before they can be used by manufacturers and/or consumers. The current techniques (e.g., Gamma Radiation, Ethylene Oxide, Ozone, and Ultra Violet Light) used in the industry result in a negative environmental effect, while other treatments introduce residual components into the samples that are carried through the process and provide a negative effect on the properties of the final product. The present invention provides a dry steam sterilization process that does not harm the product, leave residual chemicals, or damage the environment. The present invention provides a combination of elevated temperature, dry steam and vacuum (e.g., negative pressure) to reduce the bioburden. The present invention provides 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 50, 100 or more (incremental variations thereof) cycles to inactive thermo resistant composition, e.g., thermo resistant spores. [0032] The present invention provides methods and apparatus to produce products sterilized with superheated steam instead of dry air. In one embodiment of a substantially closed system, the superheated steam is recirculated. The part of the steam that condenses during the process will generally be discharged from the device. The superheated steam is passed through the drying chamber and ensures that water evaporates from the product. After leaving the drying chamber, the steam including the steam coming from the product can again be compressed and heated to the desired degree of superheating, and the resulting superheated steam can be returned to the drying chamber. Consequently, the required drying energy is much lower than when conventionally drying with dry air, which cannot be reused so easily. The conditions of drying are selected subject to the product. Those skilled in the art are deemed to reach a suitable optimization on the basis of their normal expert knowledge. In most of the cases, the temperature will range between 150 and 500° C. [0033] It may be clear that the quality of the injected steam must be in accordance with the required quality of the product to be dried. For example, the steam drying of a food product requires that the injected steam be of food grade, and therefore in essence free from mineral oil, moisture droplets, microorganisms, and dirt. [0034] The steam drying according to the invention has the additional advantage that because of the fact that steam is already introduced into the mixing chamber of the nozzle, atomization and pasteurization or sterilization takes place simultaneously, and in a substantially closed system the excess steam can be reused for atomization. Optionally, a product partially dried through drying can be redried to a lower moisture content in a conventional manner, such as, for instance, with a fluid bed-drying device. [0035] Moreover, it has turned out that in a powder dried according to the invention undesired organoleptic changes have been hardly effected, if effected at all, and that a powder dried according to the invention has sufficient solubility for various applications. A method according to the invention is thus suitable for preparing a product consumable without health risks, optionally after reconstitution in a suitable liquid. [0036] Furthermore, the present invention can be used for the manufacture of products or other powdered products that, besides heat-sensitive components, also contain other ingredients in which germs are killed and the activity of heat-sensitive substances, if present, can be retained. It has turned out that such a sterilized and optionally dried product prepared according to the present invention has a suitable microbiological quality. It has also been found after evaluation of a product that during drying according to the invention much fewer undesired reactions, such as oxidation, reduction, irreversible denaturation, and the like, take place than when using conventional techniques. The invention will now be illustrated further with reference to some examples. [0037] The steam treatment apparatus according to the present invention provides a rapid temperature rise by subjecting powders to dry steam at a partial pressure less than about 760 mm Hg. The steam is saturated, and thus the temperature of the steam is held at a desired final temperature. The steam temperature-pressure relationships are well known, and need not be reviewed herein. [0038] The steam in one preferred embodiment is provided by a steam generator, which boils, for example, potable or distilled water. This water is degassed prior to use, so that the steam contains few impurities and almost no non-condensing impurities. The steam generator may be at any temperature above the final temperature, e.g., 150 C, as the thermal treatment of the droplets derives mainly from the latent heat of vaporization of the droplets, and very little from the absolute temperature of the steam. Preferably, the steam is saturated, which will define its temperature in a given atmosphere. [0039] Thus, the mass flow rate of the saturated steam entering into the treatment system (in relation to the product flow rate and any withdrawal of steam or external heat transfer), controls the process treatment temperature. In the case of an over-pressure steam generator, the mass flow rate is restricted to prevent the treated droplets from reaching too high a temperature, or supersaturation conditions. [0040] The steam is derived from a boiler. Tight control of temperature may require a high temperature boiler with a control valve near the reactor vessel. In other words, in order to ensure adequate flow of steam into the reactor, an excess capacity should be available from the boiler. Control is effected near the reactor, to avoid time response delays or oscillation. The water in the boiler is preferably degassed to eliminate non-condensable components. The boiler may have a superheater at its outlet, to heat the steam over a condensation equilibrium level. [0041] The steam is injected into the reactor vessel through a number of steam injection ports, spaced within the chamber, so that the region distant from the fluid injection port maintains a relatively constant water vapor pressure. The walls of the reactor vessel should be maintained at least at or slightly above the final operating temperature, to avoid condensation of steam on the wall and unnecessary product dilution. This may be accomplished by any suitable heating system. [0042] One embodiment of the present invention provides a dry steam sterilization process to produce a clean sterilization process and apparatus that is natural and organic with no harm to the product, no residual chemicals and no damage to the environment. The product is controlled and monitored for consistent, homogenous treatment results and preserves product integrity and optimal sensory properties to the product with little or no aesthetic changes. The present invention can use a wide range of products including herbs, botanicals and spices, to free-flowing powders can be treated with this process. [0043] The present invention includes devices and methods that reduce (e.g., >4 log reduction) the presence of TPC, yeasts and molds, with little or no aesthetic changes while preserving product integrity and optimal sensory properties. In addition, the present invention can accommodate numerous samples that are similar or different and allows each individual sample to be controlled and monitored to ensure consistent and homogenous treatment results. [0044] The present invention provides a dry steam sterilization process. The samples are placed in a sample container. The sample container is placed into a sterilization chamber to provide dry steam and exert both temperature and pressure on the sample. The sterilization chamber undergoes a controlled dry steam cycle for a predetermined temperature at a predetermined pressure based on the sample, batch size, product density. For example, the controlled dry steam cycle may be for 5-300 minutes at between 100 to 300° F. at 0-15 psi. One specific embodiment has a controlled dry steam cycle for 15-25 minutes at 150° F. at 5 psi. Sterilization chambers can be formed in any particular dimensions to accommodate the sample containers. The sterilization chamber is cooled to cool the sample container before transfer to a clean room. The sample container can then be prepared for use, storage or shipping. [0045] One embodiment includes placing the samples on a rack having numerous shelves to separate and hold the samples. The rack is then placed into the sterilization chamber. In some instances the rack is a rolling cart that can be rolled into the sterilization chamber. The samples are dried at a temperature of between 185 and 230° F. for between 8 and 12 hours. The sterilization chamber then receives a flush with steam for about 1 hour. The sterilization chamber was held at 220° F. for 45 minutes and a vacuum of about 3 inches of Hg applied to the sterilization chamber for about 30 minutes. The sterilization chamber was then vented to the atmosphere and allowed to cool. [0046] One sample of 10 kg of Peppermint Leaves and Walnut shells were placed into bags and positioned in the sterilization chamber for sterilization using the dry steam vacuum of the present invention and showed a greater than 5 log reduction for both gram negative and gram positive spore-forming bacteria after 2 and 5 minutes of treatment. [0047] More general parameters include samples that are dried by heating the sterilization chamber to a temperature of between 150 and 350° F. for between 1 and 24 hours. The sterilization chamber then receives a flush with steam for between 1 and 24 hours. The sterilization chamber was held at between 150 and 350° F. for between 0 and 24 hour and a vacuum of about from about −35 psi to 35 psi applied to the sterilization chamber for about 30 minutes. The sterilization chamber was then vented to the atmosphere and allowed to cool. [0048] Aerobic Plate Count Testing was used to indicate the level of microorganisms in the raw material and the finished product. Bacteria (BBL 11764) was incubated at 33-35° C. for 48-72 hours with tryptic soy agar with lecithin and TWEEN. Mold (BBL 11550) was incubated at 20-25° C. for 5 days with potato dextrose agar. Diluent (BBL 12201) was used with tat broth. [0049] FIGS. 1 a and 1 b are graphs that illustrate the plate count testing (cfu/gm) as a function of time starting before sterilization and including at 2 minutes at 230° C. and 5 minutes at 230° C. [0050] FIG. 2 illustrates a graph of the vacuum and temperature profile for the steam sterilization cycle as a function of time for rosemary leaves, walnut shells, comfrey leaves, licorice root, rosemary cube, horsetail leaf, and calendula flower. [0051] FIG. 3 is an image of another embodiment C 154 of the present invention that provides numerous samples distributed on six shelves on two racks. The samples are distributed flat on the shelf with an adsorbent powder placed below the samples. The samples are placed on cart 1 and cart 2 and placed into the sterilization chamber. The sterilization chamber was pre-heated. At 4 hours 30 minutes the steam and air pressure were turned off and the vessel was allowed to sit overnight. The temperature slowly decreased to 160-190° F. The next morning, the steam and air pressure were turned on and the vessel heated another 6 hours until the product was above 180° F. Eighteen thermocouples (not shown) were placed in bags (not shown) throughout the product. During the heat up process four locations (not shown) indicated thermocouple noise and are considered abnormal readings: thermocouple # 4 (not shown) in Bag R 2 - 5 (not shown); thermocouple # 8 (not shown) in Bag R 2 - 26 (not shown); thermocouple # 9 (not shown) in Bag R 2 - 26 (not shown) and thermocouple # 16 (not shown) in Bag R 1 - 15 (not shown). The remaining fourteen thermocouples (not shown) appeared to function normally. The samples (not shown) were treated with a 15-minute exposure, with eighteen thermocouples (not shown) placed in bags (not shown) throughout the product (not shown). During the run cycle, one location (not shown) indicated thermocouple noise and is considered an abnormal reading: thermocouple # 16 (not shown) in Bag R 1 - 15 (not shown) but the remaining seventeen thermocouples (not shown) appeared to function normally. During exposure, the eighteen thermocouples (not shown) temperatures ranged from 220°-253.44° F. At the end of the run cycle, thermocouple # 1 in Bag R 2 - 1 showed an abnormal increase in temperature after the cycle. [0052] FIG. 4 is a table of the weights of the samples. The coldest run position was located in rack 1 (not shown), Bag 26 (not shown) (thermocouple # 17 ) of FIG. 3 at 40 minutes. The hottest run position was in rack 2 , bag 13 (thermocouple # 6 (not shown)). The pre-sample micro read was APC 77,000 cfu/g and Yeast/Mold <10 cfu/g. The post-process micro read was APC <10 cfu/g and Yeast/Mold <10 cfu/g. The disposition was 5 log reduction. The samples (not shown) underwent post processing by removing 2 oz., were taken from eighteen of the 96 bags (not shown) placed throughout representative of the vessel area (not shown). Sampling locations are indicated in yellow on the cart mapping diagram of FIG. 3 . Each bag was sampled in three locations: left, middle and right, with one sample location corresponding with the thermocouple placement in the bag (not shown). A total of 54 samples (not shown) were gathered and tested for the run. [0053] FIGS. 5-7 are graphs of the temperature as a function of time for the samples. [0054] FIGS. 8 a and 8 b are tables of the results from the sterilization of the samples. [0055] FIGS. 9 and 10 are graphs of the results from the sterilization of the samples. The average percent loss per product after grind has been determined to be on average <1%. The sterilization results are shown below: [0000] Product Cinnamon Cassia Powder Bag # APC Yeast/Mold 1 20 <10 9 <10 <10 18 <10 <10 21 <10 <10 29 <10 <10 [0056] FIG. 11 is an image of another embodiment of the present invention that provides numerous samples distributed on six shelves on two racks. The samples are distributed flat on the shelf with an adsorbent powder placed below the samples. The samples are placed on cart 1 and cart 2 and placed into the sterilization chamber. The sterilization chamber was pre-heated. At 4 hours 30 minutes the steam and air pressure were turned off and the vessel was allowed to sit overnight. The temperature slowly decreased to 160-190° F. The next morning, the steam and air pressure were turned on and the vessel heated another 6 hours until the product was above 180° F. The samples were treated with a 15-minute exposure. [0057] FIG. 12 is a table of the weights of the samples. The post-process micro read was APC <10 cfu/g and Yeast/Mold <10 cfu/g. [0058] FIGS. 13 and 14 are graphs of the temperature as a function of time for the samples. [0059] FIGS. 15 a and 16 a are tables of the results from the sterilization of the samples and FIGS. 15 b and 16 b are graphs of the results from the sterilization of the samples. [0060] FIG. 17 is an image of another embodiment C 156 of the present invention that provides numerous samples distributed on six shelves on two racks. The samples are distributed flat on the shelf with an adsorbent powder placed below the samples. The samples are placed on cart 1 and cart 2 and placed into the sterilization chamber. The sterilization chamber was pre-heated with the jacket temperature set at 200° F. and allowed vessel to sit overnight, approximately 15 hours. The next morning the jacket temperature was increased to 230° F., and in approximately one hour all product reached 180° F. Eighteen (18) thermocouples were placed in bags throughout the product. During the heat up process two (2) locations indicated thermocouple noise and are considered abnormal readings: thermocouple # 18 in Bag R 1 - 28 and thermocouple # 21 in Bag R 1 - 3 . The remaining sixteen (16) thermocouples appeared to function normally. The samples were treated with a 15-minute exposure, with eighteen (18) thermocouples placed in bags throughout the product. During the run cycle, three (3) locations indicated thermocouple noise and is considered an abnormal reading: thermocouple # 8 in Bag R 2 - 26 ; thermocouple # 16 in Bag R 1 - 15 and thermocouple # 14 in Bag R 1 - 11 but the remaining fifteen (15) thermocouples appeared to function normally. During exposure, the eighteen (18) thermocouples temperatures ranged from 220°-249.04° F. [0061] FIGS. 18-19 are tables of the weights of the samples: The coldest run position was in rack 1 , Bag 26 (thermocouple # 17 ) at 36 minutes. The hottest run position was in rack 2 , bag 13 (thermocouple # 15 ). The pre-sample micro read was APC 148,000 cfu/g and Yeast/Mold N/A. The post-process micro read is listed below: [0000] Post Actipure Micro All Sample Sample Sample Samples 1 2 3 Yeast/ Log Cart 1 APC APC APC Mold Reduction Bag 1 Chamomile 60 1670 290 <10 4 Powder Bag 3 Chamomile 80 830 10 <10 4 Powder Bag 5 Chamomile 6240 8320 580 <10 3 Powder Bag 11 Nopal 60 30 <10 <10 4 Powder Bag 13 Nopal 10 <10 <10 <10 4 Powder Bag 15 Nopal 20 <10 <10 <10 4 Powder Bag 26 Damiana 30 440 20 <10 3 Powder Bag 28 Yucca 32240 6240 2680 <10 2 Root Powder Bag 30 Wild 13000 45240 790 <10 2 Yarn Powder [0000] Post Actipure Micro All Sample Sample Sample Samples 1 2 3 Yeast/ Log Cart 2 APC APC APC Mold Reduction Bag 1 Chamomile 210 110 7800 <10 3 Powder Bag 3 Chamomile 20 20 10 <10 5 Powder Bag 5 Chamomile 1110 1430 60 <10 3 Powder Bag 11 Chamomile 620 1100 8320 <10 3 Powder Bag 13 Chamomile 40 680 210 <10 4 Powder Bag 15 Chamomile 190 2840 1090 <10 3 Powder Bag 26 Chamomile 20 40 650 <10 4 Powder Bag 28 Chamomile <10 550 40 <10 4 Powder Bag 30 Chamomile 1720 220 30 <10 4 Powder [0062] The disposition was 5 log Reduction. The samples underwent post processing by removing 2 oz., were taken from eighteen (18) of the 96 bags placed throughout representative of the vessel area. Sampling locations are indicated in yellow on the cart mapping diagram. Each bag was sampled in three (3) locations: left, middle and right, with one (1) sample location corresponding with the thermocouple placement in the bag. A total of 54 samples were gathered and tested for the run. The average percent loss per product for the run is as follows: [0000] Product % Loss Aloe Vera Powder 4% Chamomile Powder 7% Damiana Powder 4% Napal Powder 4% Wild Yam Powder 5% Yucca Root Powder 3% [0063] FIGS. 20 , 21 and 22 are graphs of the temperature as a function of time for the samples. FIGS. 23 and 24 are graphs of the APC Micro test results showing cfu/g as a function of samples location. FIGS. 25 a and 26 a are tables of the weights of the samples and FIGS. 25 b and 26 b are graphs of the APC Micro test results showing cfu/g as a function of samples location. [0064] It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method, kit, reagent, or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention. [0065] It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims. [0066] All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. [0067] The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects. [0068] As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. [0069] The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, MB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. [0070] All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.
The present invention provides a system for the sterilization of natural products without negatively effecting the properties of the system having a sterilization chamber; a sample area within the sterilization chamber to hold one or more steam permeable containers; a heater source connected to the sterilization chamber for heating the sterilization chamber to a predetermined temperature; a heater control unit connected to the heater source for controlling the predetermined temperature; a pressure source connected to the sterilization chamber for pressurizing the sterilization chamber to a predetermined pressure; a pressure control unit connected to the pressure source for controlling the predetermined pressure; a steam aperture for supplying steam to the sterilization chamber; a steam control unit connected to the temperature and duration of the steam; and an interface connected to the heater control unit, pressure control unit, and steam control unit.
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RELATED APPLICATION This application is a continuation-in-part of U.S. Ser. No. 07/580,552 filed Sep. 11, 1990 now abandoned. BACKGROUND OF THE INVENTION The present invention relates to a mill for comminuting a food product. Devices for comminuting a product, such as a food product, are well known in the art and typically comprise a rotating impeller having a plurality of generally radially extending blades disposed within a generally annular array of fixed, circumferentially spaced apart knives. During the past 25 years, these devices have been manufactured with an inside diameter of the annular knife array of approximately 6 inches. Although the impellers of these known devices may be operated at speeds up to 12,000 revolutions per minute, they are typically restricted to approximately 10,300 revolutions per minute to prolong the impeller bearing life. These devices have proven superior in their size reduction ability to any other commercially available equipment. Examples of such devices can be found in the following U.S. Pat. Nos. 3,251,389; 3,51,557; 3,608,598; and 3,888,426. Recently, homogenizers have been introduced into the commercial arena that are capable, under some circumstances, of producing a comminuted product similar to that produced by the aforementioned mills. The homogenizers, which have found particular acceptance in the field of manufacturing peanut butter and ketchup, typically comprise a reciprocating piston moveable in an open ended cylinder. The open end of the cylinder is closed by a ball or plate that is tightly pressed against the end of the cylinder by a heavy spring. Movement of the piston away from the open end draws the product into the cylinder. Then, as the piston is advanced toward the open end, the pressure exerted on the product forces the ball or plate slightly away from the open end such that a thin stream of product is squirted out of the cylinder at a very high speed against a stationary surface. The destructive forces acting on the product rupture it into small particles. The homogenizers, while generally successful, require extensive, and therefore costly, maintenance and pose some danger to the operating personnel due to the high internal pressures applied to the homogenizer structure. Also, the product must first be reduced to a liquid before it can be pumped into the homogenizer. In all of today's methods of making peanut butter, the roasted and de-skinned peanut halves are first converted into a hot liquid by passing them through a Bauer-type mill. The Bauer-type mill consists of two circular plates with the flat surfaces slightly separated and facing each other. These facing surfaces have bumps or protrusions that grind the peanuts when they are fed to the centers of the plates with one of the plates rotating at a high speed. One of the present methods of making a high quality peanut butter is to pass the product from the Bauer-type mill through a series of rotating mills of the afore-described type. Passing the product through this plurality of rotating mills (typically two such mills are utilized) further reduces the sizes of the peanut particles. A swept wall heat exchanger is used between the two rotating mills to cool the peanut butter before it enters the second mill. It is also known to substitute the use of a homogenizer for the plurality of rotating mills to produce the final peanut butter product. Tomato ketchup is made from ripe tomatoes after removing the skin, the seeds, and a portion of the water. Vinegar, sugar and spices are added to produce the flavor. The amount of insoluble material and its characteristics vary considerably with different batches of tomatoes. All ketchup manufacturers use some method to reduce the particle size of the insoluble material in the ketchup. Generally speaking, the smaller the particle size, the thicker will be the ketchup. The small particle size presents more surface area to collect the liquid, thereby increasing the viscosity of the product. At the present time, some manufacturers use rotating mills to produce their product, others use only homogenizers, while still others utilize a combination of the two devices. The Bostwick test is a standardized test to determine the viscosity of a ketchup product. The test is made with a channel which is 5 cm wide by 3.8 cm in depth with the ends of the channel closed. A moveable gate is located across the channel at a distance of 5.2 cm from one end. The ketchup is poured into the box so as to be level with its top and the gate is raised to permit the ketchup to run lengthwise beyond the gate opening. The bottom of the channel is marked in centimeters and, after 30 seconds, the viscosity is determined by measuring the distance in centimeters the ketchup has moved into the channel. This distance represents the Bostwick number for any particular test. SUMMARY OF THE INVENTION A rotating mill for comminuting a product, such as a food product, is disclosed in which the shape and orientation of the impeller blades, as well as the increased peripheral speed of the impeller, produce a finely comminuted product that was heretofore only capable with a multi-stage production process. The impeller rotates within an annular array of knives and the product is fed into the center area of the impeller. Initial contact with inner portions of the impeller blades breaks the product and urges it back toward the center of the impeller. Continued contact between the impeller blades and the product imparts rotation to the product. As the rotational speed of the product increases, centrifugal force urges it across product directing surfaces of the impeller blades and into the knife array. The product contacting the knives and passing between the knives is further comminuted by the process. The increased peripheral speed of the impeller was achieved by enlarging the diameter of the impeller, thereby increasing the peripheral speed without requiring higher revolutions per minute, thereby preserving the impeller bearing life. Since the energy exerted on the product increases with the square of the relative peripheral speed, the energy generated on the product by this invention has markedly increased over the known devices, thereby resulting in a finer comminuted product using the same rotational speed of the impeller. The impeller has a generally circular impeller body that is rotatable about a generally centrally located rotational axis and a plurality of impeller blades attached to the impeller body. Each of the impeller blades has a product directing surface, which may be concave and which extends along an axis extending in a generally chordal direction across the impeller body. As the product is fed onto the rotating impeller it initially contacts an inner portion of the rapidly moving impeller blades. Such contact breaks the product and, due to the orientation of the blades, urges the product toward the center of the impeller. The contact with the inner portions of the blades also imparts forward rotational movement to the product. Subsequent contact between the inner portions of the blades and the product increases the rotational speed of the product such that centrifugal force urges it radially outwardly and into contact with the product directing surfaces on the impeller blades. The concave product directing surfaces direct the food product towards the longitudinal center of the impeller blades to prevent any leakage of the product from the impeller wheel through the space between it and the knife array. When the product is forced off of the blades by centrifugal force, it contacts the center of a surrounding array of knives. Each impeller blade defines a product impact surface on a generally radially inwardly facing portion which makes initial contact with the product as it passes radially outwardly over the impeller body. This initial contact contributes toward the partial size reduction of the product, imparts a forward speed to the product and also tends to deflect the product back toward the center of the impeller. This causes the product to be struck as many times as possible before it reaches sufficient rotational speed to move outwardly along the product directing surfaces of the impeller blades. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front view of the comminuting mill according to the present invention. FIG. 2 is a side view of the mill shown in FIG. 1. FIG. 3 is a partial, cross sectional view of the mill according to the present invention. FIG. 4 is a partial, perspective view, partially broken away, illustrating the impeller and the annular knife assembly according to the present invention. FIG. 5 is a perspective view of one of the knives utilized in the annular knife array. FIG. 6 is a plan view of the impeller according to the present invention. FIG. 7 is a cross-sectional view of the impeller taken along line VII--VII in FIG. 6. FIG. 8 is a cross-sectional view of one of the impeller blades taken along line VIII--VIII in FIG. 6. FIG. 9 is a partial, perspective view of the impeller illustrating the product impact surfaces. FIGS. 10-13 are partial views of an impeller blade tip and the knife array illustrating the known orientations of the knives in the array. FIG. 14 is a partial, schematic view illustrating the impeller blade tip and the knives showing a first embodiment of the knife orientation according to the present invention. FIG. 15 is a view, similar to that shown in FIG. 14, illustrating a second embodiment of the orientation of the knives in the annular array. FIG. 16 is a sectional view, similar to FIG. 3, illustrating an alternative product feed mechanism. FIGS. 17A-17E are plan views of impeller blades showing alternative variations of the blade design. FIG. 18 is a perspective view of an alternate embodiment of a knife utilized in the annular knife array. FIG. 19 is a cross-sectional view taken along lines XIX--XIX in FIG. 18. FIG. 20 is a partial schematic view illustrating the impeller blade tip and the knives of FIG. 18 in a first orientation. FIG. 21 is a partial, schematic view illustrating the impeller blade tip and the knives of FIG. 18 in a second orientation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The comminuting apparatus according to the invention is shown in FIGS. 1 and 2 and generally comprises a comminuting mill structure 10, a feed mechanism 12 to feed the product into the comminuting mill 10 and an electric motor 14 to drive the impeller of the comminuting mill 10. A drive transfer mechanism 16, which may comprise drive belts or drive gears, may be interposed between the electric motor 14 and the impeller of the comminuting mill 10 to transfer the rotary motion from the motor output shaft to the impeller. These elements may be mounted on a base support 18, which may also support the control panel 20 containing the known elements to control the operations of the motor and/or the feed mechanism 12. The feed mechanism 12 is illustrated as comprising a feed screw-type conveyor 22 actuated in known fashion by an interconnection with feed screw drive motor 24. Feed screw 22 contacts the product placed in hopper 26 and transfers it to the comminuting mill 10. Comminuting mill 10 is surrounded by a mill housing 32 having an open bottom portion 32a. Thus, in the comminuting operation, the product travels into hopper 26 in the direction of arrow 28, is transported to the comminuting mill 10 via screw conveyor 22 and the comminuted product exits through the bottom 32a of the mill housing 32 in the direction of arrow 34. As best seen in FIGS. 3, 4 and 6, the comminuting mill 10 comprises an impeller 36 rotatably located within an annular knife assembly 38 so as to rotate about axis 76. The impeller 36 comprises an impeller body 40 having a plurality of impeller blades 42 attached thereto. Each of the impeller blades 42 has a product directing surface 44 extending along its length. The product directing surface 44 is a linear surface extending parallel to, and may be concavely curved about, a straight axis extending in a generally chordal direction across the impeller body 40, as illustrated in FIG. 6 by axis 46. In known fashion, a hardened metal tip element 48 may be attached to the radially outermost portion of each of the impeller blades. The straight, chordal product directing surfaces 44 have been found to be a marked improvement over the curved leading surfaces of the impeller blades shown in U.S. Pat. No. 3,888,426. The curved leading blade surfaces cause the product to actually wear holes through the blade behind the blade tip. Straight surfaces 44 oriented in a generally chordal direction have been found to alleviate this problem and such blades have shown little wear after extensive use. As can be seen from FIG. 6, the tip element 48, as well as the radially outermost forward portion of each blade 42, extends in a generally radial direction. Since the chordal product directing surface 44 extends at an angle to the radial blade tip portion, the product passing along surface 44 is suspended without touching any surface for an instant after leaving surface 44 before it is contacted by the associated blade tip. Once the blade tip contacts the product, it carries it in a rotational path over the knives. The concave product directing surfaces 44 perform three basic functions: 1) their radially innermost portions direct part of the incoming product back toward the center of the impeller; 2) they convey the product past the point where it could ordinarily leak out of the assembly if the leading surface of the blade was flat; and, 3) they deposit the product in the middle of the knives. A radially inner portion of each impeller blade 42 defines a product impact surface 43 illustrated by shading in FIG. 9. Surface 43 makes initial contact with the product as it passes radially outwardly over the impeller 40, which contact contributes toward the partial size reduction of the product. With sixteen blades on an impeller rotating at 9,300 revolutions per minute, the incoming product is struck by these surfaces at approximately 2,480 times per second. Product impact surfaces 43 impart a forward rotational speed to the product and also direct the product back toward the center of the impeller 40. When the product initially enters the impeller, it has only a very small rotational velocity. The rotational speed differential between the impeller blades and the product is so great that the product cannot enter between the impeller blades because they are moving past the product too rapidly. Each contact between the product and the impact surfaces 43 imparts a greater rotational speed to the product. At some point, the rotational speed of the product becomes great enough that the centrifugal force acting on the product will force it between the impeller blades and into contact with the product directing surfaces 44. The product will then pass along surfaces 44 and into contact with knives 50. As illustrated by the shaded portion in FIG. 9, product impact surfaces 43 comprise convex portions 43a on either side of product directing surface 44, as well as by a radially innermost portion 44a of concave surface 44. The orientation of surfaces 43a and 44a is such that they tend to deflect the product back toward the center of the impeller, thereby causing the product to be struck as many times as possible before it moves outward between the blades. Alternatively, the radially inner portions of impeller blade 42 may assume, but are not limited to, the configurations illustrated in FIGS. 17A-17E. The annular knife assembly comprises, as best illustrated in FIGS. 3 and 4, a plurality of knives 50 supported in a spaced apart, annular array around the periphery of the impeller 36 by knife holding rings 52 and 54. The edges of the knives 50 may be beveled, as at 50a and 50b in FIG. 5, so as to engage correspondingly angled surfaces 52a and 54a formed on knife holding rings 52 and 54, respectively. A resilient ring 56 extends circumferentially around the knife holding ring 52 so as to resiliently bear against an end of each of the knives 50. The blades are prevented from moving radially outwardly by contact with the legs of knife locating ring 58. Ring 58 is attached to knife supporting rings 62 and 64, to which are also mounted knife holding rings 52 and 54. A cover plate 66 may be attached to knife support ring 64, while knife support ring 62 is fixedly attached to locating plate 68. Inner knife locating rings 70 and 72 are attached to cover plate 66 and locating plate 68, respectively, and are located on either side of the impeller blades 42. These elements prevent the radially inward movement of any of the knives 50 and also define a pocket-like cavity in which the outwardly projecting portions of the impeller blades 42 travel. The mounting and support structure for the knives 50, as well as the mechanism by which the product is comminuted by passing radially outwardly over the rotating impeller, into contact with and through the spaces between the knives 50 is set forth in U.S. Pat. Nos. 3,251,389; 3,251,557; 3,608,598; and 3,888,426, each of which is incorporated herein by reference. The knife orientations disclosed in the aforementioned patents are illustrated in FIGS. 10, 11, 12 and 13. As illustrated in FIG. 10, each of the individual knives 50 may be oriented such that their upstream side (measured in relation to the direction of travel of blade 40, indicated by arrow 75) lies along a radius 74 passing through the rotational axis 76 of the impeller 40. Thus, the trailing edge of each knife lies at a greater radius than the leading edge of the adjacent knife. As variations on this general orientation, and as illustrated in FIGS. 11 and 12, the knives can be tilted about their upstream, radially innermost cutting edges 51 in either direction. Finally, in another known knife orientation, each of the downstream surfaces can be oriented in alignment with a radius line 74 as illustrated in FIG. 13. It has been found that the knife orientations shown in FIGS. 14 and 15 can be used with the comminuting mill according this invention to produce a more finely comminuted product than was possible with the known devices. While any of the known knife orientations can be used with the mill according to this invention, those orientations shown in FIGS. 14 and 15 have proven particularly suitable. In FIG. 14, the knives 50 are each oriented such that their upstream surface extends generally parallel to a radius line 74, but the radius line 74 is displaced toward the downstream surface a small distance from the upstream surface. The trailing or downstream edge of each knife lies at a greater radius than the leading edge of the adjacent knife. In FIG. 15, the radius line 74 passes approximately through the center of the knives 50 such that it lies in a plane passing through the center of the knife. In this instance, the trailing or downstream edge of each knife is at approximately the same radius at the leading or upstream edge of the adjacent knife. The centrifugal force exerted on the product by the blades causes a portion of the product to be extruded into the space between the knives. This portion is subsequently sheared off and forced between the knives by the blade tip. Depending upon the specific product to be comminuted, the circumferential spacing between each of the individual knives 50 may be varied to produce the desired end product. The degree of size reduction, with any particular knife configuration, is controlled by the number of knives in a particular assembly. In general, the greater the number of knives, the greater will be the size reduction. The knife orientation shown in FIG. 14, when used in conjunction with the mill according to the present invention, has been found to be particularly effective in making peanut butter. A single mill according to this invention, in one test, produced a superior quality peanut butter at approximately 11,000 pounds per hour using 175 horsepower. This single comminuting mill thus replaces the two Bauer-type mills (using 75 horsepower each), and 4 rotating comminuting mills (each using 40 horsepower each, 6 motor driven pumps and 1 swept wall heat exchanger. Use of this mill quite obviously saves vast amounts of energy, as well as producing a superior quality product in a single-step operation. TABLE I______________________________________Test Number 1 2 3 4______________________________________Inside Diameter of Knife 12 12 12 6Assembly In InchesRevolutions per Minute 4,400 6,400 9,400 8,800Peripheral Speed in 230 335 492 230Feet per SecondDepth of Cut in Inches .0062 .0062 .0062 .0059Space Between Blades .0236 .0236 .0236 .0270in InchesVolume under 31 Microns, 77.7% 81.8% 90.5% 76.5%.0012 InchesVolume over 88 Microns, 5.9% 2.4% 0.0% 5.5%.0035 InchesVolume over 176 Microns, 2.8% 0.0 0.0 2.1%.0069 InchesMean Value in Microns 27.17 20.64 14.66 26.89______________________________________ Test results of the mill according to the present invention in comparison with a known rotary mill are noted in Table I above. These tests were conducted by milling half peanuts in a single pass. Tests 1-3 were conducted with the rotating mill according to this invention, while Test 4 utilized a known rotary mill having a diameter of 6 inches across the innermost ends of the knives. The test results illustrate the effect of changing the peripheral speed of the impeller and, consequently, the speed of the peanuts over the knives, on the quality of the resulting peanut butter product. In Tests 1, 2 and 3, the mill according to this present invention, which has a diameter inside the knife assembly of 12 inches, was tested at varying impeller speeds. As the impeller speed was increased from 4,400 revolutions per minute (Test 1) to 9,400 revolutions per minute (Test 3), the very small particles increased in volume from 77.7% to 90.5%. The number of particles larger than 88 microns decreased from 5.9% in Test 1 to 0% in Test 3. Peanut butter made in Test 3 would be considered to be the highest quality, while that made in Test 1 would be of poor quality. Test 4 was made with a 6 inch diameter knife assembly, but having a similar depth of cut and circumferential spacing between the knives to the mill in Test 1. The mill in Test 4 utilized a rotational speed of 8,800 revolutions per minute. The peripheral speed of the impeller blade tips is approximately the same for Tests 4 and 1 and the resulting product has approximately similar characteristics. Thus, these tests are indicative that the peripheral speed of the impeller blade tips and, consequently, the peripheral speed of the product over the knives produces the unexpected results, which are not the result of merely increasing the diameter of the impeller. Tests have also proven that the present invention improves the viscosity over the known mill types. Tests were made by passing ketchup having a Bostwick number of 9.5 through a known comminuting mill with a 6" diameter and through a mill according to the present invention having a 12" diameter. After a single pass, the 6" mill improved the viscosity of the ketchup to a Bostwick number of 6.9, while the mill according to the present invention improved the viscosity to a Bostwick number of 3.6. It is believed that the 3.6 viscosity is equal to or better than that produced by known homogenizers. By using a 12" inside diameter knife array with an impeller rotating at a speed of 9,300 RPM, the product moves over the knives at 487 feet per second or 332 miles per hour and is pressed against the knives at 14,747 times it own weight. Tests using high speed photography were conducted using the present invention to mill half roasted peanuts. It was observed that the peanut halves were reduced to butter by the time the product had reached the knives. It was also observed that the product directing surfaces 44 caused the peanut butter to be laid down in a narrow ribbon in the middle of the knives. As a result of the observances, additional tests were conducted without the knife array. The peanut halves were directed onto the 12" impeller rotating at 9,300 RPM and were discharged against housing 32. The product resulting from the test was peanut butter. This clearly demonstrates that the instant invention performs a two-stage operation, with the action of the impeller blades impacting on the product as a first stage size reduction and the action of the knife array a second stage size reduction. Analysis of the peanut butter produced using only the impeller indicated that 59.5% of the particles were under 31 microns, 9.9% were over 88 microns and the mean value of particle size was 37.48 microns. The mill according to the present invention also reduces the unwanted heat and the excessive power that is caused by friction between the fast moving product and the stationary knife assembly. As the product moves radially outwardly on the impeller, it reaches the limit of the impeller, at which time it is discharged into a relatively deep pocket defined between the inner knife locating rings 70 and 72, and the faces of the knives 50. The concave product directing surfaces 44, formed in each of the impeller blades 42, causes the product to be deposited generally in the middle of the knives 50 to greatly reduce the friction between the fast moving product and the stationary faces of rings 70 and 72. The stationary rings 70 and 72 are necessary to prevent the product from escaping between the outer limits of the impeller and the inner surfaces of the knife array without it coming in contact with the knives 50. The knife orientation illustrated in FIG. 15 has, in preliminary, tests, proven to be of great benefit in making a high quality tomato ketchup. In controlled tests, the knife orientation shown in FIG. 15 was compared with that illustrated in FIG. 13 with the result that the power requirements were decreased by approximately 23.7% without a change in the viscosity of the product. The comminuting mill according to the invention may be used with a variety of feed mechanisms. Although a screw-type conveyor 22 has been described, if the feed product is fluid, it may be pumped by known pumping devices onto the impeller 40 through feed input conduit 80, as illustrated in FIG. 16. The structure and operating characteristics of the mill shown in FIG. 16 are the same as the previously described mill. Although the comminuting mill according to the invention has proven remarkably successful, it has been noted that, under certain circumstances, the product being size reduced may be compacted in the spaces between the individual knives. When this compacting occurs, additional pressure must be produced on the inner side of the knives to force the material through and out of the spaces between the knives. It is sometimes necessary to build up a product layer inside the inner knife surfaces in order to generate sufficient centrigugal force to cause the product to exit between the knives. This results in excessive power requirements with a corresponding and undesired increase in the temperature of the product. The milling of certain kinds of materials with the comminuting mill may cause the product to be compacted between the knives to the extent that more material cannot be milled. FIGS. 18 and 19 illustrate an alternative embodiment of a knife design intended to alleviate these problems. The knife 82 may have beveled edges 82a and 82b, as well as a first side surface 82c and a second side surface 82d that extends non-parallel to the first side surface. The side surface 82d is angled such that the inner surface 82e has a width greater than that of an outer surface 82f. The knife 82 may be used in any of the knife orientations illustrated in FIGS. 10-15. FIG. 20 illustrates the preferred orientation of the knives 82, which is similar to that illustrated in FIG. 14. As can be seen, the angled side surface 82d provides increased clearance area between the adjacent knives in order to prevent the compacting of the milled material between the adjacent knives. In FIG. 20, the sides 82c of the knives face in the upstream direction relative to the blade 42 which is moving in the direction of arrow 75. When the upstream inner edges of the knives become worn, the knives may be changed to the orientation illustrated in FIG. 21 wherein the sides 82c face in the downstream direction. In this orientation, angled sides 82d still provide sufficient clearance between the adjacent knives to prevent the comminuted material from compacting in this space. Comparison tests have been conducted between the comminuting mill of the present invention utilizing the knives illustrated in FIG. 5 and utilizing the knives illustrated in FIG. 18. In these tests, roasted peanut halves were milled at 11,000 pounds per hour with peanut oil being added. One hundred thirty pounds of peanuts were used in each test. Maximum particle sizes, as indicated by a Hegman gauge were the same. Milling the peanut halves with knives as illustrated in FIG. 5 required 150 horsepower and resulted in the temperature of the milled product being approximately 160° F. With the knives illustrated in FIG. 18, only 112 horsepower was required and the final temperature of the milled product was 135° F. Quite obviously, the use of the knives illustrated in FIG. 18 lowers the power required for the milling process and decreases the temperature of the milled product. The foregoing description is provided for illustrative purposes only and should not be construed as in any way limiting this invention, the scope of which is defined solely by the appended claims.
A rotating mill for comminuting a product, such as a food product, is disclosed in which the shape and orientation of the impeller blades, as well as the increased peripheral speed of the impeller, produce a finely comminuted product that was heretofore only capable with a multi-stage production process. The impeller rotates within an annular array of knives and the product is fed into the center area of the impeller. Centrifugal force urges the product across the rotating impeller, and into contact with the impeller blades and the knife array. The impeller has a generally circular impeller body that is rotatable about a generally centrally located rotational axis and a plurality of impeller blades attached to the impeller body. Each of the impeller blades has a product directing surface that extends parallel to an axis extending in a generally chordal direction across the impeller body and a product impact surface.
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