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BACKGROUND OF THE INVENTION [0001] The present invention concerns liners, top sheets or cover sheets for personal care products like feminine hygiene products, diapers, training pants and the like. [0002] Liners are designed to be permeable to liquid and to be non-irritating to the skin since they are the outermost layer of a personal care product and so in contact with the wearer. Liners feel soft to the skin and allow urine and menses to penetrate quite easily. Liners have been made from various materials including nonwoven webs, apertured films, foams and combinations thereof. The nonwovens and films may be made from synthetic polymers, including polyolefins like polyethylene and polypropylene. The nonwovens may also be made from natural fibers or combinations of natural and synthetic fibers. Liners may also be made from creped materials such as creped nonwoven webs. [0003] Liners have advanced significantly over the years, though rewet of the wearer's skin and leakage, especially in the case of feminine hygiene products, remains an important issue. There remains a need, therefore, for a liner that will rapidly take in fluids like urine and menses and retard or prevent it from moving upwardly towards the wearer again. SUMMARY OF THE INVENTION [0004] In response to the discussed difficulties and problems encountered in the prior art, a new liner has been developed wherein the liner has a hydrophilic first apertured nonwoven layer laminated with a hydrophobic second apertured nonwoven layer. The apertures may be aligned. The first layer may, further, be made of durably hydrophilic fibers and the second of non-durably hydrophilic fibers (later made hydrophobic). The liner may be made by a spunlace process. The liner may further have a treatment applied to the hydrophilic layer, where the treatment is aloe, vitamin E, mineral oil, baking soda and combinations thereof. [0005] Another embodiment of the liner of the present invention has a first nonwoven layer made from staple, naturally hydrophilic fibers hydroentangled to form a laminate with a second nonwoven layer made from hydrophobic fibers, where the laminate is apertured with an area of 10 to 50 percent. The liner may further have a first layer made from hydrophilic fibers of rayon, pulp, cotton, naturally hydrophilic fibers, and mixtures thereof. The hydrophobic fibers may be made from polymers like polyolefins, polyesters, acrylics and mixtures thereof. [0006] Also provided is a pantiliner having a liquid permeable liner, a liquid impervious baffle, and an absorbent core positioned therebetween. The liner has a hydrophilic first apertured nonwoven layer laminated according to a spunlace process with a hydrophobic second apertured nonwoven layer. The apertures of the first layer and the second layer may be aligned. [0007] The liner of this invention may be used in other personal care products like diapers, training pants, disposable swim wear, absorbent underpants, adult incontinence products, bandages, veterinary and mortuary products, and feminine hygiene products like sanitary napkins. [0008] Also disclosed is a process of making a liner for personal care products involving hydroentangling a hydrophilic first nonwoven layer with a hydrophobic second nonwoven layer and aperturing the layers. The layers may be apertured simultaneously to produce aligned apertures. BRIEF DESCRIPTION OF THE FIGS. [0009] [0009]FIG. 1 is a diagram of a rate block used in testing the materials of this invention. DEFINITIONS [0010] “Disposable” includes being disposed of after a single use and not intended to be washed and reused. “Hydrophilic” describes fibers or the surfaces of fibers that are wetted by the aqueous liquids in contact with the fibers. The degree of wetting of the materials can, in turn, be described in terms of the contact angles and the surface tensions of the liquids and materials involved. Equipment and techniques suitable for measuring the wettability of particular fiber materials can be provided by a Cahn SFA-222 Surface Force Analyzer System, or a substantially equivalent system. When measured with this system, fibers having contact angles less than 90° are designated “wettable” or hydrophilic, while fibers having contact angles equal to or greater than to 90° are designated “nonwettable” or hydrophobic. [0011] As used herein the term “nonwoven fabric or web” means a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted fabric. Nonwoven fabrics or webs have been formed from many processes such as for example, meltblowing processes, spunbonding processes, and bonded carded web processes. The basis weight of nonwoven fabrics is usually expressed in ounces of material per square yard (osy) or grams per square meter (gsm) and the fiber diameters useful are usually expressed in microns. (Note that to convert from osy to gsm, multiply osy by 33.91). [0012] As used herein the term “meltblown fibers” means fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity, usually hot, gas (e.g. air) streams which attenuate the filaments of molten thermoplastic material to reduce their diameter, which may be to microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly dispersed meltblown fibers. Such a process is disclosed, for example, in U.S. Pat. No. 3,849,241 to Butin et al. Meltblown fibers are microfibers which may be continuous or discontinuous, are generally smaller than 10 microns in average diameter, and are generally tacky when deposited onto a collecting surface. “Spunbonded fibers” refers to small diameter fibers that are formed by extruding molten thermoplastic material as filaments from a plurality of fine capillaries of a spinneret. Such a process is disclosed in, for example, U.S. Pat. No. 4,340,563 to Appel et al. and U.S. Pat. No. 3,802,817 to Matsuki et al. The fibers may also have shapes such as those described, for example, in U.S. Pat. No. 5,277,976 to Hogle et al. which describes fibers with unconventional shapes. [0013] As used herein “hydroentangling” means a process wherein a nonwoven web, or layers of a non-woven web, are subjected to streams of a non-compressible fluid, e.g., water, at a high enough energy level and for a sufficient time to entangle the fibers thereof. The fluid may advantageously be used at a pressure of between about 200 and 5000 psig (14-351 kg/cm 2 gauge) from a distance of a few inches (centimeters) above the web while the web is supported by a mesh structure. This process is described in detail in U.S. Pat. No. 3,486,168 to Evans et al. incorporated herein by reference. Nonwoven webs subjected to hydroentangling are referred to as, for example, “spunlace” fabrics. “Bonded carded web” refers to webs that are made from staple fibers which are sent through a combing or carding unit, which separates or breaks apart and aligns the staple fibers in the machine direction to form a generally machine direction-oriented fibrous nonwoven web. This material may be bonded together by methods that include point bonding, through air bonding, ultrasonic bonding, adhesive bonding, etc. [0014] “Airlaying” is a well-known process by which a fibrous nonwoven layer can be formed. In the airlaying process, bundles of small fibers having typical lengths ranging from about 3 to about 52 millimeters (mm) are separated and entrained in an air supply and then deposited onto a forming screen, usually with the assistance of a vacuum supply. The randomly deposited fibers then are bonded to one another using, for example, hot air or a spray adhesive. Airlaying is taught in, for example, U.S. Pat. No. 4,640,810 to Laursen et al. “Personal care product” means products for the absorption of body exudates, such as diapers, training pants, disposable swim wear, absorbent underpants, adult incontinence products, bandages, veterinary and mortuary products, and feminine hygiene products like sanitary napkins and pantiliners. [0015] “Target area” refers to the area or position on a personal care product where an insult is normally delivered by a wearer. Test Methods and Materials [0016] Basis Weight: A circular sample of 3 inches (7.6 cm) diameter is cut and weighed using a balance. Weight is recorded in grams. The weight is divided by the sample area. Five samples are measured and averaged. [0017] Material caliper (thickness): The caliper of a material is a measure of thickness and is measured at 0.05 psi (3.5 g/cm 2 ) with a STARRET®) bulk tester, in units of millimeters. Samples are cut into 4 inch by 4 inch (10.2 cm by 10.2 cm) squares and five samples are tested and the results averaged. [0018] Density: The density of the materials is calculated by dividing the weight per unit area of a sample in grams per square meter (gsm) by the material caliper in millimeters (mm). The caliper should be measured at 0.05 psi (3.5 g/cm 2 ) as mentioned above. The result is multiplied by 0.001 to convert the value to grams per cubic centimeter (g/cc). A total of five samples would be evaluated and averaged for the density values. [0019] Absorption Time and Rewet: This test is used to examine the fluid handling properties of a fabric. The following procedure and equipment are used: [0020] 1. Stack nonwoven intake test sample on top of fluff pad. Record dry weights, dimensions and thickness of each layer. [0021] 2. Center rate block on top of sample. A funnel is placed in a small upper hole in the rate block. [0022] 3. Attach pipette tip is attached to Pipetman. Set Pipetman bottle to deliver 6.0 mL of fluid into the funnel on the rate block. [0023] 4. Insult 6.0 mL of Z-date simulant to absorbent material using the Pipetman bottle. Use the stopwatch to measure the length of time from delivery of fluid to materials until all fluid is fully absorbed. Record this time as the absorption time. [0024] 5. Wait 60 seconds. [0025] 6. Remove rate block from sample and fluff pad. [0026] 7. Place absorbent material sample and fluff pad on the hot water bottle of the pressure stand. Place two pieces of pre-weighed blotter paper on top of the sample. The test button on the pressure gauge is then depressed, starting a program that applies 1.0 psi of pressure to the system for 3 minutes. At the end of 3 minutes, the pressure stand lowers, releasing the pressure from the absorbent materials. [0027] 8. Reweigh the wet blotter papers. Record weights. The moisture pick-up in the blotter reflects the fluid the paper absorbs from the system, in grams. [0028] 9. Weigh and check thicknesses on the embossed fluff and nonwoven test sample. Record results. [0029] Equipment Used [0030] Gilson Pipetman P5000, using RC-5000 pipette tips and pipetman filters [0031] Omega Engineering pressure gauge with timer, Model HHP-701-20 [0032] Blotter rewet pressure stand with water bottle [0033] Stopwatches [0034] Intake fabric sample materials, approximately 5″×5″ [0035] Desorption Material—600 gsm sine-wave embossed fluff [0036] Z-Date fluid, available from the BASF Corp., 2901 North Conkey St., Appleton, Wis. [0037] Plexiglass rateblock (see FIG. 1): The rate block 10 is 3 inches (76.2 mm) wide and 2.87 inches (72.9 mm) deep (into the page) and has an overall height of 1.125 inches (28.6 mm) which includes a center area 19 on the bottom of the rate block 10 that projects farther from the main body of the rate block 10 and has a height of 0.125 inches (3.2 mm) and a width of 0.886 inches (22.5 mm). The rate block 10 has a capillary 12 with an inside diameter of 0.186 inches (4.7 mm) that extends diagonally downward from one side 15 to the center line 16 at an angle of 21.8 degrees from the horizontal. The capillary 12 may be made by drilling the appropriately sized hole from the side 15 of the rate block 10 at the proper angle beginning at a point 0.726 inches (18.4 mm) above the bottom of the rate block 10 ; provided, however, that the starting point of the drill hole in the side 15 must be subsequently plugged so that test fluid will not escape there. The top hole 17 has a diameter of 0.312 inches (7.9 mm), and a depth of 0.625 inches (15.9 mm) so that it intersects the capillary 12 . The top hole 17 is perpendicular to the top of the rate block 10 and is centered 0.28 inches (7.1 mm) from the side 15 . The top hole 17 is the aperture into which the funnel 11 is placed. The center hole 18 is for the purpose of viewing the progression of the test fluid and is actually of an oval shape into the plane of FIG. 1. The center hole 18 is centered width-wise on the rate block 10 and has a bottom hole width of 0.315 inches (8 mm) and length of 1.50 inches (38.1 mm) from center to center of 0.315 inch (8 mm) diameter semi-circles making up the ends of the oval. The oval enlarges in size above 0.44 inches (11.2 mm) from the bottom of the rate block 10 , for ease of viewing, to a width of 0.395 inches (10 mm) and a length of 1.930 inches (49 mm). The top hole 17 and center hole 18 may also be made by drilling. DETAILED DESCRIPTION OF THE INVENTION [0038] Modern personal care products usually have an outer cover, an inner core portion and a liner that goes against the wearer's skin. [0039] The outer cover or “baffle” is designed to be impermeable to liquid in order to keep the clothing or bedding of the wearer from becoming soiled. The impermeable baffle is preferably made from a thin film and is generally made from plastic though other materials may be used. Nonwoven webs, films or film coated nonwovens may be used as the baffle as well. Suitable film compositions for the baffle include polyethylene film which may have an initial thickness of from about 0.5 mil (0.012 millimeter) to about 5.0 mil (0.12 millimeter). The baffle may optionally be composed of a vapor or gas permeable, microporous “breathable” material, that is permeable to vapors or gas yet substantially impermeable to liquid. Breathability can be imparted in polymer films by, for example, using fillers in the film polymer formulation, extruding the filler/polymer formulation into a film and then stretching the film sufficiently to create voids around the filler particles, thereby making the film breathable. Generally, the more filler used and the higher the degree of stretching, the greater the degree of breathability. Other suitable thermoplastic materials like other olefins, nylons, polyesters or copolymers of, for example, polyethylene and polypropylene may also be used. [0040] The core portion of a personal care product is designed to absorb liquids and secondarily to contain solids. The core, known also as an absorbent core, a retention layer, and the like, may be made with pulp and/or superabsorbent materials. These materials absorb liquids quite quickly and efficiently in order to minimize leakage. Core materials may be made according to a number of processes including the coform process, airlaying, and bonding and carding and should be between 50 and 350 gsm. [0041] Various other layers may be included in some personal care products. These include surge layers, usually placed between the liner and core and designed, as the name suggests, to contain large surges of liquid so that the core may absorb it over time. Distribution layers also are included in many personal care products. Distribution layers are usually located next to the core and accept liquid from the surge or liner layer and distribute it to other areas of the core. In this manner, rather than absorbing liquid exclusively in the vicinity of the target area, more of the absorbent core is used. [0042] The liner is designed to be highly permeable to liquid and to be non-irritating to the skin. The liner may optionally have more than one layer or may have one layer in a central area with multiple layers in the side areas. The opposite configuration is also possible with two or more layers in the central area and only one on the sides. [0043] More sophisticated types of liners may incorporate treatments of lotions or medicaments to improve the environment near the skin or to actually improve skin health. Such treatments include aloe, vitamin E, mineral oil, baking soda and other preparations as may be known or developed by those skilled in the art. These treatments are applied to the surface of the liner which will be in contact with the skin of the wearer. [0044] The inventors have found that it is advantageous to have a hydrophilic layer as the outermost bodyside part of the liner, in contact with the wearer. This results in a very rapid absorption of fluids. A hydrophilic liner over an absorbent core, however, will in many cases allow liquid to move upwardly from the core toward the wearer again and “rewet” the skin of the wearer. It will also allow liquid to spread from the target area to the sides of the pad so that the stained area is much larger than that, for example, of a film covered pad. These are regarded as significant negative factors in the design of disposable personal care products since they can result in staining of clothing and bedding, and discomfort to the wearer. [0045] If a hydrophobic layer is placed below the hydrophilic liner, the ability of liquid to move is upwardly from the wetted core is significantly reduced. This results in much better “rewet” values, smaller stain sizes, reduced stain color intensity, and helps keep the wearer drier. [0046] Unfortunately, a hydrophobic layer immediately below the hydrophilic layer also impedes the movement of liquid from the wearer to the absorbent core, causing pooling of liquid on the liner. This can ultimately result in runoff and staining of the clothing and bedding, the very problem that the hydrophobic layer was attempting to solve. [0047] The inventors have solved the problem posed by the hydrophobic layer in two ways; [0048] by aperturing the layers and by joining them using a laminating process involving no chemical or thermal bonding processes. [0049] Aperturing of the hydrophilic layer and hydrophobic layer provides a rapid, open pathway to the absorbent core for liquid from the surface of the liner. This solves the problem posed by the hydrophobic layer's barrier to liquid passage. Once liquid passes through the apertures, it tends to spread out below the hydrophobic layer and go into the absorbent core. Since the apertures are but a small percentage of the surface area of the hydrophilic/hydrophobic liner, the amount of liquid going back upward through them is significantly smaller than the amount of liquid that can pass upwardly through the hydrophilic liner alone. [0050] Aperturing of the laminate may occur after, during or before hydroentangling, which is discussed below, though doing so afterwards is preferred. Aperturing may be carried out by any means known in the art, including using mechanical pin aperturing, by die cutting or by forming the materials in such a way that they are produced with holes in place. The apertures may also be made through the use of high pressure water jets, which may occur while the fabrics are being hydroentangled. The surface area of the liner may be apertured to produce from between 10 and 50 percent open area, more particularly between 20 and 40 percent, and still more particularly about 25 percent. [0051] The use of the hydroentangling process to join the layers, instead of chemical or thermal bonding means, produces a laminate without melted fiber cross over points. This avoids the production of relatively large masses of thermoplastic that can impede fluid movement. High pressure water entangling can also be used to remove a non-durable hydrophilic surface treatment from the hydrophobic layer during processing. [0052] The fibers from which the hydrophilic layer may be made include naturally hydrophilic fibers such as cotton and Rayon, or synthetic fibers that are naturally hydrophobic but which have been treated to be hydrophilic. If the fibers are synthetic fibers treated to be hydrophilic, the treatment must be sufficiently durable to withstand the rigors of hydroentangling. It is not required that all of the fibers of the layer be hydrophilic, just that the layer be predominately hydrophilic. The layer may be made from a blend of fibers. [0053] The fibers from which the hydrophobic layer may be made include naturally hydrophobic fibers like synthetic polymer fibers. It is not required that all of the fibers of the layer be hydrophobic, just that the layer be predominately hydrophobic. The layer may be made from a blend of fibers. As mentioned above, hydroentangling can also be used to remove a previously applied non-durable hydrophilic surface treatment from the hydrophobic layer during processing, thus rendering it hydrophobic again. [0054] The fibrous layers of this invention may be made from any nonwoven process know in the art, including airlaying, spunbonding, meltblowing and carding of staple fibers. The layers may have basis weights from 0.25 to 3 osy (8.5 to 102 gsm) each. [0055] Synthetic fibers include those made from polyolefins, polyamides, polyesters, acrylics, LYOCELL®) regenerated cellulose, Lenzing's viscose rayon, and any other suitable hydrophobic synthetic fibers known to those skilled in the art. Many polyolefins are available for fiber production, for example polyethylenes such as Dow Chemical's ASPUN® 6811A liner low density polyethylene, 2553 LLDPE and 25355 and 12350 high density polyethylene are such suitable polymers. The polyethylenes have melt flow rates, respectively, of about 26, 40, 25 and 12. Fiber forming polypropylenes include Kolon Glotec's T-1001, Exxon Chemical Company's ESCORENE® PD 3445 and Montell Chemical Co.'s PF304. Other polyolefins are also available. Fibers having a lower melting polymer component, like conjugate and biconstituent fibers are suitable for use as well. Such fibers include conjugate fibers of polyolefins, polyamides and polyesters like the sheath core conjugate fibers available from KoSa Inc. (Charlotte, N.C.) under the designation T-255 and T-256. [0056] Natural fibers include wool, cotton, flax, hemp and wood pulp. Wood pulps include standard softwood fluffing grade such as CR-1654 (US Alliance Pulp Mills, Coosa, Ala.). Pulp may be modified in order to enhance the inherent characteristics of the fibers and their processability. [0057] The bodyside layer of this invention is preferably made from a blend of hydrophilic fibers with a minor amount of hydrophobic fibers. The hydrophilic fibers should be present in an amount from about 50 to 100 percent, more particularly from 70 to 100 weight percent and still more particularly 80-100 weight percent. [0058] The layer away from the body should have predominately hydrophobic fibers. The low cost of polypropylene fibers makes it an excellent choice for such a product and polypropylene fibers in an amount of as much as 100 weight percent may be used. Blends of polypropylene with other fibers like PET also function well. [0059] The following helps illustrate the invention. EXAMPLE 1 [0060] A two layer laminate was made having a top or bodyside facing layer and a bottom or absorbent core facing layer. The top layer was a 0.40 osy (13.5 gsm) carded web and had 90 weight percent Rayon, naturally hydrophilic fiber and 10 weight percent polyethylene terephthalate (PET) fibers. The bottom layer was a 0.47 osy (16.5 gsm) carded web having 73 weight percent PET and 27 weight percent polypropylene (PP) fibers. The layers were hydroentangled at a water pressure of 435-725 psi (30-51 kgf/cm 2 ) and apertured afterwards at a density of approximately 50 apertures per cm 2 by the hydroentanglement process at 580 psi (41 kgf/cm 2 ). The apertures were approximately 0.06 mm in diameter or about 0.3 mm 2 in area. The apertures were roughly diamond shaped because the mesh upon which the laminate was supported was diamond shaped. Support media with other shapes would result in other shapes and sizes for the apertures. [0061] Control [0062] A single layer liner having hydrophilic properties. The liner was made from 80 weight percent Rayon and 20 weight percent PET fibers. This liner had a basis weight of 0.89 osy (30 gsm) and was apertured in the same manner and pattern as Example 1. [0063] Example 1 and Control were tested according to the intake rate and rewet tests above and the results given in the Table. It's clear that the liner of this invention had a faster intake rate than that of the control liner. The rewet rate is also better. It was further noted that, in a comparison test using equal amounts of swine blood, the stain size was different for the Control and Example 1. The stain length was about the same, but the shape and width was different, with the Control having a wider, more elliptical shape and Example 1 having a narrower, more rectangular shape. TABLE Intake Rate(sec) Rewet (g) Control 14.4 1.5 Example 1 13.7 1.3 [0064] As will be appreciated by those skilled in the art, changes and variations to the invention are considered to be within the ability of those skilled in the art. Such changes and variations are intended by the inventors to be within the scope of the invention.
There is provided a liner for personal care products having a hydrophilic first apertured nonwoven layer laminated with a hydrophobic second apertured nonwoven layer. The apertures may be aligned. The first layer may, further, be made of durably hydrophilic fibers and the second of non-durably hydrophilic fibers. The liner may be made by a spunlace process. The liner may further have a treatment applied to the hydrophilic layer, where the treatment is aloe, vitamin E, mineral oil, baking soda and combinations thereof. Also provided is a pantiliner having a liquid permeable liner, a liquid impervious baffle, and an absorbent core positioned therebetween. The liner has a hydrophilic first apertured nonwoven layer laminated according to a spunlace process with a hydrophobic second apertured nonwoven layer. The apertures of the first layer and the second layer may be aligned.
3
CROSS REFERENCES TO RELATED APPLICATIONS [0001] This application is a continuation of International Patent Application No. PCT/JP03/11754, filed on Sep. 16, 2003, and claims priority to Japanese Patent Application No. 2002-271944; filed on Sep. 18, 2002, both of which are incorporated herein by reference in their entireties. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates to compositions for treating stress-related diseases. These compositions when used as a drug are very useful in the treatment, prevention, prevention of development, and/or improvement of stress-related diseases in animals such as humans. [0004] The present invention also relates to a method for the treatment or prevention (including treatment, prevention, prevention of development, and improvement) of a stress-related disease and to the use of the above-mentioned active ingredient as a drug (including a drug for treatment, prevention, prevention of development, and improvement) for the treatment or prevention of a stress-related disease. [0005] 2. Discussion of the Background [0006] Stress affects various general organs such as circulatory organs and digestive organs to cause stress-related diseases such as depression, anxiety, gastro-duodenal ulcer, irritable bowel syndrome, bronchial asthma, hypertension, autonomic imbalance, and the like. In a case of depression, the employed basic therapeutic principles are: “taking sufficient rest,” “using an appropriate anti-depressant,” and “supportive psychotherapy like cognitive therapy.” Though tricyclic or tetracyclic anti-depressants have so far been used in the drug therapy, they are accompanied by side effects, such as dry mouth, constipation, dysuria, disorder of eye control, and the like, making their use difficult. Recently, selective serotonin reuptake inhibitors (SSRIs) and selective serotonin/norepinephrine reuptake inhibitors (SNRIs), which allow decrease of adverse reactions, have been proposed, but the side effect of gastric mucosa disorder has been observed, and it is desired to avoid such a side effect. [0007] In another stress-related disease, irritable bowel syndrome, a certain drug therapy has been made in addition to psychotherapy and dietary therapy. In the drug therapy, however, a sufficient effect has not yet been attained, though an anti-cholinergic agent, anti-diarrheal agent or laxative as well as a minor tranquilizer has been used mainly for the relaxation of the disease condition (abdominal pain, diarrhea, constipation, etc.). Thus, a highly effective therapeutic agent is desired. [0008] Thus, there are several problems in the treatment (therapy) of stress-related diseases with drugs, that is: (1) insufficient effect; and (2) occurrence of adverse reactions to reduce the usefulness. In order to solve or improve these problems, a variety of studies have been attempted up to now, but no satisfactory therapeutic method has been achieved. [0009] Thus, there remains a need for an anti-stress agent in which the above-mentioned problems have been improved. There also remains a need for improved methods for treating and preventing stress-related diseases. SUMMARY OF THE INVENTION [0010] Accordingly, it is one object of the present invention to provide novel compositions for treating and preventing stress-related diseases. [0011] It is another object of the present invention to provide novel methods for treating and preventing stress-related diseases. [0012] It is another object of the present invention to provide novel anti-stress agents (a drug effective to a stress-related disease), for example, a drug in which the effect (drug efficacy) is enhanced more than that of the conventional drugs with lesser adverse reaction. [0013] It is another object of the present invention to provide novel combinations of lysine with a drug for stress-related diseases, other than the lysine, (i.e., a drug exhibiting an anti-stress effect) administrable at the same time or separately as a composition (drug, drug for animal use, food, drink, feed, etc.) or a drug (drug exhibiting an anti-stress effect) for treating stress-related diseases. [0014] These and other objects, which will become apparent during the following detailed description, have been achieved by the inventors' discovery that compositions prepared by blending one of amino acids, lysine, with an anti-stress agent (drug for stress-related diseases) or a combination of lysine with such an agent exhibits an enhanced effect (drug efficacy) and reduced adverse reaction in comparison with the anti-stress agent per se containing no lysine. [0015] In this connection, recently, some of the present inventors found that one of essential amino acids, lysine, has anti-stress effect; this finding has been filed as a patent application PCT/JP02/02571. Therefore, since lysine corresponds to one of anti-stress agents, lysine and another anti-stress agent are employed as active ingredients. [0016] In the present invention, it is considered that there is a possibility of lysine enhancing the effect of the drug used as a therapeutic for the above-mentioned diseases, resulting in a decrease of the incidence of side effects by reduction of the dosage of the drug. Thus, the combined use of lysine increases synergistically or additively the effect of the anti-stress agents. In particular, among the drugs so far used in treatment of stress-related diseases, those of which the effect is insufficient in single use or the expected efficacy is reduced by their side effect, are expected to contribute to the treatment (therapy) of these stress-related diseases as medical or food stuffs since their usefulness is increased in combination with lysine. BRIEF DESCRIPTION OF THE DRAWINGS [0017] A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein: [0018] FIG. 1 shows the combined effect of lysine and a minor tranquilizer alprazolam in an irritable bowel syndrome model (Example 1), *: significant in comparison with a control (p<0.05); and [0019] FIG. 2 shows a reducing effect of lysine for exacerbation of intragastric hemorrhage by SSRI in a gastric ulcer model (Example 2), SSRI: paroxetine, *: significant in comparison with a control (p<0.05). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0020] Thus, in a first embodiment, the present invention provides novel compositions for treating stress-related diseases which comprise at least lysine and another anti-stress agent other than lysine as active ingredients (a composition of the invention). [0021] The lysine may be used in a form of one or more salts such as the hydrochloride and the glutamate. The lysine may be used in any form of the optical isomers including D-isomer, L-isomer, and DL-isomer; preferably, the L-isomer is used in the view that it is naturally occurring. The subjects to be treated with the anti-stress agent include humans (a patient or a person who needs the prevention) as well as animals which have a stress-related disease or possibly suffering from such a disease, for example, a domestic animal. [0022] The above-mentioned composition may be used in the form of a drug (including animal drugs), a food or drink, and a feed. [0023] As for the above-mentioned anti-stress agents, one or more of the following drugs (1) to (3) may be selected: [0024] (1) drugs acting on the neurotransmission system participating in the central and autonomic nervous system; [0025] (2) drugs acting on the immune system; and [0026] (3) drugs which relieve a disease condition by a mechanism other than the neurotransmission system and immune system. [0027] The above-mentioned anti-stress agents, one or more, may be selected from the following drugs: anti-depressants, anti-anxiety agents, agents for treating irritable bowel syndrome, agents for treating gastro-duodenal ulcer, agents for treating bronchial asthma, anti-hypertensive agents, agents for treating angina pectoris, anti-diabetics, and anti-rheumatism agents. [0028] The above anti-depressants include selective serotonin reuptake inhibitors and selective serotonin/norepinephrine reuptake inhibitors; the above anti-anxiety agents include benzodiazepine derivatives, diphenylmethane derivatives, and drugs acting on serotonin 5-HT1A receptors; the above agents for treating irritable bowel syndrome include anti-cholinergic agents, anti-diarrheal agents, and laxatives; the above agents for treating gastro-duodenal ulcer include histamine H2 receptor antagonists, proton pump inhibitors, and prostaglandin-type agents; the above agents for treating bronchial asthma include adrenaline β2 receptor agonists and anti-histaminics; the above anti-hypertensive agents include Ca-channel antagonists, angiotensin converting enzyme inhibitors, angiotensin II receptor antagonists, and diuretics; the above agents for treating angina pectoris include organic nitric acid esters and adrenaline β receptor blockers; and the above anti-diabetics include insulin secretion promoters, insulin preparations, and sulfonylureas. [0029] The above-mentioned drugs are exemplified by anti-stress agents (drugs with an anti-stress effect) and can be used in the treatment, prevention, improvement, and prevention of the development of such diseases. [0030] There is no particular limitation in the ratio of the above-mentioned anti-stress agent (active ingredient) to lysine to be used. The ratio (by weight) of the anti-stress agent to lysine when calculated in the free form of lysine is preferably in the range of approximately 1:0.5 to 1:100000, more preferably 1:1 to 1:10000, and even more preferably 1:2 to 1:5000. [0031] The above-mentioned composition of the present invention comprises at least lysine and an anti-stress agent other than lysine (one or more of active ingredients), and further it may contain other ingredients as far as they do not adversely affect the purpose of the invention. For example, an amino acid other than lysine may be used as an additive. For example, arginine, glutamic acid, aspartic acid, and so on may be added. [0032] In another embodiment of the invention, the anti-stress agent includes a combination of lysine with an anti-stress agent other than lysine which may be administered at the same time or separately (a combination of the invention). [0033] In the same manner as in the above invention, the lysine may be used in a form of one or more salts such as the hydrochloride, glutamate, and the like. The lysine may be used in any form of the optical isomers including D-isomer, L-isomer and DL-isomer; preferably, the L-isomer is used since it is naturally occurring. The subject to be treated with the anti-stress agent includes humans as well as animals possibly suffering from stress-related diseases, for example, domestic animals. [0034] The combination of the invention includes the above composition of the invention as a form for concurrent administration of the above two active ingredients. The description of the above-mentioned composition of the invention applies to the combination of the present invention except for that of “composition” per se. [0035] The combination of the invention may be used in any form including the above-mentioned drugs (including drugs for animals), a food, a drink, and a feed. In particular, the anti-stress agents may be administered as a drug or a drug for animal use (single preparation); on the other hand, lysine may be given (administration, diet, or supply) in a form of a drug, a food, a drink, or a feed (single preparation of lysine, drink containing lysine, feed containing lysine, etc.), respectively at a different point in time. In this operation, it is naturally possible that they may contain additional ingredients necessary for the drug (including a drug for animal use), food, drink, or feed, or they may further be processed if necessary. [0036] In another embodiment, the present invention provides a method for preventing or treating a stress-related disease (including treatment, prevention, prevention of development, improvement, etc.), which comprises ingesting or administering lysine and an anti-stress agent other than lysine to the living body. The lysine may be used in the form of one or more salts. [0037] The ingestion or administration may be made by ingesting or administering the above-mentioned composition or in a form of the above-mentioned combination of the invention. [0038] Still in another embodiment, the invention relates to the use of (or the preparation of) the drugs for preventing or treating stress-related diseases (including treatment, prevention, prevention of development, etc.) comprising lysine and an anti-stress agent other than lysine. Once again, the lysine may be in a form of one or more salts. [0039] The stress-related diseases are as described above in the present description. As for the drugs for preventing or treating stress-related diseases, the above-mentioned composition or combination of the invention or one further containing the above-mentioned ingredients may be exemplified as a preferred embodiment. [0040] The combination of the present invention as mentioned above can be used in the form of a drug (including drugs for animal use), a food, a drink, or a feed. In this invention, the two active ingredients, i.e., lysine and the anti-stress agent (active ingredient), each can be used separately in a different form. Hereinafter, a representative formulation of the invention will be explained as an example of the products (pharmaceutical preparations) which contain the above two active ingredients in the same preparation, though it is just a typical example and the invention is not limited thereto. [0041] The term stress-related diseases in the context of the invention mean those caused by any stress (see: “Karada no Kagaku” ( Body Science ), vol. 223, pp. 58-61 (2002)), and will be explained in detail by the followings. [0042] The autonomic nervous system and immune system are affected by stress to cause the following stress-related diseases. The diseases include depression or anxiety in the psychic nervous system; gastro-duodenal ulcer or irritable bowel syndrome in the digestive organ system; bronchial asthma or hyperventilation syndrome in the respiratory system; hypertension or angina pectoris in the circulatory system; diabetes mellitus in the endocrine system; migraine headache or autonomic imbalance in the neuromuscular system; and chronic articular rheumatism or collagen disease in the immune and allergy system. [0043] The drugs used in these diseases can roughly be classified into three groups. The first group includes drugs acting on the neurotrasmission system participating in the central and autonomic nervous systems which are activated by stress per se. The second group includes drugs acting on the immune system altered by stress, and the third group includes drugs for improving (alleviating) the condition per se recognized in the respective diseases which are accompanied by alteration of the above neurotransmission system and immune system. [0044] The effect of lysine on stress-related diseases is considered to occur as an effect on the serotonin nervous system and the modification of a benzodiazepine receptor. [0045] A drug for which the effect is expected to increase in combination with lysine may be, for example, a conventional drug or a drug which may be developed in future, includes preferably those of which the action mechanism is different from that of lysine. That is, it includes: (1) those drugs which act on the neurotransmission system participating in the central and autonomic nervous system, which has the site of action different from that of a serotonin nervous system and benzodiazepine receptor in which lysine is possibly involved; (2) those drugs which act on the immune system; and (3) those drugs which alleviate the condition based on a mechanism other than a neurotransmission system and immune system. [0046] Concrete examples are: (1) the group of drugs which act on the neurotransmission system participating in the central and autonomic nervous system, including those SSRIs which have recently been used as an anti-depressant, e.g., paroxetine and fluvoxamine, SNRIs, e.g., milnacipran; benzodiazepine derivatives as anti-anxiety agents, e.g., diazepam, oxazepam, and flutoprazepam; diphenylmethane derivatives, e.g., hydroxyzine; and serotonin 5-HT1A receptor agonists, e.g., tandospirone; as well as other drugs controlling neurotransmission (catecholamine, serotonin, acetylcholine, neuropeptides, etc.); adrenaline β-receptor blockers, e.g., propranolol, pindolol, and timolol; adrenaline α1-receptor blockers, e.g., prazosin and bunazosin; adrenaline α,β-receptor blockers, e.g., labetalol; muscarine receptor antagonists, e.g., tiquizium and trospium; serotonin 5-HT3 receptor antagonists, e.g., alosetron; and serotonin 5-HT4 receptor agonists, e.g., tegarerod; [0047] (2) the group of drugs which act on the immune system and which includes non-specific immunoactivators, e.g., lentinan and schizophyllan; interleukin production inhibitors, e.g., cyclosporin, suplatast, and tazanolast; and [0048] (3) the group of drugs which alleviate the condition based on a mechanism other than the neurotransmission system and the immune system. Specific drugs which act on gastro-duodenal ulcers include, for example, histamine H2 receptor antagonists which directly inhibit the secretory mechanism of an aggressive factor, i.e. acid, e.g., famotidine, cimetidine, ranitidine, and nizatidine; and proton pump inhibitors, e.g., lansoprazole, omeprazole, and rabeprazole. Drugs for treating irritable bowel syndrome include those which improve constipation, e.g., polycarbophil calcium, methylcellulose, and ragnolose. The antihypertensive agents include Ca-channel antagonists which directly relax the vascular smooth muscle to decrease blood pressure, e.g., cilnidipine, amlodipine, and efonidipine; angiotensin converting enzyme inhibitors which directly inhibit the hypertensive factor renin-angiotensin system, e.g., enalapril, captopril, and temocapril; and angiotensin II receptor antagonists, e.g., losartan, valsartan, and candesartan cilexetil. The drugs for treating bronchial asthma include adrenaline β2 receptor agonists, e.g., procaterol, trimethoquinol, hexoprenaline, and salbutamol; the drugs for treating diabetes mellitus include those which directly control insulin secretion, e.g., tolbutamide or nateglinide, glibenclamide, and chlorpropamide. [0049] In using the anti-stress agents as mentioned above, they may be given in any conventional way corresponding to the respective drugs; the dose of the active ingredient may be determined in the conventional way, which may be properly increased or decreased in consideration of the effect of the invention (dose of approximately 10-80%). In other words, as a result of the inclusion of lysine in the present combinations, compositions, and methods, the dosage of the other anti-stress agent may typically be reduced to 10 to 80% of the amount in which it is conventionally administered. [0050] Therefore, it is considered that the occurrence of side effect caused by these drugs could be reduced by decreasing the dose with the effect enhanced by a combined use of lysine. [0051] The lysine used in combination with a drug for treating stress-related diseases can be incorporated into the above pharmaceutical preparations. Of course, it may be used alone or as a pharmaceutical composition prepared by blending with any known pharmaceutically acceptable carrier, diluent, and the like. In such a case, there is no particular limitation in a way of administration, and it may be used as an oral preparation such as tablets, capsules, powders, granules, pills, and the like, or as a parenteral preparation such as injections, syrup, ointment, suppositories, and the like. The dose of lysine is variable depending on the subject to be administered, the route of administration, and conditions; it may be administered preferably at a daily dose of about 10 mg to 50 g, and more preferably about 100 mg to 20 g, at once or in several divided doses a day regardless of its formulation as lysine alone or as a combination drug. [0052] The present invention, as mentioned above, also relates to a method for preventing or treating stress-related diseases (including treatment, prevention, prevention of development, improvement, etc.), which comprises ingesting or administering lysine and an anti-stress agent other than lysine to the living body, or alternatively the use of (or in preparation of) a drug for preventing or treating stress-related diseases (including treatment, prevention, prevention of development, improvement, etc.), which comprises lysine and an anti-stress agent other than lysine. In these cases, the lysine may be in the form of one or more salts. [0053] The present invention can readily be carried out based on the above explanation of the composition of the invention and a combination of the invention or the working examples as mentioned below, or if necessary by referring to a conventional known technology. [0054] Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof. EXAMPLES Example 1 Effect of the Combined Use of Alprazolam and Lysine in an Animal Model for Irritable Bowel Syndrome [0000] Method [0055] An animal model of irritable bowel syndrome was prepared according to the method as described by Williams et al. (Williams, C. L., Villar, R. G., Peterson, J. M., Burks, T. F., “Stress-induced changes in intestinal transit in the rat: a model for irritable bowel syndrome,” Gastroenterol., vol. 94, pp. 611-621 (1988)). That is, a cotton tape was placed around the anterior limbs of seven-week-old Wistar male rats, the rats were kept in a bracket cage, and then the amount of feces excreted during 2 hours was measured. A test compound was orally administered 40 minutes before starting the wrap-restraint stress. The following groups were examined: 1) control group; 2) a group to which lysine hydrochloride (1 g/kg) alone was given; 3) a group to which a minor tranquilizer alprazolam (10 mg/kg; Takeda Chem. Ind.) alone was given; and 4) a combination group to which lysine hydrochloride (1 g/kg) and alprazolam (10 mg/kg) were given. Each group consisted of 10 animals. [0000] Results [0056] The results are presented graphically in FIG. 1 . The amount of feces excreted over 2 hours during which time wrap-restraint stress was in force was about 1.4 g for the control group; this value was significantly higher than that of no stress. In comparison with this increase induced by stress, no clear effect was observed in the group to which lysine hydrochloride or alprazolam alone was given. In the group to which a combination of lysine and alprazolam was given, however, the increase of feces was significantly inhibited (see FIG. 1 ). That is, the results in FIG. 1 indicate that lysine acts to increase the effect of the minor tranquilizer alprazolam. Example 2 Effect of the Combined Use of SSRI and Lysine in a Model for Gastric Ulcer [0000] Method [0057] A widely used model for gastric ulcer caused by water immersion under restraint was used. That is, rats were placed in a stress cage and immersed in water to the chest for 5 hours (at a temperature of 22-25° C.). The stomach was removed and the degree of intragastric hemorrhage was observed and the hemorrhage area was calculated using an NHI image software. [0058] The test compound was evaluated as follows. Five-week-old Wistar male rats were divided into three groups. The first group was bred with a normal powdered feed; the second group with a powdered feed to which was added a selective serotonin reuptake inhibitor (SSRI) (paroxetine; Glaxo-SmithKline; 298 mg/kg diet) alone; and the third group with a powdered feed containing the same amount of the same SSRI and lysine hydrochloride (13.3 g/kg diet) to which was additionally added arginine (13.3 g/kg diet). Each group consisted of 10 animals. Rats could freely feed before they reached 14 weeks of age. Thereafter, no feed and water were given for 2 days, and on day 3, all of the rats were subjected to the water-immersion restraint stress for 5 hours. [0000] Results [0059] The results are shown graphically in FIG. 2 . As can be seen, the SSRI significantly exacerbated the intragastric hemorrhage, but no exacerbation by the SSRI was observed in group which was fed the combination with lysine (see FIG. 2 ). That is, the results in FIG. 2 indicate that exacerbation of the intragastric hemorrhage by the SSRI is reduced. [0060] From the above results, the effect of lysine combined with an anti-stress agent was confirmed. EFFECT OF THE INVENTION [0061] As clearly seen from the above explanation, the present invention provides a combination of lysine and an anti-stress agent, particularly a composition comprising the two active ingredients, for example, a drug such as a combination drug (including a drug for animal use). In comparison with a single preparation of anti-stress agent, particularly a conventional anti-stress agent, the combined use of lysine exhibits an improvement of pharmacological effect and a reduction of side effects, and accordingly the products of the invention exhibit a very high efficacy. The present invention further provides a method for preventing or treating stress-related diseases (including the treatment, prevention, prevention of development, improvement, etc.) and use of the above-mentioned active ingredients in drugs for preventing or treating stress-related diseases (including the treatment, prevention, prevention of development, improvement, etc.). The present invention can widely be applied in the field of drugs (including drugs for animal use), medication, food and feed, and is very useful industrially. [0062] 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. [0063] All patents and other references mentioned above are incorporated in full herein by this reference, the same as if set forth at length.
Administering or ingesting a combination of lysine with another agent for stress-related diseases other than lysine provides an improvement in the treatment and prevention of stress-related diseases (enhanced drug efficacy) and reduced side effects. Such combinations of lysine with another agent for stress-related diseases other than lysine can be employed in the form of a medicine (including a medicine for animals), a food, a drink or a feed, and are highly useful in preventing, treating, or ameliorating various stress-related diseases and preventing the progress of such diseases. The two ingredients as described above can be administered or ingested either at the same time or at different points and in different forms.
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CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority to U.S. Provisional Application Ser. No. 62/008,754 filed Jun. 6, 2014 which is incorporated herein by reference in its entirety. BACKGROUND [0002] In order to create an improved experience during the use of virtual reality (VR), an auditory virtual reality (AVR) can be created by replicating sound scattering that would occur as a sound source interacts both with a simulated representation of a physical environment and with the specific anatomy of the listener, including the listeners head, ears, and torso. [0003] To understand a sound landscape, it is possible to measure the changes that sound undergoes as it interacts with the physical environment and the listener, as shown in the prior art, using a Head-Related Transfer Function (HRTF) that is specific to the listener. Various means for obtaining listener-specific HRTFs are shown in prior art FIGS. 1 and 2 . [0004] In FIG. 1 , a source (speaker) is placed at a given location and a generated sound is then recorded using a microphone placed in the ear canal of an individual. In order to obtain the HRTF corresponding to a different source location, the speaker is moved to that location and the measurement is repeated. HRTF measurements from thousands of points are needed and the process is time-consuming, tedious, and burdensome to the listener. [0005] In FIG. 2 , a transmitter is located within the ear of the individual and a plurality of pressure wave sensors (microphones) are arranged in a microphone array surrounding the individual's head. The sound emanating from the transmitter is collected at the microphones in the form of pressure waves which are analyzed to extract the HRTF. To pinpoint the location of the sensors in reference to the transmitter, a microphone and head tracking system is attached to the individual's head to monitor position. [0006] A Head-Related Impulse Response (HRIR) filter is a listener-dependent and direction-dependent filter which can be derived from the inverse Fourier transform of the HRTF. Knowledge of the HRIR filter is useful because it can be applied to additional sound sources which have not been measured in order to understand the reaction of these sound sources to the listener and the environment via a convolution operation. [0007] Since the computational cost of the convolution operation depends on the size of the HRIR filter, identifying a sparse HRIR filter representation will allow efficient, zero-latency processing in a time domain as an alternative to the albeit low complexity but latency-laden processing using fast Fourier transforms (FFT) in the frequency domain. SUMMARY [0008] Methods of signal processing and spatial audio synthesis are disclosed. [0009] In one example implementation, a method of signal processing is disclosed. The method includes accepting a physical signal having a characteristic indicative of a physical property in a first state and processing the physical signal to effect a transformation of the physical signal from the first state to a second state by applying a representation of a base filter to the physical signal. The representation of the base filter is a convolution of a plurality of shorter filters. [0010] In another example implementation, a method of spatial audio synthesis is disclosed. The method includes approximately decomposing a plurality of impulse responses each characterized by a spatial characteristic into a convolution of a characteristic-independent first filter and a characteristic-dependent second filter; accepting an auditory signal; and generating an impression of an auditory virtual reality by processing the auditory signal to impute the spatial characteristics on the auditory signal via convolution with the plurality of impulse responses. The processing is performed in a series of steps, the steps including: performing a first convolution of the auditory signal with the first filter and performing a second convolution between the result of the first convolution and the second filter. [0011] In another example implementation, a computing device is disclosed. The computing device includes one or more processors for controlling operations of the computing device and a memory for storing data and program instructions used by the one or more processors. The one or more processors are configured to execute instructions stored in the memory to: approximately decompose a plurality of impulse responses each characterized by a spatial characteristic into a convolution of a characteristic-independent first filter and a characteristic-dependent second filter; accept an auditory signal; and generate an impression of an auditory virtual reality by processing the auditory signal to impute the spatial characteristics on the auditory signal via convolution with the plurality of impulse responses. The processing is performed in a series of steps, the steps including: precomputing a first convolution of the auditory signal with the first filter and performing, in real time, a second convolution between the result of the first convolution and the second filter. BRIEF DESCRIPTION OF THE DRAWINGS [0012] The description makes reference to the accompanying drawings wherein: [0013] FIG. 1 is a schematic of an exemplary arrangement of HRTF measurement according to the prior art; [0014] FIG. 2 is a schematic of another exemplary arrangement of HRTF measurement according to the prior art; [0015] FIG. 3 is a block diagram of a computing device; [0016] FIG. 4 is a representation of semi-non-negative matrix factorization generalizing time-domain convolution; [0017] FIG. 5 is a comparison of the number of operations between a FFT and direct convolution of a physical signal; [0018] FIG. 6 shows exemplary reflection maps corresponding to horizontal and vertical plane HRIRs (left-ear) trained under various transformations; [0019] FIG. 7 is a magnitude-frequency representation of resonance filters for CIPIC HRIRs (left-ear); [0020] FIG. 8 is a representation of cross-correlation between anthropometry and magnitude-frequency representations of resonance filters for representative CIPIC subjects; [0021] FIG. 9 is a magnitude-frequency representation of reflection filters on a vertical plane; [0022] FIG. 10 shows varying reconstruction errors under window and convolution transformations as applied to HRIRs; [0023] FIG. 11 shows that low-pass filtering of varying bandwidth improves spectral distortion reconstruction error for a sample HRIR; [0024] FIG. 12 shows that the lowest-restricted spectral distortion reconstruction error for a maximum frequency bin M H is inversely related to bandwidth σ for a sample HRIR; [0025] FIG. 13 shows that sample reflections produced by L 1 -NNLS for varying λ preserve the dominant excitations in the time domain and the shape of the magnitude spectra; [0026] FIG. 14 shows that spectral distortion and the number of nonzero entries is lower (more accurate) for left-ear sparse reflections (L 1 -NNLS with a constant penalty term λ) near the ipsilateral side of the spherical coordinate grid; and [0027] FIG. 15 shows sparsity to spectral distortion reconstruction trade-off for L 1 -NNLS and L 1 -LS solutions of varying λ on horizontal and vertical plane HRIRs. DETAILED DESCRIPTION [0028] A structured decomposition of HRIRs based on an extension to a non-negative matrix factorization algorithm is disclosed. The HRIR is re-expressed as a convolution between a direction-independent filter which is correlated with anthropometry and a direction-dependent filter where sparsity can be tuned at a slight cost to the HRIR reconstruction error. These filters can be applied to time-domain convolution with arbitrary source-signals at a rate much faster than convolution via a FFT. A simplified representation of the HRIR filter may also support prediction of changes to the HRIR filter based on a particular listener's anthropometry without obtaining measurements. Further, this same technique can be applied to simplify the representations of other types of impulse responses. [0029] FIG. 3 is a block diagram of a computing device, for example, for use in signal processing and spatial audio synthesis as described here. The computing device can be any type or form of single computing device or can be composed of multiple computing devices. The processing unit in the computing device can be a conventional central processing unit (CPU) or any other type of device, or multiple devices, capable of manipulating or processing information. A memory in the computing device can be a random access memory device (RAM) or any other suitable type of storage device. The memory can include data that is accessed by the CPU, using, for example, a bus. [0030] The computing device can also include secondary, additional, or external storage, for example, a memory card, flash drive, or any other form of computer readable medium. Applications installed within the computing device can be stored in whole or in part in the memory or in the external storage and then loaded into the memory as needed for processing. The applications installed within the computing device can include those configured for signal processing and spatial audio synthesis as described in more detail below. INTRODUCTION [0031] HRTFs represent spectral characteristics of a subject's anthropometry (head, torso, outer-ear or pinna). Recent works on pinna-related transfer functions (PRTFs) (pinna contribution to the HRTF) have led to re-synthesis models based on the decomposition into ear-resonance and ear-reflection parts. A PRTF can thus be expressed as a convolution between a resonance component derived from the spectral envelope and a reflection component derived from estimated notches in amplitude. [0032] This disclosure addresses a similar decomposition formulation for a collection of HRIRs with two added constraints. Suppose an HRIR x is expressed as the time-domain convolution: [0000] x=f*g,g≧ 0.  [1] [0033] Equation 1 includes “resonance filter” f shared by all HRIRs belonging to a subject and a sparse non-negative “reflection filter” g unique to the measurement direction. The resonance filter f is assumed direction-independent, mixed-signed, and can be interpreted as the averaged response over all anthropometry. The filter g is assumed direction-dependent, non-negative, and inclusive of values that are interpreted as instant reflections in time. The length of g is typically short as only the early reflections are modeled; f is conversely long due to sound scattering distances over the head. Moreover, jointly learning filters f and g is a well-posed problem using a modified semi-non-negative matrix factorization (semi-NMF) method. [0034] As shown in FIG. 4 , semi-NMF approximately factorizes a mixed-signed matrix X into a mixed-signed matrix F and non-negative matrix G where X≈FG T is optimal in the least-squares sense. This disclosure modifies the factorization so that the matrix F has a Toeplitz structure where the convolution operation is equivalent to a formulation of Toeplitz matrix-vector multiplication. The HRIRs, arranged as columns of the input matrix X, are obtained as a matrix-vector product of the Toeplitz matrix F characterized by the resonance filter f, and the reflection filters g arranged as the rows of matrix G. [0035] This Toeplitz constrained semi-NMF of HRIR x allows for efficient convolution with an arbitrary source-signal y via the associative and commutative property: [0000] y*x =( y*f )* g =( y*g )* f   [2] [0036] For a known source-signal y the convolution (y*f) is direction-independent and can be stored with little overhead costs. During run-time, the direct convolution with a sparse reflection filter g (or multiple sparse filters in G) is fast. Conversely for a streaming source-signal y of small block-sizes, multiple convolutions with different g in y*g is fast during run-time as the remaining convolution with the longer resonance filter f occurs only once. [0037] As shown in FIG. 5 , direct-convolution between long and short signals generally requires fewer operations than convolution via the FFT. The theoretical cost analysis between direct and FFT-based convolutions gives an approximate cross-over point at filter length K=68 where theoretical floating point multiplications (FPMs) of direct convolutions grow at a rate K per output compared to FFT implementation at a rate [0000] 34 9  N   log 2  N N + K [0000] for sample size N=3×44100. [0038] The sparsity of reflection filters in G can be tuned by solving a regularized (L 1 norm penalty) non-negative least squares problem (L 1 -NNLS). The cost of direct convolution decreases linearly with respect to the number of nonzero entries (NNZs) in the reflection filter g. This presents a trade-off between run-time computational gains of convolution with a sparse g and the loss of quality in the HRIR reconstructed from g. The reconstruction errors are expressed by the root-mean square error (RMSE) and spectral distortion (SD) with respect to the reference HRIR/HRTF given by: [0000] RMSE =  X - F ~   G T  F 2 MN ,  SD  ( H { j } , H { * j } ) = 1 M  ∑ i = 1 M  ( 20  log 10   H i { j }   H i * j  ) 2  . [ 3 ] [0039] The SD is the sum of component magnitude ratios between the Fourier transform of a reference HRIR (HRTF) H {j} =F{X j } and the reconstruction H {*j} =F{FG J T } which can be interpreted as a perceptual distance in the frequency domain. All factorizations are separately done on HRIRs that share the same ear and subject identity. All HRIRs can be pre-processed as taken from subjects in the Center for Image Processing and Integrated Computing (CIPIC) database, though HRIRs belonging to other subjects and from other databases are also possible. The methods described below can be generalized to any large collection of IRs (e.g. room IRs) for which a similar decomposition holds. Semi-Non-Negative Toeplitz Matrix Factorization [0040] The original non-negative matrix factorization (NMF) was introduced in the statistics and machine learning literature as a way to analyze a collection of non-negative inputs X in terms of non-negative matrices F and G where X≈FG T . The non-negative quantities have seen useful interpretations for spectral clustering of multimedia data such as images and sound spectrograms. As mentioned before, here we hypothesize that they correspond to instantaneous reflections of resonant response on listener's anthropometry. For mixed-signed HRIR inputs, we adopt a related factorization below. [0041] Semi-NMF is a relaxation of the original NMF where the input matrix X and filter matrix F have mixed-signs but the elements of matrix G are constrained to be non-negative. Formally, the input matrix Xε M×N is factorized into matrix Fε M×K and matrix Gε N×K by minimizing the residual Frobenius norm cost function: [0000] min F,G ∥X−FG T ∥ F 2 =tr (( X−FG T ) T ( X−FG T )).  [4] [0042] In equation 4, tr is the trace operator. The RMSE criterion in equation 3 is subsequently minimized at the solutions whereas the SD reconstruction error is not. Described further below, certain transformations of the cost function may decrease the SD error. [0043] The semi-NMF algorithm is as follows: For N samples in data matrix X, the i th sample is given by the M-dimensional row vector X i =X :,i and is expressed as the matrix-vector product of F and the K-dimensional row vector G i =G i,: . The number of components K is selected beforehand or found via data exploration and is typically much smaller than the input dimension M. The matrices F and G are jointly trained using an iterative updating algorithm that initializes a randomized G and performs successive updates as follows: [0000] F ← XG  ( G T  G ) - 1 , G ij ← G ij  ( X T  F ) ij + + [ G  ( F T  F ) - ] ij ( X T  F ) ij -  [ G  ( F T  F ) + ] ij ,  ( Q ) ij + =  Q ij  + Q ij 2 , ( Q ) ij - =  Q ij  - Q ij 2 . [ 5 ] [0044] The positive definite matrix G T Gε K×K in equation 5 is small (fast to compute) and the entry-wise multiplicative-updates for G ensure that it retains non-negative entries. The method converges to the optimal solution that satisfies Karush-Kuhn-Tucker conditions as the update to G monotonically decrease the residual in the cost function in equation 4 for a fixed F and the update to F gives the optimal solution to the same cost function for a fixed G. The minimizer of this cost function is not equivalent to that of the SD error but is often a close approximation in practice. Nearest Toeplitz Minimizer [0045] To modify semi-NMF for learning the resonance and reflection filters, a notation for a related problem is introduced: suppose F is approximated by a Toeplitz-structured matrix {tilde over (F)} where {tilde over (F)} ij =Θ i−j for parameters Θ=[Θ 1−M , . . . , Θ K−1 ] T ; entries along diagonals and sub-diagonals of {tilde over (F)} constant. The Toeplitz notation is given by the following: [0000] Top  ( Θ ) = [ Θ 0 Θ 1 … Θ K - 2 Θ K - 1 Θ - 1 Θ 0 Θ 1 … Θ K - 2 ⋮ ⋱ ⋱ ⋱ ⋮ Θ 2 - M … Θ - 1 Θ 0 Θ 1 Θ 1 - M Θ 2 - M … Θ - 1 Θ 0 ] . [ 6 ] [0046] This notation is fully specified by parameters {Θ 0 , . . . , Θ K−1 } and {Θ 0 , . . . , Θ 1−M } along the first row and column. One useful form is to represent the Toeplitz matrix as a linear combination of shift matrices S k ε M×K (ones along the k th sub-diagonal and zero entries otherwise) as given by: [0000] {tilde over (F)}=Σ k=1−M K−1 S k Θ k ,S ij k =δ i,j−k .  [7] [0047] The nearest Toeplitz matrix approximation of an arbitrary F minimizes the residual Frobenius norm cost function given by: [0000] J =  F - F ~  F 2 = tr  ( F T  F - 2  F T  F ~ + F T  F ~ ) ,  ∂ J ∂ Θ k = 2  tr  ( ( F - F ~ ) T  ∂ F ~ ∂ Θ k ) , ∂ F ~ ∂ Θ k = S k [ 8 ] [0048] In equation 8, the partial derivative of J with respect to a parameter Θ k is linear and independent of Θ j≠k due to the trace term. By equating the derivatives to zero, the solutions Θ are given by: [0000] Θ k = tr  ( F T  S k ) min  ( k + M , K - k , K , M ) . [ 9 ] [0049] Equation 9 is simply the means of the sub-diagonals of the full matrix F. It is thereby possible to obtain an approximate resonance filter from the unconstrained solution to F=XG (G T G) −1 in equation 5 although this would not be the minimizer of the semi-NMF objective function in equation 4. Unique Toeplitz Minimizer [0050] We define the Toeplitz constrained semi-NMF problem and solution as follows: Suppose F is specified by a Toeplitz matrix given in equations 6 and 7. Then, the cost function in equation 4 is quadratic (convex) with respect to each Θ k and the set of parameters Θ has a unique minimizer. The partial derivatives of the cost function are given by: [0000] ∂  X - F ~  G T  F 2 ∂ Θ k = ∂ tr  ( ( X - F ~  G ) T  ( X - F ~  G T ) ) ∂ Θ k = 2  tr  ( ( G T  G  ∑ i = 1 - K M - 1  S k T  S i  Θ i ) - S k T  XG ) . [ 10 ] [0051] In equation 10, the product of shift matrices S k T S i can be expressed as the square shift matrix S i−k . Unlike the nearest Toeplitz approximation, the partial derivatives of in equation 10 with respect to Θ 1−M≦k≦K−1 are linearly related to each other. Setting the partial derivatives to zero, the set of parameters Θ are jointly solved in a second linear equation AΘ=b defined as follows: Aε |Θ|×|Θ| , where |Θ|=M+K−1 is a Toeplitz square matrix and bε M×1 is a vector with entries are given by: [0000] A M+k,M+i =tr ( G T G S i−k ), b, m+k =tr ( S k T XG ).  [11] [0052] For positive-definite A, the matrix {tilde over (F)} is parameterized by the solution to the linear system given by: [0000] {tilde over (F)}=Top (Θ),Θ= A −1 b.   [12] [0053] Equation 12 is the real and unique minimizer of equation 4. Iterating between equation 12 and computing the multiplicative-update to matrix G via equation 5 gives the optimal solution upon convergence. The overall training process is given in algorithm 1 listed at the end of this detailed description. Transformed Toeplitz Minimizer [0054] The original cost function in equation 4 can be generalized under linear transformations of the residuals with the aim of finding solutions with lower SD reconstruction errors. The modified semi-NMF problem minimizes a fixed linear transformation Dε M*×M of the reconstruction error given by: [0000] min {tilde over (F)},G ∥D ( X−{tilde over (F)}G T )∥ F 2 .  [13] [0055] In equation 13, F and G are subject to the same constraints as before, and D T D must have full-rank. The solution to {tilde over (F)} in equation 12 of the modified linear system is given by: [0000] A M+k,M+i =tr ( G T GS k T D T DS i ), b M+k =tr ( S k T D T DXG ).  [14] [0056] The multiplicative update rule for G is given by [0000] G ij ← G ij  ( X T   T     F ~ ) ij + + [ G  ( F ~ T   T     F ~ ) - ] ij ( X T   T     F ~ ) ij - + [ G  ( F ~ T   T     F ~ ) + ] ij . [ 15 ] [0057] {tilde over (F)} and G can be iterated until convergence. [0058] Two common transformations D from signal-processing are considered whose bandwidth parameters σ can be tuned. First, the window transform is characterized by the squared exponential filter [0000] υ σ  ( x ) =  - x 2 σ 2 [0000] and is given by: [0000] D W =diag(υ σ (0: M− 1))ε M×M .  [16] [0059] Equation 16 is the convolution of a signal with an exponential filter in the frequency domain (treated as if it were the time-domain) and is equivalent to element-wise multiplication between time-domain residuals and the squared exponential filter υ σ (x) of inverse bandwidth; early time-bin residuals contribute more to the overall error in equation 13. Conversely, the convolution transform is characterized by the Gaussian filter [0000]  σ  ( x ) = 1 σ  2  π   - x 2 2  σ 2  [0000] and is given by: [0000] D C =Top (Θ C )ε M×M ,Θ 1:M−1 C =N σ (1: M− 1),Θ 0:1−M C =N σ (0:1− M ).  [17] [0060] This is equivalent to element-wise multiplication of the frequency-domain residuals with a Gaussian filter of inverse bandwidth; low-frequency residuals contribute more to the overall error in equation 13. Resonance and Reflection Filter Training [0061] For the general convolution operation between a resonance and a reflection filter f and g, the native Toeplitz matrix representation of {tilde over (F)} given in equation 6 must be further constrained to simulate zero-padding the signals which preserves associative and commutative properties. Direct-convolution can be exactly expressed as the constrained Toeplitz matrix-vector product given by: [0000] X i = [ Θ 0 0 … 0 Θ - 1 Θ 0 0 … ⋮ … ⋱ 0 Θ K - M … Θ - 1 Θ 0 0 Θ K - M … Θ - 1 ⋮ … ⋱ ⋮ 0 … 0 Θ K - M ]  [ G i   1 ⋮ G iK ] . [ 18 ] [0062] In equation 18, the parameters {Θ K−M−1 , . . . , Θ 1−M , Θ 1 , . . . , Θ K } are set to constant zero. Only the parameters {Θ 0 , . . . Θ K−M } are solved for in a smaller M−K+1×M−K+1 sized linear system following equations 11 and 12 and assigned to the resonance filter given by: [0000] f={Θ 0 , . . . Θ k−M }ε M−K+1   [19] [0063] The resonance and reflection filters are jointly trained in Algorithm 1 for HRIRs (same-ear, same-subjects) for 50 iterations under window transformations D W , σ={15, 30, ∞}, convolution transform D C , σ={0.1, 0.75, 1.0}, number of samples N=1250, initial time-bins M=200, and filter length K=25. Note that the identity transform D=I is equivalent to the window convolution case D W , σ=∞. Finding an optimal transformation is difficult as the bandwidth parameters σ for window and convolution transformations are not easily trained; the cost function is non-linear when both F and G are fixed. [0064] As shown in FIG. 6 reflecting experiments with various filter lengths K, most of the signal energy in the min-phase HRIRs is concentrated in the first 25 taps; this corresponds to 0.5625 ms or a rough distance of 19 cm that the sound travels through air after the onset reflection. For K=25 and the identity transform, the early reflections in the HRIRs can be summarized by three to five non-negative bands in the reflections. The later dense reflections along the HRIR tails (beyond 25 taps) are implicitly modeled by the convolution between the early reflections in G and the resonance filter f. The window transform D W for small σ flattens later time-domain residuals allowing earlier reflections to be more accurately modeled. The convolution transform D C for large σ flattens high-frequency domain residuals allowing long periodic reflections to be more accurately modeled. Spectral Filter Analysis [0065] While the resonance and reflection filters are trained in the time-domain, their frequency-domain representations may provide insights to their relationship with anthropometry. [0066] As shown in FIG. 7 , filters trained under the identity transformation D=I include resonance filters f trained on left-ear HRIRs across several CIPIC subjects. These resonance filters f have magnitude-frequency responses the are indistinguishable up to 3 kHz and share resonant frequency centers along the ranges of 4-5, 6.5-7, 9-12, 15-16, and 19-20 kHz. The lowest resonant frequency may correspond with Shaw's omni-directional frequency mode and the higher-frequency centers with individual pinna-related anthropometry. [0067] To provide a comprehensive investigation, and as shown in FIG. 8 , Pearson-correlations between magnitude-frequency resonance filters f and the anthropometry features across 35 CIPIC subjects are computed. Anthropometry features include both pinna-related (left or right-ear) and non-pinna related features. The left-ear resonance filters are cross-correlated with only the left-ear pinna-related and non-pinna related features. Then, the analogous process is repeated for the right ear. The agreement between the two sets of cross-correlations is computed by taking their product between same-type features. More positive entries implies a high correlation with anthropometry and agreement between ear types. The results show that non-pinna related features x 6,9 are most correlated to low-frequency resonances at 1-8 kHz, x 1 ,d 8 for mid-frequencies 9-11 kHz, and d 3,7 for higher-frequencies 13-16 kHz. The t 2 pinna flare angle is interestingly correlated to the 4 kHz resonance. [0068] For completeness, FIG. 9 shows the magnitude-frequency representation of the reflection filters on the vertical plane. The effects of torso and shoulder reflections are captured in the magnitude spike along the low frequency 0-2 kHz range most apparent along low-elevations. Three common notch bands increase in frequency toward higher elevations (top of the head) which agrees with similar observations in the prior art. Error Analysis [0069] FIG. 10 shows varying reconstruction errors under different transformations, that is, under window and convolution transformations of HRIRs. The transformed root mean squared error (TRMSE) is proportional to the cost function in equation 13 and monotonically decreases until convergence. The resonance filters resemble periodic functions that decay in time which is most pronounced in the case of transformation D C , σ=15. For the fixed set of transformations (bandwidths σ), the effects on the trained filters' SD reconstruction error are as follows: the identity transform (window transform D W , σ=∞) achieves the lowest mean SD error of 2.9 dB. Aggressive windowing (D W , σ=15) or smoothing in the frequency domain increases the mean SD error to 4.5 dB. Aggressive convolution or applying a low-pass Gaussian filter (D C , σ=1.0) gives the highest mean SD error of 8.9 dB. Optimizing Bandwidth σ for Individual HRIRs [0070] While the filters learned under non-identity transformations do not improve upon the mean SD reconstruction error, an alternative approach for improving SD reconstruction errors of individual HRIRs can be considered. For a fixed resonance filter f trained under the identity transformation, one can separately solve for reflections G i under different transformations (D W , D C varying σ) of the residuals in a non-negative least squares (NNLS) problem given by: [0000] min G i ∥D ( {tilde over (F)}G i T −X i )∥ 2 2 ,s·t·G i ≧0.  [20] [0071] Tuning the bandwidth parameter σ for each HRIR X i produces reflection filters G i with different SD reconstruction errors. Moreover, the computed reflections can be substituted in place of matrix updates to G in equations 5 and 15 but are computationally more demanding as the substitution requires O(K 3 ) operations for each of the N reflections. The choice of the bandwidth term σ in the window transform D W causes a variable amount of smoothing in the frequency domain of the residuals. [0072] As shown in FIG. 11 , the SD errors, if taken along adjacent frequency bands, are correlated with the smooth magnitude HRTFs in the frequency domain. As bandwidth σ→∞, the NNLS reflections tend toward the original reflections under the identity transformation. However, the actual minimum SD occurs at a finite σ=30 for the sample HRIR. [0073] The choice of the bandwidth term σ in the convolution transform D C affects the SD reconstruction error in equation 3 along different frequency bands. Consider the restricted SD criterion given by: [0000] SD M H  ( H { j } , H { * j } ) = 1 M H  ∑ i = 1 M H  ( 20   log 10   H i { j }   H i { j * }  ) 2  . [ 21 ] [0074] As shown in FIG. 12 , the maximum frequency bin M H in equation 21 is constrained to be 1≦M H ≦M. For M H ≦80 (17.64 kHz), the optimal bandwidth term σ is inversely related to the maximum frequency bin M H . Reconstruction errors beyond M H >80 are more sensitive due to low magnitude of high-frequency residuals; a much wider frequency-domain window bandwidth would be necessary. Sparse Reflection Reconstruction [0075] To introduce sparsity or to restrict the NNZ entries for reflection filters in G, the trained Toeplitz filter {tilde over (F)} can be fixed and solved for each reflection filter G i in a penalized L 1 -NNLS problem given by: [0000] min G i ∥D ( FG i T −X i )∥ 2 2 +λ|G i | 1 ,s·t·G i ≧0.  [22] [0076] The addition of a regularization term λ on the L 1 norm of the reflection filter G i affects the sparsity as increasing λ decreases the NNZ. For the identity transform D=I, the residual norm is directly minimized while penalizing for non-sparsity in the reflection filter G i . It is also practical to discard solution entries that fall below a constant threshold as they contribute little to the overall reconstruction. In a given reflection G i , all entries G ij ≦10 −4 are zeroed. [0077] Referring back to FIG. 6 , the sparse reflections are illustrated where early reflections of the original HRIRs are shown for horizontal and vertical plane HRIRs. The lower NNZ count in the L 1 -NNLS solutions sparsifies the non-negative components of the original reflections into distinct bands. Penalizing the L 1 norm magnifies the effect of each type of transform as late and non-periodic components are discarded in the window and convolution transforms respectively. The SD reconstruction error to NNZ trade-offs are shown below in Table 1 where the identity transform achieves the expected lowest SD error and loss of accuracy before and after half the nonzero entries are discarded. For vertical-plane HRIRs, SD reconstruction error degrades little for sparser reflections. [0000] TABLE 1 [Mean Spectral Distortion/Number of Nonzero Entries] D W , σ = ∞ D W , σ = 15 D C , σ = 1.0 H-Plane   3/22.74 8.1/24.2 4.7/21.4  H-Plane Sparse 5.3/11.7 9.5/9.94 6.2/14.72 M-Plane 8.6/22.5   10/23.98 8.4/21.04 M-Plane Sparse  8.6/11.34   11/10.02 9.3/13.9  Optimizing Regularization Term λ for Individual HRIRs [0078] Sparsity reduces the cost of the direct convolution X i =f*G i to O(|Θ| 0 |G i | 0 ) operations where |Θ| 0 and |G i | 0 are the number of nonzero entries in the filter parameters. [0079] As shown in FIG. 13 , by varying the regularization term λ in equation 22, different sparsity and reconstruction errors are achieved: a 4 dB SD with 8 NNZs degrades to 6 dB SD at 4 NNZs. [0080] FIG. 14 shows the variability between sparsity and reconstruction error on the full set of HRIRs over the spherical coordinate grid. Variance due to total energy in the HRIRs is accounted for as the HRIRs are normalized in the preprocessing step. Measurements closer to the ipsilateral side of the head achieve lower NNZ. These HRIRs are better summarized by fewer early reflections and obtain the lowest SD errors. Measurements closer to the contralateral side of the head experience distortions along later dense reflections that are not fully accounted for in the model described here. Comparison with Unconstrained Solutions [0081] One method of empirical validation is to compare our solutions to the unconstrained regularized least squares reconstructions (L 1 -LS) of HRIR X i given by: [0000] min {circumflex over (x)} ∥D ( {circumflex over (x)}−X i )∥ 2 2 +λ|G i | 1 .  [23] [0082] In equation 23, the {circumflex over (x)}ε M×1 and the {circumflex over (x)} j <10 −4 entries are identically zeroed. Without the non-negative constraints under the identity transform D=I, the solution {circumflex over (x)} contains only the large magnitude components {circumflex over (x)}≈X i (low magnitude components are discarded to induce sparsity). Thus, the L 1 -NNLS sparse reflections found in equation 22 can be empirically evaluated against the L 1 -LS reference solutions found in equation 23 in terms of the sparsity and reconstruction errors. [0083] In FIG. 15 , for evenly spaced horizontal and vertical plane HRIRs, the two methods are evaluated over a grid of penalty terms λ where the minimum SD reconstruction errors are recorded over the first 25 NNZ bins. For all HRIRs, the L 1 -NNLS solutions achieve the minimum reconstruction error under 2 dB SD. In half the cases, the L 1 -NNLS solutions have SD errors strictly less than the L 1 -LS solutions. This implies that the decomposition described here finds a sparse set of early reflections that explains the spectral characteristics of the HRIR better than the dominant magnitude components of the original HRIR. [0084] In practice, the penalty term λ for each HRIR can be independently tuned via a binary search for a target sparsity and reconstruction error range. The target NNZ is device dependent and can be optimized for a sparsity range such that direct convolution is faster than the FFT implementation; digital signal processors perform efficient direct convolution via hardware delay-lines. The target reconstruction error can depend on the desired fidelity of spatialization; multiple low-magnitude reverberations from sound scattering off of distant geometry in the environment may be coarsely modeled. CONCLUSION [0085] A modified semi-NMF algorithm for Toeplitz constrained matrices has been presented here. The factorization decomposed a collection of HRIRs into convolutions between a common resonance filter and a collection of reflection filters. Resonance filters were direction-independent and shown to correlate with anthropometry. Reflection filters were direction-dependent and composed of non-negative entries whose sparsity and reconstruction error could be tuned via an L 1 -NNLS solver under window and convolution transformations of various bandwidths. The reconstructed HRIRs from the decomposition can be compared to L 1 -LS reference solutions where the former had a better sparsity to SD error trade-off necessary for both efficient and accurate direct convolution. In short, the decomposed filters described here may be useful for predicting HRIRs from anthropometry, a problem of current interest. [0086] Algorithm 1, shown below, factorizes input HRIR matrix X into Toeplitz matrix {tilde over (F)} and sparse and non-negative reflections G. [0000] [Algorithm 1: Modified Semi-NMF for Toeplitz Constraints] Require: Filter Length K, transformation matrix D ∈    M * ×M , HRIR matrix X ∈    M×N , max-iterations T 1: G ← rand(N,K) \\ Randomize reflections 2: for t = 1 to T do 3:   Θ ← A −1 b \\ Solve for resonance via equations 14, 12 4:   {tilde over (F)} ← Top(Θ) \\ Form Toeplitz matrix in equations 6, 18 5:   Update G \\ Element-wise multiplicative update via equation 15 or NNLS solutions via equation 20 6:   end for 7:   Fine-tune G. \\ Adjust λ in equation 22 for varying sparsity 8:   return {tilde over (F)},G [0087] While this disclosure includes what is presently considered to be the most practical and preferred embodiments, it is to be understood that the disclosure is not to be limited to the disclosed embodiments but, on the contrary, is intended to cover various modifications and equivalent arrangements.
This application describes methods of signal processing and spatial audio synthesis. One such method includes accepting an auditory signal and generating an impression of auditory virtual reality by processing the auditory signal to impute a spatial characteristic on it via convolution with a plurality of head-related impulse responses. The processing is performed in a series of steps, the steps including: performing a first convolution of an auditory signal with a characteristic-independent, mixed-sign filter and performing a second convolution of the result of first convolution with a characteristic-dependent, sparse, non-negative filter. In some described methods, the first convolution can be pre-computed and the second convolution can be performed in real-time, thereby resulting in a reduction of computational complexity in said methods of signal processing and spatial audio synthesis.
7
FIELD OF THE INVENTION The present invention relates to actuation of downhole tools and sending information to the surface, particularly by use of nonconducting wireline. BACKGROUND OF THE INVENTION In the operation of oil well tools, it is necessary to actuate the tool at a desired location downhole. Various systems for actuating the tools have been used. One system uses an electric line cable to transmit control signals which actuate the downhole tool to receive data from the tool. Electric line well intervention can be costly, requires special tools and trained personnel, and can cause rig delays. Offshore, space for electric line equipment could be a problem since equipment for other procedures scheduled before or after running the tool may already occupy what little space is available. Another system uses established profiles in the well to set and actuate the tools. However such systems are only useful when profiles are present in the completed well. In such systems the tool becomes supported by the recessed profile with the resulting weight shift actuating the tool. These systems are subject to inexact actuation when the tool encounters restrictive passages downhole and exhibits the same conditions as being suspended in the profiles. A third system uses a pressure sensor to actuate the tool when the pressure downhole exceeds a predetermined level. Such systems are subject to inexact actuation due to deviations in downhole temperature and pressure conditions and sensitivities of known pressure transducers. A fourth system uses an accelerometer with a time delay, actuating the tool when no motion has been detected for a predetermined period. Such systems are obviously subject to premature actuation if the tool becomes lodged downhole. It is the object of the present invention to actuate downhole tools and to transmit collected data uphole using only a nonconducting cable. The present invention allows control over and communication with downhole tools using readily available rig equipment and personnel. SUMMARY OF THE INVENTION Actuation of downhole tools is accomplished by inducing motion in the wireline. The downhole tool monitors such motion for predetermined patterns. Detection of a predetermined pattern actuates performance of a desired function. The pattern selected is sufficiently unique to avoid random or premature actuation. The tool may thus be actuated using ordinary nonconducting cable. In like fashion the tool can transmit stored information to the surface by a mechanical means such the resonant frequency of a mechanical signal in the cable. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram of the components necessary for an operable actuator system according to the present invention. FIG. 2 is a representation of a circular buffer, the preferred configuration of the memory device used in the actuator system. FIG. 3 is a timing diagram representing generally unit inputs of motion and corresponding intervals which may constitute a predetermined pattern. FIG. 4 is an exemplary timing diagram showing one possible predetermined pattern. FIG. 5 is an exemplary timing diagram showing the timing of induced motion necessary to actuate the tool which is set to respond to the predetermined pattern of FIG. 4. FIG. 6 is a block diagram of the components necessary to allow transmission of data from the downhole tool according to the present invention. FIG. 7 portrays a time-based signal corresponding to induced motion of different frequencies in the wireline. FIG. 8 is a block diagram representative of a secondary safety device interposed to prevent premature actuation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Motion induced in a nonconducting wireline is used to actuate a downhole tool. Motion may be induced either manually or by a solenoid 61 attached to the wireline. A predetermined pattern of motion will cause the tool to actuate. A motion detector 10 in the downhole tool transmits a signal to a microprocessor 11 or other suitable control circuit when it detects motion. Upon receipt of a signal from the motion detector, the microprocessor reads the time value corresponding to that signal from a real-time clock 12 and stores that time value in a memory device 13. In the simplest embodiment of the present invention, the memory device is configured as a circular buffer 20 consisting simply of an fixed array of addressable memory locations 21. A pointer 22 indicates the memory location to be addressed and advances to the next memory location in the array when the indicated memory location is addressed. When the pointer reaches the last memory location in the array it cycles 23 back to the first memory location in the array. Thus, once every memory location in the buffer has been previously addressed, the oldest time value is replaced by the time value corresponding to the most recently detected motion. The number of memory locations i in the circular buffer preferably corresponds to the number necessary to determine if the predetermined pattern of motion has occurred. The microprocessor 11 uses the time values to determine if the predetermined pattern 30 of motion has occurred. Each time a signal is received from the motion detector and the corresponding time value is stored in a memory location n, the microprocessor compares the new time value to the time value stored in the preceding memory location n-1. If the interval between the two time values correlates to the last interval 31 of the predetermined pattern, the interval between the preceding time values n-1 and n-2 is determined and compared to the preceding interval 32 of the predetermined pattern. Each time the interval between time values matches the corresponding interval in the predetermined pattern, the preceding intervals are compared until either unmatching intervals are found or the predetermined pattern is detected. If unmatching intervals are found, the microprocessor simply awaits a new signal from the motion detector and repeats the process with a new time value. If the predetermined pattern is detected, the microprocessor transmits a signal 14 which actuates the tool. By way of example, suppose the selected pattern consisted of two two-minute intervals. The tool is lowered downhole and remains motionless for ten minutes. To actuate the tool downhole, motion is induced in the wireline three times at proper two minute intervals. When the first motion 51 is detected, the corresponding time value is stored and the microprocessor compares the interval since the last detected motion 56 with the last interval of the predetermined pattern 41. Since the intervals do not match, the microprocessor simply awaits further input from the motion detector. When the second motion 52 is detected, the corresponding time value is stored and the microprocessor again compares the interval since the last detected motion 55 with the last interval of the predetermined pattern 41. Since the intervals match, the microprocessor also compares the preceding interval between detected motions 56 with the preceding interval in the predetermined pattern 43. These intervals do not match, and the microprocessor again awaits further input from the motion detector. When the third motion 53 is detected, the same comparisons are made and the microprocessor, determining that intervals 54 and 55 match intervals 41 and 43 respectively, transmits a signal 14 which actuates the tool. A virtually infinite number of predetermined patterns may be used. As few as two elements of motion or nonmotion may be used to define the predetermined pattern, although the pattern must be sufficiently unique to virtually preclude unintentional actuation. Overly complex patterns should be avoided since they will merely annoy individuals actuating the tool. Unit impulses of motion separated by intervals of nonmotion provide the simplest patterns for actuation. However timed intervals of motion may be used as part of the predetermined pattern as well as intervals of nonmotion. With an appropriate motion detector, motion direction may also form part of the predetermined pattern. In either of these cases, the modifications necessary for pattern detection will be obvious to one of ordinary skill in the art. In another embodiment of the present invention, the microprocessor 11, real time clock 12, and memory device 13 are replaced by an application specific integrated circuit (ASIC) asychronously clocked by the motion detector. The ASIC compares intervals between signals from the motion detector with intervals in the predetermined pattern and sets or resets flags accordingly. When the requisite number of flags are set, the ASIC transmits a signal actuating the tool. In still another embodiment of the present invention, the predetermined pattern may be frequency-based rather than time-based. Motion induced in the wireline will propagate as a decaying sinusoidal wave having a natural resonant frequency. A variable damping mechanism may be used to alter that natural resonant frequency between a high frequency and a low frequency. The frequency of these waves may be detected, with initial synchronization patterns used to set thresholds for distinguishing high and low frequencies. Patterns of high and low frequencies may be used to transmit control codes in binary form to the downhole tool. Induced motion may also be used to allow the downhole tool to transmit data to the surface. Motion induced in the wireline will reflect off the tool, propagating in both directions as a decaying sinusoid with a frequency equalling that of the natural resonant frequency of the system. An electronically controlled variable damping mechanism 65 such as a dash pot may be placed on the tool. Thus the tool can control the natural resonant frequency of waves propagating in the wireline, varying it between a high frequency and a low frequency. The high and low frequencies correspond to bits of data to be transmitted. The tool includes devices 68 for collecting and storing data of the desired type. The data could be, for example, the number of tubing collars which the tool detects as it is lowered. This data may be gathered in the same manner presently used in electric line operations, but the data would be stored at the tool instead of contemporaneously transmitted to the surface. Similar to the first embodiment described, a predetermined pattern of motion is used actuate the tool's asynchronous mechanical transmission of data to the surface. In transmitting the data, the tool adjusts the variable damping mechanism 65 through a microprocessor or ASIC 67 and the appropriate control circuitry 66. This alters the natural resonant frequency to either a first frequency 71 or a second frequency 72, depending on the first bit of data to be transmitted. Motion is induced in the wireline at the surface, exciting the system into resonance. The motion travels as a decaying sinusoid at the resonant frequency before reflecting off the tool. At the surface, the frequency of the reflected wave is measured by an accelerometer 64 and interpreted for its binary value using conventional electronics 6-3. Meanwhile the tool, upon detecting the motion, waits an appropriate length of time before adjusting the variable damping mechanism, altering the natural resonant frequency to correspond to the next bit of data to be transmitted. If the value of the second bit of data matches the value of the first bit, the variable damping mechanism need not be adjusted. Motion is again induced in the wireline and the frequency of the reflection measured and interpreted. The tool again adjusts the variable damping mechanism, altering the natural resonant frequency to correspond to the next bit of data. This asynchronous process continues until all data is received at the surface. Receipt of data from the downhole tool is especially useful, for example, when accurate placement of the tool is necessary before actuation. Surface cable counters are inaccurate due to slippage and cable stretch under downhole temperature conditions. However maps of the well, including locations of tubing collars, are normally available. Therefore the tool can be configured to count tubing collars as it is lowered and transmit the number of collars counted to the surface. A specific collar may be located by lowering the tool until the collar count is either the correct number or ±1, then raising or lowering the tool incrementally until the collar count changes, indicating that the desired collar has just been passed. Since the distance between tubing collars is short enough to render any error caused by slip or temperature stretch neglegible, once a specific collar is located the tool may be accurately placed using the surface cable counter. In order to permit accurate detection of transmitted data at the surface, a synchronization code may be used to set thresholds and ranges for frequencies corresponding to bits of data. The tool first sends a predetermined pattern of high and low frequencies which is detected at the surface and used to determine the thresholds and ranges defining later bits of information. The tool then sends the data, which may be directly interpreted. With any embodiment of the present invention, a secondary safety device 81 may be used to prevent premature actuation. For example, a pressure transducer or a temperature-actuated relay may be electrically connected to the actuator system such that actuation cannot occur until certain downhole pressure or temperature conditions are detected. The actuating signal 14 from the microprocessor is only relayed 80 to the tool if those conditions are detected. Such safety devices will insure that actuation does not occur before the tool has reached a threshold depth, preventing premature actuation and allowing use of simple motion patterns for actuation. The foregoing disclosure and description of the invention are illustrative and explanatory thereof, and various changes in the size, shape and materials, as well as in the details of the illustrated construction, may be made without departing from the spirit of the invention.
Actuation of downhole tools is accomplished by inducing motion in the wireline. The downhole tool monitors such motion for predetermined patterns. Detection of a predetermined pattern actuates performance of a desired function. The pattern selected is sufficiently unique to avoid random or premature actuation. The tool may thus be actuated using ordinary nonconducting cable. In like fashion the tool can transmit stored information to the surface by a mechanical means such the resonant frequency of a mechanical signal in the cable.
4
BACKGROUND OF THE INVENTION The invention relates to an adaptive vehicle drive system which shifts from two-wheel drive to four-wheel drive upon sensing certain conditions, and more specifically to an adaptive system which detects high magnitude and rapid repetition wheel spin transients and shifts to four wheel drive operation for a predetermined time period. The performance advantages of four-wheel vehicle drive systems are well recognized. Improved vehicle stability while traversing rain soaked or ice or snow covered highways, handling and control on gravel or uneven pavement and simply maintaining traction in off road situations are all readily acknowledged benefits. Concomitant and less desirable attributes of four-wheel drive systems relate to reduced gas mileage from increased drive line friction and increased vehicle weight. Such increased drive line friction occurs in part time four-wheel drive systems which rotationally couple the front and rear vehicle propshafts. Such vehicle weight increases are particularly pronounced if the system is designed with a differential between the front and rear drive shafts for full-time engagement and operation rather than intermittent operation when conditions specifically demand it. Furthermore, while part time four-wheel drive systems which lock the front and rear propshafts together provide obvious benefits of traction and stability in straight line driving, the disparity between the ground speed at the front wheels and the ground speed at the rear wheels during cornering can itself result in wheel slip and hopping of the vehicle. Thus, allowing the front and rear output shafts of the transfer case to operate at different speeds during cornering is beneficial. Many four-wheel drive systems employing diverse control and torque distribution strategies have been designed and utilized. These various approaches are embodied in United States patents. For example, U.S. Pat. No. 4,417,641 teaches a four-wheel drive system having an electromagnetic clutch and steering sensor. When the steering wheels are turned greater than a predetermined angle, the electromagnetic clutch is de-energized, disconnecting two drive wheels. U.S. Pat. No. 4,718,303 discloses a transfer case having an electromagnetic ramp clutch which is modulated to adjust torque distribution in a full time four-wheel drive system. In U.S. Pat. No. 4,937,750, a microcomputer compares signals from front and rear driveline speed sensors. If the difference is greater than a certain value, a clutch is engaged to interconnect the front and rear drivelines. U.S. Pat. No. 4,989,686 discloses a four-wheel drive system including wheel speed detectors. The detectors control a proportional clutch which delivers torque to whichever driveline is rotating more slowly. U.S. Pat. No. 5,002,147 discloses a four-wheel drive system which achieves torque splitting between the front and rear axles. The system utilizes four wheel speed sensors and a steering angle sensor. In U.S. Pat. No. 5,060,747, a torque distribution system is taught which includes both vehicle and front and rear wheel speed sensors. Vehicle speed data is utilized to adjust the wheel speed difference value and this adjusted value is utilized to engage a clutch. U.S. Pat. No. 5,090,510 discloses a four-wheel drive system having a differential and a hydraulic clutch disposed in parallel between the front and rear drive shafts. A nearly universal problem of the foregoing active torque distribution systems is their operation in extreme off-road conditions, such as sand or mud, where randomly repeated, high magnitude speed difference transients repeatedly activate and deactivate the torque distribution clutch. Such operation is often justly characterized as unpleasant by the vehicle operator and occupants because of the abrupt, random and repeated cycling of the torque distribution clutch which is counter to the smooth, adaptive torque distribution goal of such systems. A control strategy that will recognize operation under such conditions and provide a smooth and comfortable operational solution to such conditions is therefore desirable. SUMMARY OF THE INVENTION An on demand four-wheel vehicle drive system monitors vehicle performance and operating conditions and inhibits proportioning torque distribution operation when certain operating parameters associated with severe operating conditions such as sand are detected. The vehicle drive system includes a transfer case having primary and secondary output shafts driving primary and secondary drivelines, a plurality of speed sensors and a microcontroller. The speed sensors include a primary (rear) and secondary (front) driveline speed sensor and driveline status sensors. The secondary axle may include coupling components such as locking hubs or axle disconnects. The transfer case may either be a single speed device or may include a planetary gear assembly or similar device providing high and low speed ranges as well as neutral. The transfer case includes a modulating electromagnetic clutch controlled by the microcontroller which selectively transfers torque from the primary output shaft to the secondary output shaft. The transfer case also includes a locking clutch which is in mechanical parallel with the modulating clutch and may be activated to directly couple the primary output shaft to the secondary output shaft. Selection of the on demand vehicle drive system both activates the secondary axle engaging components and may provide a minimum (standby) current to the modulating clutch which establishes a minimum torque transfer level. When the speed of one of the drive shafts overruns the speed of the other drive shaft by a predetermined value related to the vehicle speed and the identity of the overrunning shaft, indicating that wheel slip is present, clutch current is increased to increase clutch engagement and torque transfer to the secondary drive shaft until the speed difference between the drive shafts and thus wheel slip is reduced below the predetermined value. Reduction of the clutch current then occurs. In extreme off road conditions, such as sand, the tractive conditions may vary rapidly and dramatically, causing the on demand drive system to cycle randomly, rapidly and repeatedly between substantially fully engaged and fully disengaged clutch positions. Such operation is less than acceptable not only to the driver and passengers but also to the driveline components which are subjected to accelerated wear. A microprocessor reads and computes both average driveline speed differences and speed transients which exceed predetermined values based upon the more slowly turning driveshaft speed. When these values are exceeded, the modulating clutch is fully activated and the lockup clutch is activated after which the modulating clutch is slowly relaxed. Typically the lockup clutch will remain engaged for a five minute interval. After the five minute interval, the lockup clutch is disengaged and system operation returns to normal on demand operation. The on demand vehicle drive system may be an active full-time system, may be selectively activated by the vehicle operator or may be automatically activated by driving conditions. The system may be utilized with either primary front wheel or primary rear wheel drive configurations. Thus it is an object of the present invention to provide an on demand system which is capable of detecting operation in extreme off road conditions such as sand. It is a further object of the present invention to provide a vehicle drive system having both a modulating clutch which functions during normal on demand driving conditions and a lockup clutch which engages during extreme off road driving conditions. It is a still further object of the present invention to provide a transfer case having parallel modulating and lockup clutches which provide modulating coupling between the primary and secondary output of the transfer case as well as providing lockup between such output while deactivating the modulating clutch. It is a still further object of the present invention to provide an on demand vehicle operating system wherein the sensing of extreme off road operating conditions overrides the on demand torque distribution system and directly couples or locks up the primary and secondary drive lines for a predetermined period. It is a still further object of the present invention to provide a vehicle drive system which may be utilized in either primary rear wheel drive or primary front wheel drive vehicle driveline configurations. It is a still further object of the present invention to provide a control system for use with an on demand system to control a transfer case having modulating and lockup clutches disposed in parallel across the primary and secondary outputs. Further objects and advantages of the present invention will become apparent by reference to the following Description of the Preferred Embodiment and appended drawings wherein like reference numerals designate the same components, elements or features. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagrammatic plan view of the drive components and sensors of an on demand vehicle drive system according to the present invention; FIG. 2 is a full, sectional view of a transfer case and electromagnetic clutch assembly in an on demand system according to the present invention; FIG. 3 is an enlarged, fragmentary sectional view of the Electromagnetic clutch assembly in an on demand vehicle drive system according to the present invention; FIG. 4 is a flat pattern development of a section of one clutch ball and associated recesses incorporated in the electromagnetic clutch assembly taken along line 4--4 of FIG. 3; FIG. 5 is an exploded perspective view of the lockup clutch in a transfer case according to the present invention; FIG. 6 is a first portion of a software program for detecting extreme off road driving conditions and controlling a vehicle torque delivery system; and FIG. 7 is a second portion of a software program for detecting extreme off road driving conditions and controlling a vehicle torque delivery system. DESCRIPTION OF THE PREFERRED EMBODIMENT Part I--Mechanical Components Referring now to FIG. 1, an on demand vehicle drive system is illustrated and generally designated by the reference numeral 10. The on demand system 10 is incorporated into a vehicle having a prime mover, such an internal combustion engine 12, which drives a conventional transmission 14 which may either be a manual transmission with a clutch or an automatic transmission. The output of the transmission 14 is operably coupled to a transfer case assembly 16. In turn, the transfer case is operably coupled to and drives a rear or primary driveline 20 having a rear or primary drive shaft 22 which is operably coupled to and drives a rear or primary differential 24. The primary or rear differential 24 drives a pair of aligned primary or rear axles 26 which are coupled to primary or rear tire and wheel assemblies 28. The transfer case assembly 16 also provides torque to a front or secondary driveline 30. The secondary driveline 30 includes a front or secondary drive shaft 32 which in turn drives the front or secondary differential 24. The secondary differential 24 operates in conventional fashion and provide drive torque through a pair of aligned front or secondary axles 36. A pair of front or secondary tire and wheel assembles 38 are disposed at the front of the vehicle. A pair of locking hubs 42 are operably disposed between a respective one of the front or secondary axles 36 and the front tire and wheel assemblies 38. The locking hubs 42 may be either remotely operated and thus include electrical or pneumatic operators or may be manually activated. Alternatively, front axle disconnects (not illustrated) may be housed within the front or secondary differential 34 and the axle disconnects may be activated or deactivated to couple or uncouple the secondary axles 36 from the output of the secondary differential 34. The system 10 also include a microcontroller 44 having various programs and subroutines which receive various data from vehicle sensors and provide control outputs to achieve the design function and goals of the present invention which will be more fully described below. It should be understood that the designations "primary" and "secondary" appearing both above and below refer to drivelines and driveline components in the system 10 which are primarily and secondarily intended to propel a vehicle. That is, in the system 10 illustrated, the inventor describes a vehicle which is commonly referred to as a rear wheel drive vehicle in which the rear tire and wheel assemblies 28 primarily from both a time and torque standpoint propel the vehicle. Hence, the secondary driveline 30 and the front or secondary tire and wheel assemblies 38 typically function intermittently, that is, on an as needed basis, to provide improved vehicle performance and stability in adverse driving conditions. It should be understood, however, that the operating components and method described herein are fully and equally usable and suitable for a vehicle wherein the primary driveline and tires are disposed at the front of the vehicle, that is, a vehicle commonly referred to as a front wheel drive vehicle, and the secondary driveline and tires are located toward the rear of the vehicle. Referring now to FIGS. 2 and 3, it will be appreciated that the transfer case assembly 16 includes a multiple part, typically cast, housing 46 having various openings for shafts and fasteners and various mounting surfaces and grooves for oil seals, bearings, seal retaining rings and other internal components as will be readily appreciated. The transfer case assembly 16 also includes a planetary gear assembly 48 which is driven by an input shaft 50 rotatably supported within the transfer case assembly 16. The input shaft 50 is coupled to and driven by the output of the transmission 14. The input shaft 50 defines a re-entrant bore 52 which receives a roller bearing assembly 54. The roller bearing assembly 54, in turn, receives and rotatably supports the forward terminus 56 of a rear (primary) output shaft 58. A gerotor pump 62 is secured about and rotates with the output shaft 58, providing lubricating fluid under pressure to a passageway 64 which extends axially within the output shaft 58 and distributes lubricating and cooling fluid to components of the transfer case assembly 16. In the planetary gear assembly 48, the input shaft 50 defines an enlarged, bell-shaped region 66 having a plurality of external teeth 68 which define a sun gear 70. On the inner surface of the bell-shaped region 66 of the input shaft 50 are a plurality of female splines or gear teeth 72. Axially aligned with the sun gear teeth 68 is a ring gear 74 having a plurality of female splines or inwardly directed gear teeth 76. A plurality of pinion gears 78, one of which is illustrated in FIGS. 2 and 3 are rotatably received upon a like plurality of stub shafts 82 which are fixedly mounted within a carrier 84. The carrier 84 includes a plurality of inwardly directed female splines or gear teeth 86 on a surface generally axially adjacent but spaced from the internal gear teeth 72 defined by the input shaft 50. The planetary gear assembly 48 is more fully described in co-owned U.S. Pat. No. 4,440,042 which is herein incorporated by a reference. An axially sliding, that is, dog type, clutch 90 is received about the output shaft 58. The dog clutch 90 defines an inwardly directed plurality of female splines or gear teeth 92 which are complimentary to and mate with a like plurality of external splines or male gear teeth 94 disposed about the periphery of the output shaft 58. The dog clutch 90 thus rotates with the output shafts 58 but may slide axially therealong. The dog clutch 90 includes a region of male splines or external gear teeth 96 which are complimentary to the teeth or splines 72 and 86 disposed on the input shaft 50 and the planetary gear carrier 84, respectively. The dog clutch 90 is thus axially translatable between a first, forward position wherein the external teeth 96 couple with the gear teeth 72 and provide direct drive between the input shaft 50 and the output 58 and a second, rearward position, to the right in FIG. 2 wherein the dog clutch 90 engages the gear teeth 86 on the carrier 84 and provides a reduced speed drive between the input shaft 50 and the output shaft 58 in accordance with the gear ratio provided by the planetary gear assembly 48. A dog clutch 90 may also be moved to a third, neutral position mid-way between the forward, direct drive position and the rearward reduced speed drive position. In this middle position, the input shaft 50 is disconnected from the output shafts 58 and no torque is transferred therebetween. The position of the dog clutch 90 is commanded by an electric shift control motor 100. The electric shift control motor 100 rotates a drive shaft 102. The drive shaft 102 is suitably supported for rotation with the housing 46 of the transfer case assembly 16. The position of the drive shaft 102 may be monitored and read by an encoder assembly (not illustrated) which provides information about the current position of the drive shaft 102 and the dog clutch 90 to the microcontroller 40. The drive shaft 102 terminates in and drives a spring assembly 104. The spring assembly 104 is wrapped about the drive shaft 102 and is also engaged by an arm 106 which extends axially from a cylindrical cam 108. The spring assembly 104 functions as a resilient coupling between the drive shaft 102 and the cylindrical cam 108 to absorb lag between the movement commanded by the drive motor 100 and the driven components so that the shift motor 100 is allowed to reach its final requested position. The spring assembly 104 allows smooth and fast response to a requested repositioning of the dog clutch 90 in situations where the gear teeth 96 of the dog clutch 90 do not instantaneously engage the internal teeth 72 of the input shaft 50 or the internal gear teeth 86 of the carrier 84. When relative rotation of the dog clutch 90 allows engagement of the aforementioned clutch teeth, potential energy stored in the spring assembly 104 rotates the cylindrical cam 108 to its requested position, thus completing the shift. The cylindrical cam 108 defines a helical track 112 which extends approximately 270° about the cam 108. The helical track 112 receives a pin or cam follower 114 which is coupled to and translates a fork assembly 116. The fork assembly 116 is supported for bidirectional translation upon a fixed shaft 118 and engages the periphery of the dog clutch 90. Rotation of the shaft 102 axially repositions the cam follower 114 and axially positions the dog clutch 90 in one of the three positions described above. It will be appreciated that the planetary gear assembly 48 including the mechanism of the dog clutch 90 which provides dual range, i.e., high and low speed, capability to the transfer case assembly 16 is optional and that the vehicle drive system 10 is fully functional as a single speed direct drive unit and may be utilized without these components and the dual speed range capability provided thereby. The transfer case assembly 16 also includes an electromagnetically actuated disc pack type clutch assembly 120. The clutch assembly 120 is disposed about the output shaft 58 and includes a circular drive member 122 coupled to the output shaft 58 through a splined interconnection 124. The circular drive member 122 includes a plurality of circumferentially spaced apart recesses 126 in the shape of an oblique section of a helical torus, as illustrated in FIG. 4. Each of the recesses 126 receives one of a like plurality of load transferring balls 128. A circular driven member 132 is disposed adjacent the circular drive member 122 and includes a like plurality of opposed recesses 134 defining the same shape as the recesses 126. The oblique side walls of the recesses 126 and 134 function as ramps or cams and cooperate with the balls 128 to drive the circular members 122 and 132 apart in response to relative rotation therebetween. It will be appreciated that the recesses 122 and 134 and the load transferring balls 128 may be replaced with other analogous mechanical elements which cause axial displacement of the circular members 122 and 132 in response to relative rotation therebetween. For example, tapered rollers disposed in complementarily configured conical helices may be utilized. The circular driven member 132 extends radially outwardly and is secured to a electromagnetic coil housing 136. The coil housing 136 includes a face 138 which is disposed in opposed relationship with a clutch face 140 on an armature 142. The coil housing 136 surrounds an electromagnetic coil 144 on three sides. The electromagnetic coil 144 is provided with electrical energy preferably from a pulse width modulation (PWM) control through an electrical conductor 146. The pulse width modulation scheme increases or decreases the average current to the electromagnetic coil 144 of the electromagnetic clutch assembly 120 and thus torque throughput by increasing or decreasing the on time (duty cycle) of a drive signal. It will be appreciated that other modulating control techniques may be utilized to achieve engagement and disengagement of the electromagnetic disc pack type clutch assembly 120. Providing electrical energy to the electromagnetic coil 144 causes magnetic attraction of the armature 142 with the coil housing 136. This magnetic attraction results in frictional contact of the armature 142 to the coil housing 136. When the output shaft 58 is turning at a different speed than the armature 142 this frictional contact results in a frictional torque being transferred from the output shaft 58, through the circular drive member 122, through the load transferring balls 128 and to the circular driven member 132. The resulting frictional torque causes the balls 128 to ride up the ramps of the recesses 126 and 134, causing axial displacement of the circular drive member 122. Axial displacement of the circular drive member 122 translates a washer 148 and an apply plate 149 axially toward a disc pack clutch assembly 150. A compression spring 152 which may comprise a stack of Belleville washers provides a restoring force which biases the circular drive member 122 toward the circular driven member 132 and returns the load transferring balls 128 to center positions in the circular recesses 126 and 134 to provide maximum clearance and minimum friction between the components of the electromagnetic clutch assembly 120 when it is deactivated. The disc pack clutch assembly 150 includes a plurality of interleaved friction plates or discs 154. A first plurality of discs 154A are coupled by interengaging splines 156 to a clutch hub 158 which is coupled to the output shaft 58 for rotation therewith. A second plurality of discs 154B are coupled to an annular housing 160 by interengaging splines 162 for rotation therewith. An important design consideration of the recesses 126 and 134 and the balls 128 is that the geometry of their design and the design of the washer 148, the compression spring 152 and the clearances in the disc pack assembly 150 ensure that the electromagnetic clutch assembly 120 is not self-locking. The electromagnetic clutch assembly 120 must not self-engage but rather must be capable of controlled, proportional engagement of the clutch discs 154 and torque transfer in direct response to the modulating control input. The annular housing 160 is disposed for free rotation about the output shaft 58 and is coupled to a chain drive sprocket 162 by a plurality of interengaging splines or lugs and recesses 164. The chain drive sprocket 162 is also rotatably disposed on the output shaft 58 and is supported freely by a roller or needle bearing assembly 166. When the clutch assembly 120 is engaged, it transfers energy from the output shaft 58 to the chain drive sprocket 162. A drive chain 168 is received upon the chain drive sprocket 162 and engages and transfers rotational energy to a driven chain sprocket 170. The driven sprocket 170 is coupled to a front (secondary) output shaft 172 of the transfer case assembly 16 by interengaging splines 174. The transfer case assembly 16 also includes a first Hall effect sensor 180 having an output line 182 which is disposed in proximate, sensing relationship with a plurality of teeth 184 on a tone wheel 186 which is coupled to and rotates with the rear (primary) output shaft 58. A second Hall effect sensor 190 has an output line 192 and is disposed in proximate, sensing relationship with a plurality of teeth 194 of a tone wheel 196 disposed adjacent the driven sprocket 170 on the front output shaft 172. Preferably, the number of teeth 184 on the tone wheel 186 is identical to the number of teeth 194 on the tone wheel 196 so that identical shaft speeds result in the same number of pulses per unit time from the Hall effect sensors 180 and 190. This simplifies computations relating to shaft speeds and improves the accuracy of all logic decisions based on such data and computations. As to the actual number of teeth 184 on the tone wheel 186 and teeth 194 on the tone wheel 196, it may vary from thirty to forty teeth or more or fewer depending upon rotational speeds and sensor construction. The use of thirty-five teeth on the tone wheels has provided good results with the Hall effect sensors 180 and 190 and is therefore the presently preferred number of teeth. The first and second Hall effect sensors 180 and 190 sense the respective adjacent teeth 184 and 194 and provide a series of pulses in the lines 182 and 192, respectively, which may be utilized to compute the instantaneous rotational speeds of the rear output shaft 58 and the front output shaft 172 which, of course, correspond to the rotational speeds and the rear drive shaft 22 and the front drive shaft 32, respectively. These rotational speeds may be utilized to infer the speed of the vehicle as well as determine overrunning by either the front or the rear drive shafts relative to the other which represents wheel spin and thus wheel slip. Hall effect sensors are preferred inasmuch as they provide an output signal which alternates between a well defined high and low signal value as the sensed teeth pass. It will be appreciated that other sensing devices such as, for example, variable reluctance sensors may be utilized. Such sensors do not, however, provide the clean wave form provided by Hall effect sensors, particularly at low shaft speeds, and thus may require extra input conditioning to provide useable data. It should also be appreciated that the Hall effect sensors 180 and 190 and their respective adjacent teeth 184 and 194 are preferably located within the housing 46 of the transfer case assembly 16 but may be located at any convenient site along the primary and secondary drive lines 20 and 30, respectively. Referring now to FIGS. 2, 3 and 5, the transfer case assembly 16 also includes a locking clutch assembly 200. The locking clutch assembly 200 includes a first or internal collar 202 having internal female splines or gear teeth 204 which engage complimentarily configured male splines or gear teeth 206 formed in the output shaft 58 along a central portion of its length. The output shaft 58 also includes a step or shoulder 208 which limits axial travel of the first collar 202 therealong. A thrust bearing 212 is positioned adjacent the first collar 202. The exterior of the first collar 202 includes a first plurality of gear teeth or male splines 216 which extend fully, axially across its exterior surface. Interleaved with the first set of male splines 216 are a plurality of axial, foreshortened channels or grooves 218 which extend only from the right face of the first collar 202 to approximately its midpoint. Concentrically disposed about the first collar 202 is a second or exterior clutch drive collar 222. The clutch drive collar 222 includes a pair of peripheral, circumferential ribs 224 which cooperatively define a circumferential groove 226 which, in turn, receives a shift fork 228. The shift fork 228 is slidably disposed upon the fixed shaft 118 and includes a cam follower 232 which is received within a cam track 234 in the cylindrical cam 108. A compression spring 236 biases the shift fork 228 to the left as illustrated in FIG. 2 and 3. A compression spring 238 is also received within the second, exterior clutch collar 222 and provides a biasing force which tends to drive apart the second clutch collar 222 and a third toothed collar 242. The third or toothed collar 242 includes a plurality of internal gear teeth or female splines 244 which are complimentary to and engage the splines 216 and foreshortened grooves 218 on the first clutch collar 202. Thus, the third clutch collar 242 enjoys limited axial motion on the first clutch collar 202, having its axial translation effectively limited by the lengths of the grooves or channels 218. A snap ring 246 engages a flange 248 on the third clutch collar 242. The snap ring 246 is received within a channel 252 formed on the interior of the second clutch collar 222. Finally, the third clutch collar 242 includes a plurality of gear teeth or male splines 254 disposed adjacent and extending axially from the flange 248. The male splines or gear teeth 254 are complimentary to, aligned with and axially engageable with or disengageable from the female splines or gear teeth 256 formed in the chain drive sprocket 162. Part II--Electronic/Software Components When a typical on demand four wheel drive system, that is, a system wherein a speed difference between the front and rear wheels or prop shafts which exceeds a reference value causes an inter-driveline clutch to selectively couple the two drivelines in accordance with its control parameters, is driven in deep sand and certain other off road conditions, the system may cycle randomly, transiently and repeatedly between minimum and maximum clutch engagement and driveline coupling. In mathematical terms, the sum of the speed differences over time greatly exceeds the sum of speed differences over time of other types of driving. As noted above, this cyclic transient operation is unpleasant to the vehicle occupants and is inconsistent with the design goals of on demand vehicle torque delivery systems. Furthermore, the constant cycling of the clutch creates significant heat within the transfer case which can be deleterious to performance and service life expectancies. In order for a control scheme of an on demand torque system to address the challenge of providing appropriately smooth and predictable operation in a vehicle driving in sand, it is first necessary to establish a detection protocol to determine when this condition exists. Generally speaking, three categories of vehicle operation and driving conditions can be defined. They are: a) normal driving conditions including occasional wheel slip and on demand operation, b) situations where one or a pair of oversized or undersized tires such as compact spare tires are mounted on the vehicle and c) operation of the vehicle in sand or similar tractive conditions. Each of these three operating conditions have distinct operating signatures which aid in the detection of the latter mode. Specifically, determination of a long term average speed difference and the number of transients or spikes over such long term, when properly conditioned, can provide an indication of which one of the three operating categories represents the current vehicle driving condition. In the foregoing statement the designation "long term" means in the range of from approximately b 1 second to 30 seconds and thus is significantly longer than the operating and active response period of the on demand system which is typically measured in milliseconds. The following Table I sets forth the characteristics of these three operating categories. TABLE I______________________________________ AVERAGE SPEED SPEED TRANSIENTSDRIVING CONDITION DIFFERENCE OR SPIKES______________________________________Normal Low FewMis-sized tire High Negligibleor compact spareSand High Many______________________________________ The foregoing Table I highlights the random cyclic operation of a vehicle on demand system in sand which is characterized by rapid cycling between a high speed difference between the front and rear drivelines, followed by a low speed difference after the on demand system engages, a relaxation of the on demand system followed by an abrupt high speed difference, reengagement of the on demand system, a low speed difference, ad infinitum. Accordingly, the software and subroutines of the adaptive drive system 10 of the present invention are configured to detect this operating condition. However, it is preferred to determine experimentally the operating characteristics of each particular vehicle to determined its activity in an extreme operating environment such as sand in order to improve the capability of the control system and to differentiate between extreme conditions which override the on demand function or conditions which are not so extreme and allow the on demand function to operate conventionally. Referring now to FIG. 6, a flow chart for a typical microprocessor program 300 for the detection of extreme vehicle operating conditions such as sand is illustrated. The program 300 is intended to be utilized with an on demand system such as that described in co-owned U.S. Pat. No. 5,407,024. The program 300 begins with a start command 302 which may be commanded by the executive system of the on demand vehicle controller on a relatively frequent basis such as once every one to five seconds. The program 300 then moves to a decision point 304 which determines whether the vehicle is operating in on demand torque distribution mode either by virtue of manual or automatic selection. If it is not, the program 300 immediately moves to an end step 306A and returns to the executive system. If the vehicle is in on demand torque distribution mode, the program 300 then moves to a second decision point 308 wherein a five minute countdown timer is interrogated to determine if it is already counting. If the response is yes, the program 300 branches to a decision point 310 which will be discussed subsequently. If the five minute countdown timer is not active, the program 300 moves to a process step 312 which reads the outputs of the Hall effect sensors 180 and 190 and computes the average speed difference (delta) between the readings over the last three seconds. The program 300 then moves to a decision point 314 which compares this calculated average speed difference (delta) with a computed value representing ten percent of the slower of the two drive shafts 22 and 32. If this calculated average speed difference (delta) is less than ten percent of the speed of the slower of the two drive shafts 22 and 32, the decision point 314 is exited at NO and the program 300 moves to the end step 306A. If the calculated average speed difference (delta) for the last three seconds is greater than ten percent of the speed of the slower of the two drive shafts 22 and 32, the decision point 314 is exited at YES and the program 300 moves to a process step 316. The process step 316 determines the maximum speed difference (delta) between the two drive shafts 22 and 32 as sensed by the Hall effect sensors 180 and 190, respectively, over the last three seconds. The program 300 then moves to a decision point 318 which compares the maximum speed difference (delta) determined in the process step 316 to a value representing thirty percent of the slower of the two drive shafts 22 and 32. If the maximum speed difference (delta) is less than thirty percent of the slower of the two drive shafts 22 and 32, the program 300 moves to the end step 306A and returns to the system. If, on the other hand, the maximum speed difference (delta) over the last three seconds is greater than thirty percent of the speed of the slower of the two drive shafts 22 and 32, the decision point 318 is exited at YES and the program 300 moves to a process step 322. The process step 322 commands an electronic PWM controller (not illustrated) to provide maximum current to the electromagnetic coil 144 such that the disc pack clutch assembly 150 fully engages. When the disc pack clutch assembly 150 is fully engaged, the torque split between the primary driveline 20 and the secondary driveline 30 is equal, that is, fifty-fifty. Next, a process step 324 is undertaken which commands the shift motor 100 to rotate to translate the shift fork 228, the second clutch collar 222 and the third clutch collar 242 to engage the chain drive sprocket 162 such that the front or secondary output shaft 172 is directly coupled to and driven by the primary or rear output shaft 58. At this time, there is a parallel mechanical connection between the primary output shaft 58 and the secondary output shaft 172 through both the disc pack clutch assembly 150 and the locking clutch assembly 200. The program 300 then moves to a process step 326 which illuminates an indicator light 328 (illustrated in FIG. 1) on the instrument panel of the vehicle (both not illustrated) indicating that the vehicle is in four wheel drive operating mode. Referring now to FIG. 7, the program 300 continues with another process step 330 which starts a five minute countdown timer. This is the same five minute timer referenced in decision point 308. The program 300 then moves to an additional process step 332 which slowly reduces the control voltage or duty cycle to the coil 144 of the electromagnetic clutch assembly 120 over a ten second interval. Next, a decision point 310 is entered which determines whether any shift has been requested by the vehicle operator. The decision point 310 may also be reached from decision point 308 if an affirmative response is received to the interrogation to determine if the five minute countdown timer is active. If no shift has been requested by the vehicle operator, the program 300 moves to a decision point 334 which determines whether the speed of the vehicle is greater than thirty-five miles per hour (56 kilometers per hour). If the vehicle speed is below this threshold, the decision point 334 is exited at NO and the program 300 moves to a decision point 336 which determines whether the five minutes of the five minute countdown timer have elapsed. If they have not, the program moves to an end step 306B and returns to the system. If the five minutes of the five minute countdown timer have elapsed, the decision point 336 is exited at YES and the program 300 moves to a process step 338. Also, if in the decision point 334, it is determined that the vehicle speed is greater than the threshold speed, the decision point 334 is exited and the program 300 also moves to the process step 338. In the process step 338, the shift motor 100 is commanded to move the shift fork 116 to the left such that the clutch collar 90 directly couples the input shaft 50 to the primary output shaft 58 and the locking clutch assembly 200 releases the coupling between the primary output shaft 58 and the chain drive sprocket 162. Thus the vehicle is returned to two wheel drive high on demand operation. In the next process step 340, the electromagnetic clutch assembly 120 is returned to its normal on demand operation. Finally, the program 300 moves to a process step 342 which clears the five minute timer, preparatory to a subsequent five minute countdown, cycles to the end step 306B and returns to the executive control system. Returning to the decision point 310, if a shift has been requested by the vehicle operator, the program 300 branches to a process step 344. The process step 344 commands the control scheme of the vehicle on demand system to follow the normal strategy for the requested shift. If the shift requested is appropriate it is carried out. If the shift request is inappropriate it will typically be ignored. Again, these steps are under the control of the vehicle on demand system. After the shift request is processed in step 344, the program 300 moves to the process step 342, clears the five minute countdown timer and moves to end step 306B. It should be appreciated that the precise sequence of steps in the foregoing program 300 as well as the numerical values such as the five minute countdown timer, the 35 mile per hour threshold, the 10 second modulating clutch voltage/engagement reduction period, the three second period for averaging speed, the ten percent average speed difference threshold and thirty percent transient speed difference threshold are presented as illustrative and explanatory examples and are not to be considered as limiting of the foregoing invention. These values may and typically will be adjusted over a range of plus or minus fifty percent and perhaps a wider range in order to adapt to the weight, weight distribution, traction, time constants, torque and torque distribution characteristics of a particular vehicle. In fact, the invention may properly be considered to be the combination of hardware, that is, a transfer case having both a modulating and lockup clutch and electronic circuitry and software capable of detecting the rapid, repeated average and transient speed differences associated with operation of a vehicle on demand drive system in sand and generating control signals which sequentially engage the modulating clutch and the lockup clutch, allow the modulating clutch to relax and, after a predetermined period of time, release the lockup clutch and return to normal, on demand, operation. The foregoing disclosure is the best mode devised by the inventor for practicing this invention. It is apparent, however, that devices and methods incorporating modifications and variations will be obvious to one skilled in the art of on demand vehicle drive systems. Inasmuch as the foregoing disclosure is intended to enable one skilled in the pertinent art to practice the instant invention, it should not be construed to be limited thereby but should be construed to include such aforementioned obvious variations and be limited only by the spirit and scope of the following claims.
An adaptive torque control and distribution system for a motor vehicle having a transfer case, primary driveline and drive wheels and secondary driveline and drive wheels for operation in extreme off road conditions such as sand. The transfer case includes a modulating clutch and a lockup clutch disposed in parallel between its primary (rear) output and secondary (front) output. The system detects abnormally high magnitude and rapidly repeating wheel spin transients which are characteristic of operation in sand or similar highly randomly variable tractive conditions and overrides the on demand torque distribution program for a predetermined time interval. During this predetermined time interval, the transfer case lockup clutch is activated thereby coupling the primary and secondary drivelines and achieving a fifty-fifty torque split therebetween while the modulating clutch is inactive. The system and this operating mode reduces clutch and clutch operator cycling thereby reducing heat generation within the transfer case and increasing clutch and transfer case longevity.
8
FIELD OF THE INVENTION [0001] The present application relates generally to enabling users to avoid having their wireless devices being tracked, recorded, and correlated by providing the devices with anonymous addresses for use in network transmissions. BACKGROUND OF THE INVENTION [0002] Note that the discussion below is background information only and is not intended as an admission that anything discussed necessarily is prior art. [0003] Tracking people by means of tracking their portable computing devices (such as wireless telephones) has become endemic. So called “smart phones” often support the wireless personnel area network (WPAN) technology, Bluetooth, and the wireless local area network (WLAN), technology IEEE 802.11, marketed under the Wi-Fi brand. And furthermore, as phones, they support cellular network technology. Because of their shorter range, the WPAN and WLAN technologies provide a convenient way to physically pin-point and track shoppers in a mall so that retailers can know how much time shoppers spend in various parts of a store and in front of store fronts and displays. In this way, the overall time in a store can be measured and effectiveness of store fronts and displays in arresting a shopper's attention can be inferred. Also, the number of repeat visits over periods of time can be tracked to learn whether customers are new or repeat. Such tracking information ostensibly is useful in rendering shopping more efficient and convenient to the shopper, as tracking information can be used to design more efficient store layouts, more informative signs, and so on such that shoppers can find products more easily. [0004] To enable tracking, monitoring stations are set up e.g. in the stores that act as wireless access points (WAPs) to initiate communication with mobile devices, but where network connectivity cannot be achieved. Alternatively, depending on the density of WAPs surrounding a store, monitoring stations are set-up that listen in on the communications between the mobile devices and these nearby WAPs. From the retailers' point of view, tracking people by means of their devices can even link a shopper's online shopping with his offline shopping, for example, by capturing a customer's name. This can be accomplished by first tracking and then capturing the customer's name right at the cash register when paying with a credit card which usually includes the customer's name, and then later correlating the customer's name to online databases. The retailer can then leverage both online and offline behavior against each other to increase sales. For example, the retailer may try to provide a coupon to that customer through email or webpage in order to bring that customer back into the store to shop. [0005] It should be noted, that with the device MAC address monitoring, it may be possible to track a person to an automobile, a physical residence and place of business. It does not matter that the content delivered over the network to/from that device may have been encrypted as device identifying information, e.g. the MAC address, is typically outside the data payload being protected by encryption. [0006] While tracking the wireless device of shoppers is attractive to retailers, as understood herein, not all shoppers are enthusiastic about being surreptitiously tracked every step of the way. Moreover, not entirely unfounded concerns have arisen over the potential for misusing pervasive, perpetual tracking information that ensnares most of the public. In short, present principles understand that more than a few shoppers might wish to remain anonymous as they gallivant through a shopping mall or in general cavort through life. SUMMARY OF THE INVENTION [0007] Present principles understand that in some cases, interaction with the mobile device can be facilitated by faking the service set identifier (SSID) to popular distributed access points such as “attwifi” or “verizonwifi”. A mobile device configured to search for one these popular SSIDs will communicate in vain with the fake WAP in order to access the ATT or Verizon network. Furthermore, if combined with video from a webcam, it is possible to determine the age group and sex of the customer. Later, when that customer is detected as coming into the store, targeted advertising could be delivered using properly placed video monitors. [0008] And simply monitoring certain web data interactions, along with the MAC addresses, on the mobile devices might reveal the applications that are running on the devices. The applications, e.g. Facebook, might reveal if the customer is a child, teenager or young adult. And the MAC addresses often can reveal the type of mobile device that it is. For example, Sony's cell phone has an organizationally unique identifier (OUI) registered as “Sony_Mob” which can be assumed to be “Sony Mobile”—a MAC address assigned to Sony cellphones. By knowing what type of mobile device is, the types of loaded applications can often be inferred. For example, Apple iPhones in the ATT network might be expected to always have certain applications loaded. And Sony Experia smartphone in the Verizon network can be expected to have different applications loaded and running. In store targeted advertising can be directed to those mobile devices and applications. [0009] Thus, as understood herein, wireless device (and, hence, people) tracking is facilitated, however unwittingly, by network communication protocols, in which wireless devices are programmed to automatically seek out wireless access points (WAPs) using exploratory messages, colloquially referred to as “pings”. The wireless devices may continue to periodically ping the WAPs regardless of whether the WAP can be successfully accessed, e.g. the security keys are known or can be negotiated. Pinging enables the wireless device to ascertain the best WAP with which to communicate by determining e.g. signal strength, the name of the WAP, and whether or not a security key or credentials are required and available, so that a list of WAPs may be presented to the user for selection. After selecting one and entering any keys, if need be, the user of the device can browse Internet web pages, use email, send text messages and tweets, communicate by video conferencing, and so on using the WAP. The mobile device can usually be programmed to reconnect with the WAP in the future when the device comes into range of the WAP. As mentioned above, the retailer can take advantage of this fact by faking popular WAPs with SSIDs labeled with, for example, “attwifi” or “verizonwifi”. The device will see the SSID and maintain prolonged contact with the imposter WAP. [0010] In constantly, automatically, and unobtrusively (to the user) reaching out to the network, wireless devices send exploratory messages that include identifiers such as media access control (MAC) addresses. These are unique addresses, often one for each technology the device uses, e.g., one MAC address for Bluetooth, one for Ethernet, and one for Wi-Fi, that are unique to the device and that typically are assigned by the manufacturer of the device from a range allocated to that manufacturer and, hence, correlated to the device. [0011] MAC addresses can be used for access control to wired local area networks (LAN) and wireless local area network (WLAN). In some corporate environments with strict security policies, every device accessing a wired or wireless network must be known. And this can be done by manually including the MAC in an access control list that the WAP checks in order to create a connection with that device. Presumably, the WAP may be able to determine if the MAC is already in use elsewhere in the corporate environment. However, often times, access control may be done at a higher software layer of functionality that can use public/private key credentials using X.509 certificates and a protocol such as Transport Layer Security (TLS). TLS allows a client device to not only authenticate a server, but for the server to authenticate a client device in a process known as “mutual authentication”. By verifying the credentials of the client, e.g. the mobile device, the WAP, acting as a server, is able to grant access to the network. This can be in addition to or instead of using the MAC for access control. In large corporate environments, there may less risk of surreptitious tracking because the physical space may be controlled and there would be no WAPs other than those installed by the corporate entity. However, many corporate environments are shared with various businesses operating side-by-side. For example, someone could be parked in a car outside a place of business and wirelessly collect information from all the smart devices from the employees of that business. People can also be tracked while travelling in cars. Surreptitious tracking can therefore extend from retail, to vehicles, to residences and even places of business. It is possible to discover where people shop, drive, live and work. [0012] To allow devices to access wireless network environments where MAC access control is desired, it would be desirable to have a means to allow the WAP to recognize a device's MAC that is in use while still preventing correlation of addresses to specific devices by eavesdroppers. [0013] In public places such as coffee shops and airports, MAC addresses are usually not used for access control. In many cases, there may be no security at all. The content is sent in-the-clear. In hotels, there is often the need to input a WEP or WAP key to access a WAP. There may be the need to navigate a webpage for authorization, where a room number, name and payment information may be entered. But typically, a hotel does not require identification of the user's MAC address when accessing the wireless network. It is the same situation for most people's wireless home network. The WAP does not need to know the MAC address a priori. And so consequently, in most public places, the MAC address for a WLAN device is simply not checked against an access list. The only criteria being that the MAC must be unique among the devices accessing the WAP at a particular time and on a particular sub-net, which is important for low level routing of data packets—the so called “link layer”. Typically only the WAP cares about the MAC as the information that is sent on to remote servers are typically IP datagrams which doesn't include the MAC information on the so called “network layer”. And so for a non-MAC access controlled environment, while it may be important that the MAC be unique for a particular WAP, present principles recognize that the MAC could in fact be re-used with different mobile devices at different times. And different WAPs could have wireless devices accessing them independently with the same MAC at the same time. [0014] Thus, present principles recognize the desirability of having a means to prevent MAC tracking for situations when the WAP does not use the MAC for access control. [0015] The MAC address used in Ethernet style addressing consists of 48 bits of data. This is potentially a space of 2 48 or 281,474,976,710,656 possible MAC addresses. This is over 281 trillion addresses. The first 24 bits of the address may be an organizationally unique identifier (GUI). The remaining 24 bits are assigned by the owner or assignee of the OUI. The address space of the 24 bits is 2 24 or 16,777,216 MAC addresses. In one embodiment, a device according to present principles “pings” WAPs while roaming e.g. in public spaces uses completely random MACs using the entire 48 bit address space. The chances of a collision with another device with the same randomly chosen address are thus relatively small. Also, the device may select a random address using a reduced bit space, e.g. where the OUI bits may be set and the remaining bits are random. When selected, the MAC may be kept static for the period of the session. The addresses in this reduced bit space may still be so large that it would be unlikely for there to be a collision with another device talking to the same WAP. As a precaution, present principles recognize that it is possible for the device to monitor other devices communicating with the WAP to make sure that the random MAC chosen is not one that is in use. And if a conflict is detected with one in use, the device may simply change the MAC to a different one. It should be noted that depending on how many devices have the same OUI bits set, it may be possible to use the OUI bits to track a device. [0016] Furthermore, present principles recognize that in some embodiments, to address WAPs which may check the MAC of devices against an access control list, a device according to present teachings may “ping” WAPs using a MAC chosen from a group of possible MACs associated with a single device. Instead of an access list containing a single MAC for a device, it could contain, for example, 16 or 32 MAC addresses for a device. Ideally, there would be no correlation between MAC addresses so that by capturing one MAC address the mobile device could not be tracked through the other MAC addresses. [0017] Present principles also recognize that in some embodiments, a number of devices from a manufacturer may share a certain number of MAC addresses. When devices from the manufacturer come into the store and ping the WAP at different times, they may pick the same MAC. The device can monitor traffic to make sure that a shared MAC that is chosen is unique for the instance in time. This would confuse the store's MAC tracking system. The data collected along with the analytics would be “corrupted” with MAC addresses that represented communication from multiple devices and not just a single one. [0018] Present principles recognize a number of possible device behaviors when managing a fixed number of multiple MAC addresses. For example, whenever a public WAP is pinged while roaming around, when changing from one WAP to a different WAP, a different MAC from the group of MACs may be used. Further, the device may maintain the MAC for a period of time, e.g. 4 hours or 8 hours, before changing to another one. However, keeping the period of time short, e.g. 10 minutes, would keep a retailer from using tracking during a store visit which would typically be much long. Keeping the MAC stable may facilitate the hand-off from one WAP to another in case the device is in an active session and moving around (e.g., which may preserve the IP address). Also, if a device is in an active session, then the MAC could be made to not change during a hand-off from one WAP to another. Further still, present principles may recognize that devices may periodically log-out and back in to a WAP with a different MAC address. A device can therefore do this every 10 or 15 minutes and be hardly noticed by the user since a device can do this fairly rapidly taking a couple of seconds. [0019] In any case, the MACs are not “static” in the sense that their use is limited, meaning that a service provider (SP) of WAPs, e.g. owner of a department store, depending on the device settings cannot track the same MAC around as a person possessing the wireless device roams a store or subsequently visits the same store. [0020] If desired, once a WAP initially has been located using a MAC, and it is known to use MAC access control, user-driven data through that WAP may be conducted using the non-anonymous MAC of the device, e.g. unique or chosen from a group of MACs associated with that device, and then when communication with that WAP ceases, the device reverts to using changing anonymous, e.g. random, MACs to ping WAPs during subsequent roaming. [0021] The group of MACs through which the device cycles when roaming may be issued to the device by the manufacturer of the device, or by the SP of a network of WAPs. In any case, a device's MAC for a particular network may be non-static in that the group of MACs is cycled through during roaming, so that a monitor of WAPs cannot pin down the shopper using a particular MAC. In the case of a network with MAC access control, the MAC may be recognized as one of a number of MACs assigned to a particular device. If the WAP cannot handle multiple MACs assigned to a device, then the device may choose one of the MACs as its persistent or permanent MAC. This MAC may be assigned by the manufacturer or the service provider. [0022] In another aspect, a wireless communication device includes a wireless transceiver and a computer readable storage medium bearing a permanent address associated with the wireless transceiver and uniquely identifying the device and plural temporary addresses. The plural temporary addresses are provided by a manufacturer of the device or by a service provider (SP) of a wireless network. A processor is configured for accessing the computer readable storage medium to execute instructions which configure the processor for selecting a first temporary address from the plural temporary addresses, and sending a first wireless network message including the first temporary address through the wireless transceiver pursuant to discovering a wireless access point (WAP). The processor selects a second temporary address from the plural temporary addresses and sends a second wireless network message including the second temporary address through the wireless transceiver pursuant to discovering a WAP. If desired, the addresses can be media access control (MAC) addresses. [0023] In some implementations, the instructions when executed by the processor further configure the processor for using the permanent address for communication of user voice and/or user data messages through the wireless transceiver. This may be desired e.g. for WAPs which perform access control on the MAC and that do not have knowledge of the temporary MAC addresses. If desired, the instructions when executed by the processor further configure the processor for not using the permanent address for communication of user voice and/or user data messages through the wireless transceiver responsive to a signal from a WAP to use the permanent address, and instead using one of the temporary addresses for communication of user voice and/or user data messages through the wireless transceiver in the absence of a signal from a WAP to use the permanent address. Responsive to a signal from a WAP to use the permanent address, the device may cease communication with the WAP, and/or present an alert on the device perceptible by a person that a network does not permit anonymous communication. [0024] On the other hand, the instructions when executed by the processor may further configure the processor for using the permanent address for communication of user voice and/or user data messages through the wireless transceiver responsive to a signal from a WAP to use the permanent address. In this case one of the temporary addresses can be used for communication of user voice and/or user data messages through the wireless transceiver in the absence of a signal from a WAP to use the permanent address. [0025] In some embodiments a portion of each temporary address otherwise indicating a manufacturing entity according to a standard address format is formatted to indicate an entity that does not exist. In this way use of a temporary address does not identify the device with a manufacturing entity. The manufacturing entity is often a way to reveal the type of device. [0026] In another aspect, a method to prevent tracking a wireless device as it roams through a network of wireless access points (WAPs) includes selecting a first temporary MAC address from a group of temporary MAC addresses provided by a device manufacturer or by a service provider (SP) of the WAPs. The method also includes “pinging” for WAPs using the first temporary MAC address, and pinging for subsequent WAPs using a second temporary MAC address. [0027] The details of the present invention, both as to its structure and operation, can best be understood in reference to the accompanying drawings, in which like reference numerals refer to like parts, and in which: BRIEF DESCRIPTION OF THE DRAWINGS [0028] FIG. 1 is a block diagram of an example wireless communication device (WCD) in one intended environment; [0029] FIG. 2 is a flow chart of example setup logic; [0030] FIG. 3 is a screen shot of an example display permitting a user of the WCD to establish a privacy preference; and [0031] FIGS. 4-7 are flow charts of example roaming logic. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0032] Referring initially to FIG. 1 , a wireless communication device (WCD) 10 is shown configured for wireless communication with one or more wireless access points (WAP) 12 typically provided by a service provider (SP). Non-limiting examples of WCDs include wireless telephones, digital readers, cameras, laptop computers, notebook computers, smart watches and tablet computers. [0033] In the example shown, the WCD 10 is a wireless telephone and so includes a wireless telephony transceiver 14 controlled by one or more WCD processors 16 accessing one or more computer readable storage media 18 such as read-only memory (ROM) and variants thereof, random access memory and variants thereof, and physically embodies as, for example, disk-based or solid-state storage. The telephony transceiver 14 may be, without limitation, a Global Systems for Mobile communication (GSM) transceiver and variants thereof, code division multiple access (CDMA) transceiver and variants thereof, frequency division multiple access (FDMA) transceiver and variants thereof, time division multiple access (TDMA) transceiver and variants thereof, space division multiple access (SDMA) transceiver and variants thereof, orthogonal frequency division multiplexing (OFDM) transceiver and variants thereof, etc. [0034] The WCD 10 may include other wireless transceivers as well. For example, the WCD 10 may include a Wi-Fi transceiver 20 controlled by the processor 16 as well as a Bluetooth transceiver 22 controlled by the processor 16 . The processor 16 may output visible information in a display 24 , which may be a touchscreen display, and receive user input from a keypad 26 , which may be a physical keypad separate from the display 24 or which may be a virtual keypad presented on a touch sensitive display 24 . The processor 16 may receive position information from a position sensor, such as a global positioning satellite (GPS) receiver 27 . [0035] Typically, each network interface, in the example shown, each transceiver 14 , 20 , 22 , is assigned a respective permanent media access control (MAC) address by the manufacturer of the device at the time of manufacture. This MAC address (or addresses when multiple network interfaces are provided) are unique to the WCD 10 , i.e., a MAC address uniquely identifies the WCD with which it is associated. Messages sent through a wireless interface typically include the MAC address so that the device essentially is revealing its unique identity every time it sends a message, although some telephony transceivers may use identifiers of the WCD other than the MAC. Regardless, it is to be understood that while for disclosure purposes unique MAC addresses are used as an example of present principles, other device addresses that otherwise would uniquely identify the device may also be used. [0036] A MAC address may be e.g. 48-bits in length. For example, a MAC address may consist of six groups of two hexadecimals separated by hyphens or colons, as in 12.34.56.78.90.ab. Some of the bits identify the organization that issued the address, while the remaining bits can be assigned as the organization desires subject to the constraint of uniqueness. With this general understanding in mind, attention is now drawn to FIG. 2 . Like the other flow charts discussed herein, FIG. 2 illustrates logic that the processor 16 or other processor can be configured to execute when accessing instructions on a computer readable storage medium. The use of flow chart format is for illustration only and is not a limitation, in that other logical forms such as state logic can be used. [0037] Commencing at block 28 , a respective unique address such as a permanent MAC address is associated with each respective wireless interface of the device 10 by the manufacturer of the device 10 at time of manufacture. At block 30 one or more wireless interfaces that have been assigned a permanent MAC may also be assigned a set of plural temporary addresses. This set of temporary addresses may be assigned by the manufacturer of the device at time of manufacture, for example, or in another example may be assigned by the SP associated with the WAPs 12 at time of first contact of the device 10 with the WAPs 12 . The assigning entity of temporary MACs may or may not maintain a record of the device to which the temporary MACs were assigned. If the assigning entity records which device received which temporary MACs, that correlation information may be maintained in encrypted form and be unavailable to the network at large. [0038] In any case, the temporary MACs preferably are formatted in the same way as the permanent MAC so that they will be recognized as a valid MAC. That is, the temporary MACs preferably will have the same number of bits and same hexadecimal arrangement as the permanent MAC. However, whereas a portion of the permanent MAC indicates the manufacturer of the device 10 , the portion of each temporary MAC that otherwise would indicate a manufacturing entity according to a standard address format can be formatted to indicate an entity that does not exist, such that use of a temporary address does not identify the device with a manufacturing entity and, hence, in effect does not identify the device. Ideally, the temporary addresses may not be in a contiguous range which would indicate a single device. For example, there should not be any obvious relationship between the temporary addresses in some embodiments. In other embodiments, the temporary MACs may indicate the entity that assigned the temporary MACs to the device 10 . [0039] Similarly, temporary MACs may use the same bit as the permanent MAC in indicating whether the temporary MAC is locally or universally administered. As understood herein, by assigning temporary MACs on this basis instead of randomly generating entire bit strings can alleviate the problem of a recipient receiving data that does not fit an expected format. [0040] Proceeding to block 32 , the device 10 can prompt the user to select a privacy policy with respect to use of the temporary MACs. FIG. 3 is an example that informs. A user interface (UI) is shown that can be presented on the display 24 of the device 10 to enable the user to select ( 34 ) not to engage in private roaming according to description below, in which case the temporary MACs are not used and only the permanent MAC is conventionally used. [0041] However, the user can select ( 36 ) private roaming in which case the user may be given additional options if desired. At 38 the user can select to use the temporary MACs at least for roaming purposes according to principles below, and to automatically shift to using the permanent MAC in the event that an SP providing WAPs attempting to be contacted by the device 10 deny acceptance of temporary MACs. Or, the user can select at 40 to be first warned that an SP providing WAPs attempting to be contacted by the device 10 denies acceptance of temporary MACs prior to shifting to use of the permanent MAC. Until the user subsequently inputs a signal desiring to shift to the permanent MAC, the device 10 may cease communication with the WAP. [0042] Assuming that use of temporary MACs at least for roaming purposes is instantiated, FIG. 4 shows that at block 42 the processor 16 selects a first temporary MAC from the plural temporary MACs. Moving to block 44 , a wireless network message such as a roaming message attempting to establish contact with a WAP is transmitted containing the temporary MAC selected at block 42 . Such a message may be referred to as a “ping”. If a WAP is detected at decision diamond 46 (as indicated by, e.g., a response to a “ping” from a WAP), it is determined at decision diamond 48 in response whether the SP associated with the responding WAP permits private roaming using temporary MACs. If so, the temporary MAC selected at block 42 is used at block 50 for communications with the responding WAP. Alternatively, another temporary MAC different from the MAC that was used for the “ping” message can be used. Yet again, the permanent MAC can be used at block 50 for ensuing messages to the responding WAP, e.g., for messages attendant to user-driven voice and/or data communications. On the other hand, if it determined at decision diamond 48 that the SP associated with the responding WAP does not permit private roaming using temporary MACs, the logic moves to block 52 to operate per the user-defined privacy preferences exemplified in FIG. 3 . [0043] FIGS. 5-7 illustrate example logic for selecting new temporary MACs, it being understood that one or more selection criteria shown in FIGS. 5-7 may be employed. Commencing at decision diamond 54 , following selection of an initial temporary MAC and establishing communication with a WAP, it is determined whether communication with a WAP has been lost. If not, the currently selected temporary MAC may continue to be used in communication with that WAP at block 56 . However, upon loss of communication with a WAP the logic may select a new temporary MAC at block 58 for use in subsequently transmitted roaming messages using the newly selected temporary MAC at block 60 . In this way, if communication is again established either with the prior WAP or with a new WAP, the device 10 cannot be tracked as the user moves. [0044] In FIG. 6 , commencing at decision diamond 62 it is determined whether a currently selected temporary MAC has been used for longer than a use period, e.g., five minutes. If not, the currently selected temporary MAC is continued to be used at block 64 . However, upon elapse of the use period the logic may select a new temporary MAC at block 66 for use in subsequently transmitted roaming messages using the newly selected temporary MAC at block 68 . In this way, tracking of the device 10 cannot occur for longer than the use period. [0045] In FIG. 7 , commencing at decision diamond 70 it is determined whether, since beginning use of a temporary MAC, the WCD has moved, e.g., beyond a threshold distance since start of use of the MAC, as indicated by, for example, signals from the GPS receiver 27 in FIG. 1 . Another indication that may be used to determine whether the WCD has moved is the acquisition by the WCD of a new WAP. If the WCD has not moved according to the test at decision diamond 70 , the currently selected temporary MAC is continued to be used at block 72 . However, if the WCD has moved away from the initial MAC position by the threshold distance, the logic may select a new temporary MAC at block 74 for use in subsequently transmitted roaming messages using the newly selected temporary MAC at block 76 . [0046] Without reference to any particular figure it is to be understood that in some embodiments, a wireless communication device may include at least one wireless transceiver and at least one processor configured for accessing a computer readable storage medium to execute instructions which configure the processor for monitoring the communication traffic to one or more wireless access points (WAPs) to learn which device addresses are already in use by other wireless communication devices, creating or selecting a first temporary device address that is different than devices already in use, sending a first wireless network message including the device address through the wireless transceiver pursuant to discovering a WAP that the user wishes to communicate with, continuing to monitor the communication traffic to one or more WAPs to learn if there are any new devices with device address in use by other wireless communication devices, creating or selecting a second address that is different than the devices in use, and sending a second wireless network message including the second address through the wireless transceiver pursuant to discovering a wireless access point (WAP). [0047] Also in some embodiments, a wireless access point may include at least one wireless transceiver and at least one processor configured for accessing a computer readable storage medium to execute instructions which configure the processor for maintaining an access control list of wireless device addresses that can access the wireless access point where the access control list contains two or more entries for device addresses for a single wireless device, and granting access to the wireless network if a device address appears in the access control list. [0048] While the particular NETWORK DISCOVERY AND CONNECTION USING DEVICE ADDRESSES NOT CORRELATED TO A DEVICE is herein shown and described in detail, it is to be understood that the subject matter which is encompassed by the present invention is limited only by the claims.
To prevent tracking as it roams through a network of wireless access points (WAPs), a wireless device changes the MAC address. The device does this by randomizing some or all of the bits in the MAC address or selecting the MAC address from a group of MAC addresses assigned to the device by the device manufacturer. Furthermore, in order to further confuse tracking and make analytics not useful, a device can share MAC addresses with other devices, and check to make sure that a shared MAC address is not actively being used before selecting and using it.
7
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This is a U.S. national stage application of the International Patent Application No. PCT/CN2014/088680, filed Oct. 15, 2014, which claims priorities to Chinese Patent Application No. 201310487493.1, filed Oct. 17, 2013, both of which are incorporated herein by reference in their entirety. FIELD [0002] The present disclosure relates to pharmaceutical field, particularly the present disclosure relates to novel crystalline forms or amorphous of pyrazolopyridine compounds, more particularly the present disclosure relates to a novel crystalline form or amorphous of methyl {4,6-diamino-2-[1-(2-fluorobenzyl)-1H-pyrazolo[3,4-B]pyridine-3-yl]pyrimidine-5-yl}N-methylcarbamate. BACKGROUND [0003] Riociguat, also known as methyl{4,6-diamino-2-[1-(2-fluorobenzyl)-1H-pyrazolo[3,4-B]pyridine-3-yl] pyrimidine-5-yl}N-methylcarbamate, has formula (I). Riociguat is the first of a new class of Guanylatecyclase (sGC) agonist, directly activates sGC and increases low levels of NO sensitivity, for treating pulmonary hypertension and chronic obstructive pulmonary hypertension. [0000] [0004] Many drugs may exist in different crystalline forms, which may have significant differences from each other inappearances, solubilities, melting points, dissolution rates, bioavailabilities, stability, efficacy and the like. So it is very important to think through the situation of different crystal forms in drug development. [0005] The compound of formula (I) is first disclosed by U.S. Pat. No. 7,173,037, wherein example 8 discloses the preparation method of the compound of formula (I) wherein a crystal form of the compound of formula (I) is obtained by recrystallization from methanol. US 20110130410 disclosed a DMSO solvate of the compound of formula (I). However, we can't determine the crystal form of formula (I) for the above references do not fully characterize the polymorphs by XPRD, DSC, IR etc and their solubility, stability behavior in drug formulation. [0000] Therefore, the crystalline behavior of formula (I), methyl{4,6-diamino-2-[1-(2-fluorobenzyl)-1H-pyrazolo[3,4-B]pyridine-3-yl] pyrimidine-5-yl}N-methylcarbamate, need to be well investigated to obtain the desired crystal form in order to fulfill the formulation requirements. SUMMARY [0006] In one aspect, provided herein is a novel crystalline form of the compound of formula (I) [0000] [0007] The crystalline form of a drug compound may have different chemical and physical properties, including melting point, chemical reactivity, apparent solubility, dissolution rate, optical and mechanical properties, vapor pressure and density. These properties may have a direct effect on the ability to process and/or manufacture the drug compound and the drug product, as well as on drug product stability, dissolution, and bioavailability. Thus the crystalline forms of the compound of formula (I) may affect the quality, safety, and efficacy of a drug product comprising the compound of formula (I). [0008] According to embodiments of present disclosure, the inventors investigate whether the compound of formula (I) may present in a polymorph form. Unexpectedly, the inventors have found that the compound of formula (I) may present in many novel crystalline forms including form I, form II, form III and form IV. [0009] In some embodiments, the crystalline form of the compound of formula (I) is crystalline form I. In some embodiments, form I has an X-ray powder diffraction (XRPD) pattern comprising one or more peaks at about 25.47, 17.69 and 27.23 degrees in term of two theta. In some embodiments, form I has an XRPD comprising one or more peaks at about 25.47, 17.69, 27.23, 8.99, 6.68, 14.24, 20.27 and 19.67 degrees in term of two theta. In some embodiments, form I has an XRPD comprising one or more peaks at about 25.47, 17.69, 27.23, 8.99, 6.68, 14.24, 20.27, 19.67, 20.95, 30.76 and 20.57 degrees in term of two theta. In some embodiments, form I has an XRPD substantially as depicted in FIG. 1 , wherein the peak at about 25.47 degree in term of two theta has a relative intensity of at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at about 100% with respect to the strongest peak in the XRPD. [0010] In some embodiments, the characteristics of form I may be detected, identified, classified and characterized using well-known techniques, such as in certain embodiments, the form I has a DSC curve comprising the endothermic peak at about 268.95° C. In certain embodiments, form I has a DSC curve substantially as depicted in FIG. 2 . [0011] In some embodiments, the crystalline form of the compound of formula (I) is crystalline form II. In some embodiments, form II has an X-ray powder diffraction (XRPD) pattern comprising one or more peaks at about 25.40, 13.86, 17.21 and 22.71 degrees in term of two theta. In certain embodiments, form II has an XRPD comprising one or more peaks at about 25.40, 13.86, 17.21, 22.71, 11.13, 12.56, 24.89 and 22.47 degrees in term of two theta. In certain embodiments, form II has an XRPD comprising one or more peaks at about 25.40, 13.86, 17.21, 22.71, 11.13, 12.56, 24.89, 22.47, 26.04 and 29.92 degrees in term of two theta. In some embodiments, form II has an XRPD substantially as depicted in FIG. 3 wherein the peak at about 25.40 degree in term of two theta has a relative intensity of at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at about 100% with respect to the strongest peak in the XRPD. [0012] In some embodiments, the characteristics of form II may be detected, identified, classified and characterized using well-known techniques, such as in certain embodiments, the form II has a DSC curve comprising the endothermic peak at about 268.45° C. In certain embodiments, form II has a DSC curve substantially as depicted in FIG. 4 . [0013] In some embodiments, the crystalline form of the compound of formula (I) is crystalline form III. In some embodiments, form III has an X-ray powder diffraction (XRPD) pattern comprising one or more peaks at about 25.44, 13.88, 17.23, 15.14 degrees in term of two theta. In certain embodiments, form III has an XRPD comprising one or more peaks at about 25.44, 13.88, 17.23, 15.14, 22.75, 12.60, 11.17, 9.02, 17.66, 22.52, 24.94, 17.53 and 6.68 degrees in term of two theta. In some embodiments, form III has an XRPD substantially as depicted in FIG. 5 and the peak at about 25.44 degree in term of two theta has a relative intensity of at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at about 100% with respect to the strongest peak in the XRPD. [0014] In some embodiments, the characteristics of form III may be detected, identified, classified and characterized using well-known techniques, such as in certain embodiments, the form III has a DSC curve comprising the endothermic peak at about 267.80° C. In certain embodiments, form III has a DSC curve substantially as depicted in FIG. 6 . [0015] In some embodiments, the crystalline form of the compound of formula (I) is crystalline form IV. In some embodiments, form IV has an X-ray powder diffraction (XRPD) pattern comprising one or more peaks at about 20.01, 27.03, 8.21 degrees in term of two theta. In certain embodiments, form IV has an XRPD comprising one or more peaks at about 20.01, 27.03, 8.21, 18.15 and 27.38 degrees in term of two theta. In certain embodiments, form IV has an XRPD comprising one or more peaks at about 20.01, 27.03, 8.21, 18.15, 27.38, 19.22, 26.34, 29.38, 8.57, 14.45 and 7.15 degrees in term of two theta. In some embodiments, form IV has an XRPD substantially as depicted in FIG. 7 wherein the peak at about 20.01 degree in term of two theta has a relative intensity of at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at about 100% with respect to the strongest peak in the XRPD. [0016] In some embodiments, the characteristics of form (IV) can be detected, identified, classified and characterized using well-known techniques, such as in certain embodiments, the form IV has an DSC curve comprising the endothermic peak at about 266.88° C. In certain embodiments, form IV has a DSC curve substantially as depicted in FIG. 8 . [0017] The present disclosure contemplates that any one of the solid forms of the compound of formula (I) as described herein can exist in the presence of the any other of the solid forms or mixtures thereof. Accordingly, in one embodiment, the present invention provides the crystalline form, the liquid crystalline form or the amorphous form of the compound of formula (I) as described herein, wherein the crystalline, liquid crystalline or amorphous form is present in a solid form that includes less than 95%, less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, less than 3%, or less than 1% by weight of any other physical forms of the compound of formula (I). For example, in one embodiment is a solid form of the compound of formula (I) comprising a crystalline form of the compound of formula (I) that has any one of the powder X-ray diffraction patterns, Raman spectra, IR spectra and/or NMR spectra described above, wherein said solid form includes less than 95%, less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, less than 3%, or less than 1% by weight of any other physical forms of the compound of formula (I). [0018] Provided herein is a novel crystalline form of the compound of formula (I) comprising form I, form II, form III or form IV. The crystalline forms disclosed herein may have good solubility, low hydroscopicity and may be stable under high temperature (60° C.), high related humidity (RH is 90%±5%) and/or under light (4500+/−500 Lux), which benefit for storage, meet the requirements of drug stability and therefore make the compound of formula (I) suitable for formulation preparation and with high bioavailability. [0019] Also disclosed herein is a method for preparing the crystalline forms I to form IV of the compound of formula (I), and the process comprises dissolving any solid forms of the compound of formula (I) in a good solvent to form a solution, forming crystals by reducing the temperature of the solution or removing proportion of the solvent or adding anti-solvent to the solution, and collect the crystal. [0020] In some embodiments, the solid form of the compound is amorphous form or DMSO solvate disclosed by U.S. patent application No. 20110130410. In some embodiments, the compound of formula (I) is prepared according to the process disclosed in Chinese patent application 03816160.5. [0021] In some embodiments, dissolving the compound of formula (I) with a good solvent may be promoted by a method known to the person skilled in the art, such as stirring, heating to reflux, sonication or shaking or any combination thereof. In some embodiments, the compound of formula (I) is dissolved by stirring and heating the reaction mixture to reflux. [0022] In some embodiments, the temperature of the solution is reduced to from about −10° C. to about 40° C. The temperature for crystallization is from about −10° C. to about 40° C. In certain embodiments, the crystal is formed at room temperature. [0023] In some embodiments, the way to remove proportion of the solvent comprises distillation (atmospheric or vacuum distillation) or evaporation or any combination thereof, and the amount of the removed solvent is from about 20% to about 90% with respect to the total volume of the solution. In certain embodiments, the amount of removed solvent is about 30% with respect to the total volume of the solution. [0024] In some embodiments, the crystalline forms of the compound of formula (I) disclosed herein may be prepared by dissolving the compound of formula (I) in a good solvent at room temperature to form a solution, and forming crystals by adding the solution to an anti-solvent or adding an anti-solvent to the solution. [0025] The solubility of the compound of formula (I) in the anti-solvent is less than in the good solvent with a solubility difference being about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70% or about 80% based on the solubility in the good solvent. Therefore, the term “anti-solvent” described herein is relative to a “good solvent”, and the anti-solvent may be a polar or a non-polar solvent [0026] In some embodiments, a sufficient amount of a seed is added to promote a particular crystalline form of the compound of formula (I) such as crystalline forms I, form II, form III, or form IV. The seed refers to a small single crystal from which a larger crystal of the same or different crystalline form may be grown in certain embodiments, the small single crystal and the larger crystal are of a same solid form. In some embodiments, the small single crystal and the larger crystal are of the different solid forms. [0027] The crystals may be isolated and/or purified by vacuum filtration, gravity filtration, suction filtration or a combination thereof. The isolated crystals may carry with some mother liquor. Therefore, the isolated crystals may be further washed with suitable solvent and then dried. In certain embodiments, the isolated crystals are washed with the crystallization solvent or water. [0028] The good solvent or the anti-solvent may be one or more polar solvents, one or more non-polar solvents or any combination thereof, wherein the good solvent or the anti-solvent is selected from dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP) water, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, alkane solvents, nitrile solvents and any combination thereof, wherein the alcohol solvents are selected from methanol, ethanol, n-propanol, iso-propanol, ethylene glycol, 1,3-propanediol, 1,2-propylene glycol, 1,1,1-trichloro-2-methylpropan-2-ol and any combination thereof, wherein the ether solvents are selected from tetrahydrofuran (THF), methyl tert-butyl ether (MTBE), 1,4-dioxane and any combination thereof, and the ketone solvents may be selected from acetone, methyl ethyl ketone, 4-methyl-2-pentanone and any combination thereof, and the ester solvents may be selected from ethyl acetate, iso-propyl acetate, n-butyl acetate, tert-butyl acetate and any combination thereof, and the alkane solvents may be selected from dichloromethane, chloroform, hexane, cyclohexane, pentane heptane and any combination thereof, and the aromatic hydrocarbon solvents may be selected from benzene, toluene and any combination thereof, and the nitrile solvents may be selected from acetonitrile, malononitrile and any combination thereof. [0029] In some embodiments, the good solvent or anti-solvent is selected from one or more of NMP, DMF, ethyl acetate, water, methanol, ethanol, ethylene glycol, isopropanol, n-propanol, n-butanol, tert-butanol, THF, methylene chloride, DMSO, ethyl acetate, acetone, acetonitrile, 1,4-dioxane. [0030] In some embodiments, the good solvent or anti-solvent is selected from one or more of dichloromethane, methanol, ethanol, acetone, THF, NMP, DMF, DCM, 1, 4-dioxane, ethylene glycol, ethylene DMF, ethylene NMP, DMSO, EtOH, isopropanol, n-butanol, tert-butanol, n-propanol, acetonitrile, isopropyl acetate and n-butanone. [0031] In some embodiments, the crystalline form I of the compound of formula (I) is formed from the good solvent, wherein the good solvent is selected from one or more of methanol, ethanol, acetone, THF, ethylene glycol, 1,4-dioxane, methylene chloride. [0032] In some other embodiments, the crystalline form I of the compound of formula (I) can be formed, wherein the good solvent is selected from DMF, NMP or DMSO while the anti-solvent is selected from H 2 O, ethyl acetate or ethanol. [0033] In some embodiments, the crystalline form II of the compound of formula (I) can be formed, wherein the good solvent is selected from one or more of ethanol, isopropanol, n-butanol, ethylene glycol or tert-butanol. [0034] In some other embodiments, the crystalline form II of the compound of formula (I) can be formed, wherein the good solvent is DMSO while the anti-solvent is H 2 O. [0035] In some embodiments, provided herein is a process for preparing the crystalline form I of the compound of formula (I), comprising a solution of the compound of formula (I) in DMSO with a temperature of 70° C. to 90° C. was added slowly to water with a temperature of 70° C. to 90° C., after the solution was added completely, the temperature was reduced to 25° C. below, and stirred for 1 hour to 24 hour. [0036] In some embodiments, the crystalline form III of the compound of formula (I) can be formed, and the good solvent is selected from one or more of n-propanol, 1, 4-dioxane, acetonitrile or isopropyl acetate. [0037] In some other embodiments, the crystalline form III of the compound of formula (I) can be formed, and the good solvent is NMP, DMSO or DMF while the anti-solvent is H 2 O ethanol and any combination thereof. [0038] In some embodiments, the crystalline form IV of the compound of formula (I) can be formed, and the good solvent is butanone. [0039] In some embodiments, the crystalline form I of the compound of formula (I) can be formed comprising adding the compound of formula (I) to ethanol, heating the mixture to a temperature from about 50° C. to a refluxing temperature of the solvent system to form a solution, cooling the solution and removing proportion of the solvent to form the crystals, stirring the result solution at room temperature for about 0.5 h to 36 h and collecting the crystals. [0040] In some embodiments, the crystalline form II of the compound of formula (I) may be formed comprising adding the compound of formula (I) to ethanol, heating the mixture to a temperature from about 50° C. to the refluxing temperature of the solvent to form a solution, slowly cooling the solution to room temperature and sealing the solution, then stirring the result solution for about 1 h to 300 h and collecting the crystals. [0041] In some embodiments, the crystalline form I of the compound of formula (I) can be formed comprising mixing the compound of formula (I) with 1, 4-dioxane, heating the mixture to a temperature at about 101° C. to form a solution, after cooling down to room temperature and stirring openly to allow evaporate naturally for a while, then sealing and stirring the result solution for about 1 h to 300 h and collecting the crystals. [0042] In some embodiments, crystalline form III of the compound of formula (I) can be formed comprising mixing the compound of formula (I) with 1, 4-dioxane, heating and stirring the mixture to reflux until the solid is completely dissolved to form a solution, then slowly cooling the solution to room temperature and sealing the solution, stirring the solution for about 1 h to 300 h and collecting the crystals. [0043] In some embodiments, crystalline form I of the compound of formula (I) can be formed comprising adding the mixture of the compound of formula (I) and ethylene glycol to reaction flask, heating and stirring the mixture to about 140° C. until the solid is completely dissolved to form a solution, after cooling the solution to room temperature and openly stirring to allow evaporate naturally for a while, then sealing the solution, stirring the solution for about 1 h to 300 h and collecting the crystals. [0044] The crystalline form II of the compound of formula (I) can be formed comprising adding the mixture of the compound of formula (I) and ethylene glycol to reaction flask, heating and stirring the mixture to about 140° C. until the solid is completely dissolved to form a solution, then slowly cooling the solution to room temperature and sealing the solution, stirring for about 1 h to 300 h and collecting the crystals. [0045] According to the process of the crystal form of the compound of formula (I) herein, substantially pure crystalline form I, form II, form III and form IV of the compound of formula (I) can be prepared through transforming any forms of formula (I) to the another expected crystal form of the compound of formula (I). [0046] The process of the crystal form of the compound of formula (I) herein is simple, moderate, accorded with GMP requirement and suitable for industrialization [0047] The amorphous of the compound of formula (I) disclosed herein is substantially pure, wherein the X-ray powder diffraction pattern is depict as in FIG. 9 . In some embodiments, the amorphous of the compound of formula (I) is prepared by spray drying. [0048] As used herein, the term “spray drying” generally refers to the process comprising dispersing the liquid into tiny droplets (atomization) and quickly removing solvent from the mixture thereof. [0049] The drug formulations comprising the novel crystalline form or amorphous of the compound of formula (I) disclosed herein may be used in treating cardiovascular disease, hypertension, thromboembolic disease, ischemia and sexual dysfunction in a patient. [0050] The novel crystalline form or amorphous of the compound of formula (I) disclosed herein can be used in treating cardiovascular disease, hypertension, thromboembolic disease, ischemia and sexual dysfunction in a patient. [0051] Also provides herein is the use of the crystalline form or amorphous of the compound of formula (I) in the drug used to treating cardiovascular disease, hypertension, thromboembolic disease, ischemia and sexual dysfunction in a patient. [0052] Also provided herein is a pharmaceutical composition comprising a therapeutically effective amount of a crystalline form of the compound of formula (I), wherein the crystalline form is form I, form II, form III, form IV and one or more pharmaceutically acceptable carriers or excipients. [0053] Also provided herein is a pharmaceutical composition comprises a pharmaceutically acceptable carrier and a therapeutically effective amount of amorphous of the compound of formula (I). [0054] The pharmaceutical composition as disclosed herein can be administrated through being compacted into a dosage form, such as tablets, capsules (wherein every one of the capsules comprising formulations of sustained release or timed release), pills, powders, tinctures, deflocculants, syrupands or emulsifiers. Also can be administrated in intravenous (infusion solutions), intraperitoneal, subcutaneous, intramuscular forms. [0055] The dosage forms used herein may be known by one skilled in the art. The dosage form may be administrated singly, and usually may be administrated together with a pharmaceutical carrier selected according to the way of administration and the standard pharmacy practice. Generally achieved by using appropriate non-toxic inert medicinal excipient comprising carriers (such as microcrystalline cellulose), solvents (such as polyethyleneglycol), emulsifiers (such as sodium lauryl sulfate), dispersants (such as polyvinylpyrrolidone), Synthetic and natural biopolymers (such as albumin), stabilizer (such as antioxidant of ascorbic acid), colorants (such as inorganic pigments of iron oxides) or corrective agents and/or taste-masking agents. In some appropriate cases, the active ingredients of the compound of formula (I) may exist in one or more carriers disclosed herein in the form of microencapsulation. [0056] The pharmaceutically effective amount of the compound of formula (I) is from about 0.1% to about 99.5% base on the total weight of the pharmaceutical composition, and in some embodiments, the mass fraction of the compound of formula (I) can be from about 0.5% to about 95% in the pharmaceutical preparations thereof. [0057] In some embodiments, some other active ingredients may also be included in the above mentioned pharmaceutical preparations in addition to the crystalline form of the compound of formula (I) in present invention. BRIEF DESCRIPTION OF THE DRAWINGS [0058] These and other aspects and advantages of embodiments of the present disclosure will become apparent and more readily appreciated from the following descriptions made with reference to the accompanying drawings, in which: [0059] FIG. 1 depicts the X-ray powder diffractogram of the crystalline form I of the compound of formula (I) according to one example of present disclosure. [0060] FIG. 2 depicts the differential scanning calorimeter (DSC) curve of the crystalline form I of the compound of formula (I) according to one example of present disclosure. [0061] FIG. 3 depicts the X-ray powder diffractogram of the crystalline form II of the compound of formula (I) according to one example of present disclosure. [0062] FIG. 4 depicts the differential scanning calorimeter (DSC) curve of the crystalline form II of the compound of formula (I) according to one example of present disclosure. [0063] FIG. 5 depicts the X-ray powder diffractogram of the crystalline form III of the compound of formula (I) according to one example of present disclosure. [0064] FIG. 6 depicts the differential scanning calorimeter (DSC) curve of the crystalline form III of the compound of formula (I) according to one example of present disclosure. [0065] FIG. 7 depicts the X-ray powder diffractogram of the crystalline form IV of the compound of formula (I) according to one example of present disclosure. [0066] FIG. 8 depicts the differential scanning calorimeter (DSC) curve of the crystalline form IV of the compound of formula (I) according to one example of present disclosure. [0067] FIG. 9 depicts the X-ray powder diffractogram of the amorphous of the compound of formula (I) according to one example of present disclosure. DETAILED DESCRIPTION [0068] Before describing the present invention in detail, it is to be understood that this invention is not limited to particularly exemplified methods and may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only, and is not intended to be limiting which will be limited only by the appended claims. [0069] All publications, patents and patent applications cited herein, whether supra or infra, are hereby incorporated by reference in their entirety. However, publications mentioned herein are cited for the purpose of describing and disclosing the protocols, and reagents which are reported in the publications and which might be used in connection with the invention. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention. DEFINITION [0070] Otherwise stated, the following definitions may be use throughout the disclosure. [0071] As used herein, the term “the compound of formula (I)” refers to the compound with chemical name of methyl{4,6-diamino-2-[1-(2-fluorobenzyl)-1H-pyrazolo[3,4-B] pyridine-3-yl] pyrimidine-5-yl}N-methylcarbamate. [0072] As used herein, the term “crystal form” refers to the existing state of solid compounds especially the various parameters collection of the ions, atoms or molecular composition, the symmetric properties and the unique ordered arrangement of molecules in the crystal lattice of the compound. [0073] As used herein, the term “amorphous” refers to the order less arrangement of particles (ions, atoms or molecules) of the compound in three-dimensional space. [0074] As used herein, an X-ray powder diffraction pattern that is “substantially as depicted” in a figure refers to an X-ray powder diffraction pattern having at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the peaks shown in the figure. [0075] As used herein, the term “relative intensity” refers to the intensity of a peak with respect to the intensity of the strongest peak in the X-ray powder diffraction (XRPD) pattern which is regarded as 100%. [0076] As used herein, the term “good solvent” refers to a solvent in which the compound of formula (I) has a solubility greater than 1 g/L, greater than 2 g/L, greater than 3 g/L, greater than 4 g/L, greater than 5 g/L, greater than 6 g/L, greater than 7 g/L, greater than 8 g/L, greater than 9 g/L, greater than 10 g/L, greater than 15 g/L, greater than 20 g/L, greater than 30 g/L, greater than 40 g/L, greater than 50 g/L, greater than 60 g/L, greater than 70 g/L, greater than 80 g/L, or greater than 100 g/L of the solvent. In some embodiments, the solubility of the compound of formula (I) in the good solvent is greater than the solubility of the compound of formula (I) in the anti-solvent. In certain embodiments, the solubility difference between the good solvent and anti-solvent is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, based on the solubility of the good solvent. In some embodiments, the solubility of the good solvent is about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% higher than anti-solvent. [0077] As used herein, the term “anti-solvent” refers to a solvent which can promote super saturation and/or crystallization. In some embodiments, the solubility of the compound of formula (I) in the anti-solvent is less than 0.001 g/L, less than 0.01 g/L, less than 0.1 g/L, less than 0.2 g/L, less than 0.3 g/L, less than 0.4 g/L, less than 0.5 g/L, less than 0.6 g/L, less than 0.8 g/L, less than 1 g/L, less than 2 g/L, less than 3 g/L, less than 4 g/L, less than 5 g/L, less than 6 g/L, less than 7 g/L, less than 8 g/L, less than 9 g/L, or less than 10 g/L of the anti-solvent. [0078] As used herein, the term “room temperature” refers to a temperature from about 18° C. to about 35° C. or a temperature from about 20° C. to about 24° C. or a temperature at about 22° C. [0079] As used herein, the term “overnight” refers to a period of from about 6 hours to about 24 hours, or from about 8 hours to about 12 hours. [0080] As used herein, when referring to a spectrum and/or to data presented in a graph, the term “peak” refers to a feature that one skilled in the art would recognize as not attributable to background noise. [0081] In the following description, all numbers disclosed herein are approximate values, regardless whether the word “about” or “approximate” is used in connection therewith. The value of each number may differ by 1%, 2%, 5%, 7%, 8%, 10%, 15% or 20%. [0082] In the context, degree (°) is the basic unit of the data of two theta in the X-ray powder diffraction pattern. [0083] The 2theta (2θ) and/or the diffraction peak value at the X-ray powder diffraction (XRPD) pattern may show measurement error due to the measurement instruments or measurement samples and the like. To be specific, the measurement error may be within the range of about ±0.3, or about ±0.2 or about ±0.1 unit, for example, in the following description, “an X-ray powder diffraction pattern comprises one peak at about 25.44” it means an X-ray powder diffraction pattern comprises one peak at 25.44±0.2. [0084] The position and value of the endothermic peak at the differential scanning calorimeter (DSC) pattern may show measurement error due to the measurement instruments or measurement samples and the like. The measurement error may be 5° C. or less, 4° C. or less, 3° C. or less, 2° C. or less. Therefore, the position and value of the endothermic peak can't be regard as absolutely. EXAMPLES [0085] The embodiments of the present disclosure is a novel crystalline form and amorphous of the compound of formula (I). Although various embodiments of the invention are disclosed herein, many adaptations and modifications may be made within the scope of the invention in accordance with the common general knowledge of those skilled in this art. Such modifications include the substitution of known equivalents for any aspect of the invention in order to achieve the same result in substantially the same way is obvious to the skilled in this art and is deemed to include in the present invention. Numeric ranges are inclusive of the numbers defining the range. Furthermore, numeric ranges are provided so that the range of values is recited in addition to the individual values within the recited range being specifically recited in the absence of the range. Example 1 Preparation of Amorphous of the Compound of Formula (I) [0086] The compound of formula (I) (2 g) and dichloromethane (500 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was then transferred to BUCHI Mini Spray Dryer (B-290) spray drier and dried in the following detecting conditions: the inlet temperature was about 100° C., the outlet temperature was about 60° C., lashing velocity was 100% and the bump speed ability was 30% to form granules. The granules were collected and detected by PANalytical Empyreandiffractometer to give an X-ray powder diffractogram of the granules as depict in FIG. 9 . [0087] As used herein, the term “inlet temperature” is the temperature of the solution when coming into the spray drier and the term “outlet temperature” is the temperature of the gas when coming out of the spray drier. [0088] The inlet and the outlet temperature can be modified if necessary according to the equipment, gas or some other experimental parameters. For example, as is known that the outlet temperature can be determined by parameters such as aspirator speed, air humidity, inlet temperature, spray air flow, rate of feed or concentration. Therefore, the outlet temperature would be determined by one skilled in this art through modifying the parameters. Example 2-Example 15 Preparation of Crystalline Form I of the Compound of Formula (I) Example 2 [0089] The compound of formula (I) (0.2 g) (prepared by example 1) and methanol (21 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about 2 days to form a precipitate. The precipitate was filtered, washed with methanol and then dried under vacuum at about 40° C. for about 7 h. The precipitate has an XRFD comprising peaks at about 25.47, 17.69, 27.23, 8.99, 6.68, 14.24, 20.27 and 19.67 degrees in term of two theta, wherein the XRFD substantially as depicted in FIG. 1 . Example 3 [0090] The compound of formula (I) (0.2 g) and ethanol (37.8 mL) were added to a reaction flask, heated to 80° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was cooled down to room temperature and concentrated to about 5 mL under vacuum, then stirred at room temperature for about 1.5 h to form a precipitate. The precipitate was filtered, washed with ethanol and dried overnight under vacuum at about 30° C. to get a yellow solid. The solid was found to be crystalline form I through XRFD detecting. Example 4 [0091] The compound of formula (I) (0.2 g) and methanol (22 mL) were added to a reaction flask, heated to 65° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was cooled down to room temperature, stirred and evaporated naturally until 15 mL was left, and then sealed stirred at room temperature for about 6 h to form a precipitate. The precipitate was filtered, washed with methanol and dried overnight under vacuum at about 30° C. to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 5 [0092] The compound of formula (I) (0.2 g) and acetone (48 mL) were added to a reaction flask, heated to 56° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was cooled down to room temperature, stirred and evaporated naturally until 15 ml was left, and then sealed stirred at room temperature for about 2 days to form a precipitate. The precipitate was filtered and dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 6 [0093] The compound of formula (I) (0.2 g) and THF (18 mL) were added to a reaction flask, heated to 66° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was cooled down to room temperature, stirred and evaporated naturally until 3 mL was left, and then sealed stirred at room temperature for about a day to form a precipitate. The precipitate was filtered and washed with THF, dried overnight under vacuum at about 30° C. to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 7 [0094] The compound of formula (I) (0.2 g) and DCM (60 mL) were added to a reaction flask, heated to 44° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was cooled down to room temperature, stirred and evaporated naturally until 20 mL was left, and then sealed stirred at room temperature for about 3 days to form a precipitate. The precipitate was filtered and washed with DCM, dried under vacuum at about 40° C. for about 7 h to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 8 [0095] The compound of formula (I) (0.2 g) and 1, 4-dioxane (7 mL) were added to a reaction flask, heated to 101° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was cooled down to room temperature, stirred and evaporated naturally until 5 mL was left, and then sealed stirred at room temperature for about 3 days to form a precipitate. The precipitate was filtered and washed with 1, 4-dioxane, dried under vacuum at about 40° C. for about 7 h to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 9 [0096] The compound of Formula (I) (0.2 g) and ethylene glycol (15 mL) were added to a reaction flask, heated to 140° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was cooled down to room temperature, stirred and evaporated naturally until 12 mL was left, and then sealed stirred at room temperature for about 3 days to form a precipitate. The precipitate was filtered and washed with ethylene glycol, dried under vacuum at about 40° C. for about 7 h to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 10 [0097] The compound of formula (I) (0.2 g) and DMF (1 mL) were added to a reaction flask, heated to 70° C. and stirred until the solid was completely dissolved to form a clear solution, to the solution was added ethyl acetate, the resulting solution was slowly cooled down to room temperature and stirred for 2 h to form a precipitate. The precipitate was filtered and washed with ethyl acetate, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 11 [0098] The compound of formula (I) (0.2 g) and ethylene DMF (1.0 mL) were added to a reaction flask, heated to 70° C. and stirred until the solid was completely dissolved to form a clear solution. 5 mL of water was then added dropwise to the solution. After that, the solution was slowly cooled down to room temperature and stirred for 2 h to form a precipitate. The precipitate was filtered and washed with some water, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 12 [0099] The compound of formula (I) (0.2 g) and ethylene NMP (1.4 mL) were added to a reaction flask, heated to 70° C. and stirred until the solid was completely dissolved to form a clear solution. 5 mL of water was then added dropwise to the solution. After that, the mixture was slowly cooled down to room temperature and stirred for 3 h to form a precipitate. The precipitate was filtered and washed with some water, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 13 [0100] The compound of formula (I) (0.2 g) and ethylene DMF (1 mL) were added to a reaction flask, heated to 70° C. and stirred until the solid was completely dissolved to form a clear solution. The 70° C. solution was added dropwise to EtOH (5 mL). After that, the mixture was slowly cooled down to room temperature and stirred for 2 h to form a precipitate. The precipitate was filtered and washed with EtOH, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 14 [0101] The compound of formula (I) (1.0 g) and DMSO (3 mL) were added to a flask, heated to 80° C., after stirred for about 10 mins to the solution was added activated carbon (0.05 g) and stirred for another 30 min, then the temperature was reduced to below 50° C., filtered, the filtrate was heated to 80° C. and was added slowly to water (20 ml) with a temperature of 90° C., after adding, the temperature of the mixture was reduced to 25° C., after stirred for 2 hours, the precipitate was filtered and washed with water, dried under vacuum at about 70° C. for 12 h to get a solid. The water content of the solid is less than 1.0 wt %. Example 15 [0102] The compound of formula (I) (0.2 g) and EtOH (4 mL) were added to a reaction flask, stirred at 50° C. for 5 days, filtered and washed with EtOH, dried overnight under vacuum at about 30° C. to get a solid. The solid was found to be crystalline form I through XRPD detecting. Example 16-21 Preparation of Crystalline Form II of the Compound of Formula (I) Example 16 [0103] The compound of formula (I) (0.2 g) and ethanol (30 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about 2 days to form a precipitate. The precipitate was filtered, washed with ethanol and then dried under vacuum at about 40° C. for about 7 h. The precipitate has an XRFD comprising peaks at about 25.40, 13.86, 17.21 and 22.71 degrees in term of two theta, wherein the XRFD substantially as depicted in FIG. 3 . Example 17 [0104] The compound of formula (I) (0.2 g) and isopropanol (49 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about a day to form a precipitate. The precipitate was filtered, washed with isopropanol and then dried under vacuum at about 40° C. for about 7 h to get a solid. The solid was found to be crystalline form II through XRFD detecting. Example 18 [0105] The compound of formula (I) (0.2 g) and n-butanol (10 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about a day to form a precipitate. The precipitate was filtered, washed with n-butanol and then dried under vacuum at about 40° C. for about 7 h to get a solid. The solid was found to be crystalline form II through XRFD detecting. Example 19 [0106] The compound of formula (I) (0.2 g) and ethylene glycol (5 mL) were added to a reaction flask, heated to about 140° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about a day to form a precipitate. The precipitate was filtered, washed with ethylene glycol and then dried under vacuum at about 40° C. for about 7 h to get a solid. The solid was found to be crystalline form II through XRFD detecting. Example 20 [0107] The compound of formula (I) (0.2 g) and tert-butanol (78 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about 2 days to form a precipitate. The precipitate was filtered, washed with tert-butanol and then dried under vacuum at about 40° C. for about 7 h to get a solid. The solid was found to be crystalline form II through XRPD detecting. Example 21 [0108] The compound of formula (I) (0.2 g) and DMSO (1 mL) were added to a reaction flask, stirred at room temperature until the solid was completely dissolved to form a clear solution. The solution was added dropwise to water (5 mL). After that, the mixture was continuously stirred for 2 h, filtrated and washed with water, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form II through XRPD detecting. Example 22-29 Preparation of Crystalline Form III of the Compound of Formula (I) Example 22 [0109] The compound of formula (I) (0.2 g) and n-propanol (17 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about 2 days to form a precipitate. The precipitate was filtered, washed with n-propanol and then dried under vacuum at about 40° C. for about 7 h. The precipitate has an XRPD comprising peaks at about 25.44, 13.88 and 17.23 degrees in term of two theta, wherein the XRPD substantially as depicted in FIG. 5 . Example 23 [0110] The compound of formula (I) (0.2 g) and 1, 4-dioxane (5 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about 4 days to form a precipitate. The precipitate was filtered, washed with 1,4-dioxane and then dried under vacuum at about 40° C. for about 15 h to get a solid. The solid was found to be crystalline form III through XRPD detecting. Example 24 [0111] The compound of formula (I) (0.2 g) and acetonitrile (24 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about 2 days to form a precipitate. The precipitate was filtered, washed with acetonitril and then dried under vacuum at about 40° C. for about 15 h to get a solid. The solid was found to be crystalline form III through XRPD detecting. Example 25 [0112] The compound of formula (I) (0.2 g) and isopropyl acetate (195 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about 3 days to form a precipitate. The precipitate was filtered, washed with isopropyl acetate and then dried under vacuum at about 40° C. for about 15 h to get a solid. The solid was found to be crystalline form III through XRPD detecting. Example 26 [0113] The compound of formula (I) (0.2 g) and NMP (1.4 mL) were added to a reaction flask, heated to about 70° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and added dropwise to water (5 mL). After that, the mixture was continuously stirred for 2 h, filtrated and washed with water, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form III through XRPD detecting. Example 27 [0114] The compound of formula (I) (0.2 g) and DMSO (1 mL) were added to a reaction flask, stirred at room temperature until the solid was completely dissolved to form a clear solution. The solution was added dropwise to EtOH (5 mL) to form a mixture, after being stirred for 0.5 h, the mixture was added dropwise to water (10 mL) and continuously stirred for 5 h and then filtrated and washed with water, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form III through XRPD detecting. Example 28 [0115] The compound of formula (I) (0.2 g) and DMSO (1 mL) were added to a reaction flask, stirred at room temperature until the solid was completely dissolved to form a clear solution. Water (5 mL) was added dropwise to the solution. Then, continuously stirred for 3 h, filtrated and washed with water, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form III through XRPD detecting. Example 29 [0116] The compound of formula (I) (0.2 g) and DMF (1 mL) were added to a reaction flask, heated to about 70° C. and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and added dropwise to water (5 mL). After that, the mixture was continuously stirred for 2 h, filtrated and washed with water, dried overnight under vacuum at about 40° C. to get a solid. The solid was found to be crystalline form III through XRPD detecting. Example 30 Preparation of Crystalline Form IV of the Compound of Formula (I) [0117] The compound of formula (I) (0.2 g) and n-butanone (39 mL) were added to a reaction flask, heated to reflux and stirred until the solid was completely dissolved to form a clear solution. The solution was slowly cooled down to room temperature and sealed stirred for about 3 days to form a precipitate. The precipitate was filtered, washed with n-butanone and then dried under vacuum at about 40° C. for about 15 h. The precipitate has an XRPD comprising peaks at about 20.01, 27.03, 8.21 degrees in term of two theta, wherein the XRPD substantially as depicted in FIG. 7 . Example 31 The Instrument Parameters Settings and the Detecting Method Thereof 1. X-Ray Powder Diffractogram: [0118] Using Cu tagret/Kα/1.54 Å radiation in the power of 45 kV/40 mA of PANalytical EmpyreanX-ray diffractometer to collect the data from 3°˜40° in term of two theta. The step size is 0.0168° and the scanning rate is 10 s/step. Continuously rotate sample to reduce the impact of preferred orientations. 2. Differential Scanning Calorimeter (DSC) Curve [0119] Collect the thermographs from equipment of TA Q2000. The samples are weighed in T-zero aluminous sample plate, gland, the temperature rise from 40° C. to 300° C. in the rising speed of 10° C./min, the sample is analyzed in nitrogen atmosphere. Example 32 Stability Test of Crystalline Form I, III of the Compound of Formula (I) 1 Sample Package and Storage [0120] The sample was tied with double low density polyethylene film and was placed in the following conditions: 40° C.±2° C./75% RH±5% for 30 days. The purity of the sample was determined by HPLC at the first day and the thirtieth day. 3 the Acceleration Test Result was Showed in Table 1: [0121] [0000] TABLE 1 The acceleration test result of the crystalline form I impurity impurity Overall number A B purity impurity No. of days appearance (%) (%) (%) (%) XRD DSC 1 0 Off-white 0.06 0.26 99.6 0.44 Shows Shows powder characteristic characteristic peaks of form I peaks of form I 30 Off-white 0.06 0.26 99.6 0.43 Yes Yes powder [0000] TABLE 2 The acceleration test result of crystalline form III impurity impurity Overall A B purity impurity No. days appearance (%) (%) (%) (%) XRD DSC 1 0 pale yellow 0.05 0.35 99.4 0.65 Show Show powder characteristic characteristic peaks of peaks of crystalline III crystalline III 30 pale yellow 0.04 0.34 99.4 0.57 Yes Yes powder Conclusion: as show in table 2, the appearance and the related substance of crystalline form I and form III of compound of formula (I) did not change in the conditions of 40° C.±2° C./75% RH±5%, and the crystalline form did not change neither. Indicate that crystalline form I and form III can be stable for a month in the conditions of 40° C.±2° C./75% RH±5%. 2 Chromatographic Condition Chromatographic Column: Agilent RX C8, 4.6×250 mm, 5 μm; [0122] Detector: UV detector, wavelength: 260 nm; flow rate: 1.0 ml/min; column temperature: 40° C.; input dosage: 10 μL; running time: 59 min; Preparation the buffer solution: Sodium 1-octanesulfonate 2.0 g was dissolved in 1000 ml of water, then was added 2 mL of phosphoric acid, The resulted solution was stirred and filtered. The mobile phase includes phase A and phase B, wherein phase A is a mixture of buffer solution and acetonitrile=90:10; with a ratio 90/10 (V/V), Phase B is acetonitrile; Table 3 shows the gradient elution program of mobile phase: [0000] Time (min) Phase A (%) Phase B (%) 0 73 27 20 73 27 51 51 65 52 73 27 59 73 27 Example 33 Hygroscopicity Test of Crystalline Form I and Form III of the Compound of Formula (I) 1 Instrument and Regents 1.1 Instrument: 1/100000 Scale, XP205DR 1.2 Test Method [0123] According to “Chinese Pharmacopoeia”2010 edition, proportion II, XI X J. 1) Keep a dry glass weighing bottle with stopper (external diameter: 50 mm, height: 15 mm) in 25° C.±1° C. of thermostatic drier with saturated solution of ammonium chloride or ammonium sulfate placing on the bottom, precisely weighed (m1). 2) An appropriate amount of sample was spread in the weighing bottle by a millimeter thick, precisely weighed (m2). 3) An open weighing bottle and lid were kept together in environment of constant temperature and humidity for about 24 h. 4) Lid the weighing bottle and precisely weighed (m3). [0000] weight gain ratio=( m 3− m 2)/( m 2− m 1)×100% [0000] 5) Table 4 shows the result judgement of hygroscopicity [0000] NO. Hygroscopic properties Weight gain by sorption 1 hygroscopy Absorb sufficient moisture to form liquid 2 Strong hygroscopic ≧15% 3 hygroscopic ≧2%, <15% 4 slightly hygroscopic ≧0.2%, <2% 5 Low hygroscopic <0.2% 5) Experiment results [0000] TABLE 5 Hygroscopicity results of crystalline form I of the compound of formula (I) Weight gain by absorption # m1 (g) m2 (g) m3 (g) (%) Result 1 28.50004 29.00050 29.00098 0.1% Low hygroscopic [0000] TABLE 6 Hygroscopicity results of crystalline form III of the compound of formula (I) Weight gain by # m1 (g) m2 (g) m3 (g) absorption (%) Result 1 31.58213 31.97061 31.97077 0.04% Low hygroscopic [0124] Those illustrative embodiments herein are used to help understand the method and core ideas about this present invention. In should be noted that many adaptation and modifications may be made without departing from the scope of the appended claims in accordance with the common general knowledge of those of ordinary skilled in the art. [0125] Reference throughout this specification to “an embodiment,” “some embodiments,” “one embodiment”, “another example,” “an example,” “a specific example,” or “some examples,” means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. Thus, the appearances of the phrases such as “in some embodiments,” “in one embodiment”, “in an embodiment”, “in another example,” “in an example,” “in a specific example,” or “in some examples,” in various places throughout this specification are not necessarily referring to the same embodiment or example of the present disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments or examples. [0126] Although explanatory embodiments have been shown and described, it would be appreciated by those skilled in the art that the above embodiments cannot be construed to limit the present disclosure, and changes, alternatives, and modifications can be made in the embodiments without departing from spirit, principles and scope of the present disclosure.
A novel crystalline form or amorphous of formula (I) and preparation method thereof are disclosed in present invention, wherein the novel crystalline form is substantially pure crystalline form I, form II, form III or form IV. The novel crystalline forms disclosed herein have good solubility, low hydroscopicity and good stability at high temperature (60° C.), high humidity (RH is 90%±5%) and/or under light (4500+/−500 Lux), which benefit for storage, meet the requirements of drug stability and therefore, making formula (I) suitable for formulation preparation and with high bioavailability.
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This invention relates to an improved, dry, food mix containing sucrose and fructose and a method for its preparation. Dry beverage mixes containing sweetener, food acid, flavor and flow agent are well known. Generally, the primary sweetener in beverages has been sucrose, glucose or artificial sweeteners. While sucrose is effective to sweeten foods, nutritional reasons have recently inspired a reduction in the sucrose and/or total sugars content of some presweetened foods, especially beverages. To provide traditional levels of sweetness at reduced weight concentrations, sweeteners having more sweetening power per unit weight than sucrose (i.e., having higher relative sweetness) must be employed. While certain high potency non-nutritive or "artificial" sweeteners have been suggested for use, both current food regulations and strong consumer prejudice against artificial sweeteners have directed art attempts at providing presweetened beverage mixes employing only nutritive, carbohydrate sweetening agents. Since fructose is 10-17% sweeter than sucrose on an absolute basis and about 30% sweeter than sucrose in a 50/50 mixture, many attempts have been to employ fructose as a sweetening agent for some foods. Fructose is commercially available in basically two forms, (1) high fructose corn syrup, (hereinafter "HFCS") normally a liquid, and (2) crystalline fructose which is a solid powder. HFCS has the advantage of being relatively inexpensive compared to crystalline fructose and has been employed by soft drink manufactures to reduce cost of their carbonated beverages. Use of HFCS as a major component for presweetened dry beverages is not practical since the 20% moisture content of the HFCS makes a sticky, caked, dry food mix. Another problem with HFCS is that it is not as sweet as crystalline fructose. Fructose exists mostly in four forms as the alpha-furano, beta-furano, alpha-pyrano and beta-pyrano structures. The sweetness perception of fructose is, however, primarily a function of the amount of beta-pyrano form. Crystalline fructose, is usually manufactured as theoretically-pure, anhydrous beta-D-fructopyranose for this reason (although typical analysis indiate only 97.2% beta-pyranose). HFCS, on the other hand, is not as sweet as pure crystalline fructose since it is an amorphous mixture of these non-sweet fructose forms as well as the sweet form. HFCS also contains glucose which is less sweet than fructose. HFCS comprises only about 57-70% of the sweet beta-pyrano form (basis on total fructose). Therefore, crystalline fructose is substantially sweeter on a unit weight basis than HFCS (dry basis). Use of crystalline fructose, while having more intense sweetness, does not overcome the hygroscopic nature of fructose mixtures. In addition crystalline fructose is more expensive than sucrose, but less is needed which helps lower cost. The prior art contains many example of dry food mixes containing monosaccharides, acids, flavor and anti-caking agents. U.S. Pat. No. 4,199,610 entitled "Non-hydroscopic Dry Instant Beverage Mixes" issued Apr. 22, 1980 to Hughes et al., teaches the preparation of a dry, stable, acidulated beverage mix made by adding phosphoric acid to pulverized (instead of granular) sugar, preferably pulverized fructose sugar, with particles from 1-100 microns, then drying the phosphoric acid mixture and grinding the dry cake. U.S. Pat. No. 4,664,920 entitled "Method for Fixing Food Ingredients on a Magnesium Salt Substrate" issued May 12, 1987 to Saleeb et al.; used magnesium salts to fix juice solids, flavors, colors and high fructose corn syrup. U.S. Pat. No. 4,541,873 entitled "Method and Manufacture for easily Spray Drying Low Molecular Weight Sugars" to Schenz et al., issued Sept. 17, 1985; teaches a method of complexing saccharides, including fructose, with metallic cations to improve resistance to humidity and improve flowability. Another quick dissolving beverage is discussed in U.S. Pat. No. 4,343,819 entitled "Quick-Dissolving Powdered Drink and Method Therefore" issued Aug. 10, 1982 to Wood et al., describes a dry beverage mix having carbonates bound to sucrose particles. In U.S. Pat. No. 4,273,695 entitled "Preparing Beverage Mix Containing Dextrose, Hydrate and Coated Citric Acid", a free-flowing beverage mix is prepared by coating particles of food acid with a desicating agent such as silicon dioxide and then mixing the coated particles with a saccharide material. Many of the previously mentioned prior art techniques employ special crystallization or drying techniques. It has not hereto been possible to produce a non-caking, fructose-containing beverage mix having a high proportion of fructose using commonly-available food ingredients and simple mixing techniques. SUMMARY OF THE INVENTION The present invention relates to dry food mixes containing sucrose and fructose. The fructose is present as at least about 10% of the mix and has been processed to insure that no more than 10% of its weight is comprised of particles smaller than 150 microns, preferably no more than 5% of its weight and most preferably no more than 2% of its weight, is comprised of particles smaller than 100 microns in size. As an additional essential feature of this invention all flavors which are combined with the fructose mix have been selected to have a low water activity (i.e., 0.4 or less), most preferably one which approximates that of the crystalline ingredients of the mix. When spray dried flavor is employed, it is fixed in a matrix containing modified starch in order to maintain its water activity at or below 0.4. Anti-caking or flow agents are also employed to prevent fructose particles from fusing together. For fructose levels significantly higher than about 14% of the mix, the anti-caking agents are preferably neutral or acidic to prevent caking that could be caused by reaction of basic anti-caking agents, such as magnesium oxide or calcium silicate, and fructose. Where basic anti-caking agents are employed they must be pre-mixed with at least a portion of the acid employed in the food mix and the acid content of the mix must be 3.0% by weight or greater. While each of the modified ingredients helps prevent caking, all contribute together to yield a shelf-stable, non-caking, fructose-containing dry food mix particularly useful as a beverage mix. All percents recited herein are weight percents. DESCRIPTION OF THE INVENTION The present invention is directed to a stable, dry food mix which contains sucrose, fructose having less than 10% of its particles 150 microns or smaller, a crystallized food acid, flavors having water activity at or below 0.4, as measured at 90° F., and anti-caking agents which are neutral or acidic or have been mixed with acid to balance any alkalinity and to prevent or reduce reaction with the fructose. While each of the modifications made to the dry mix will individually reduce caking caused by the fructose, the combinations of fructose particles size, control of flavor water activity and use of neutral or acid anti-caking agents together give a dry food mix which will remain flowable for months under normal conditions of sale and use by the consumer. Anti-caking agents which are neutral or acidic are calcium citrate, calcium fumarate, tricalcium phosphate and silicon dioxide. We employ crystalline fructose which has been prepared to remove most fructose (less than 10%) particles smaller than 150 microns. By removing these fine particles the coarse fructose particles are less likely to hydrate and stick to each other since fewer particles are spaced further apart in the food mix. Particle size control can be facilitated during manufacture and/or the fructose screened prior to use. Once the desired coarse fructose has been obtained, further abuse of the material or resulting mix should be minimized. The fructose is screened, or otherwise modified to insure that it contains less than 10%, preferably less than 8%, particles smaller than 150 microns and usually less than 5%, preferably less than 2%, of the particles smaller than 100 microns. Crystalline sweeteners such as sucrose or crystalline fructose which have low water activity should be used. The fructose and sucrose content of the mix can range from 10-60% and 20-80% by weight respectively. The combined weight or fructose and sucrose will usually be at least about 40% and for soft drink mixes, such as fruit-flavored beverage mixes, will typically be at least 90%, usually about 95% or more, of the mix. We also employ crystallized food acids of equally low water activity to reduce the amount of water introduced into the dry food mix. Suitable acids include citric, malic, tartaric, fumaric, adipic and their like. From 0.5% to 10% food acid is employed. Where basic anti-caking agents are employed we try to mix the anti-caking agent with the food acid and use levels of acid above 3% by weight of the mix to reduce the likelihood of reaction between the alkaline anti-caking agent and the fructose. The food flavor can be any, suitable flavor provided the water activity is maintained at or below 0.4, preferably at or below 0.36, measured at 90° F. Some flavors can have a water activity approaching the crystalline sugars and acid employed in the mix. Spray dried flavors, normally fixed in malto-dextrin must be modified to reduce their water activity. We have found that 20-80% of a modified starch may replace a similar amount of malto-dextrin to produce suitable flavors having low water activity. A typical spray-dried flavor for use in this invention contains 30-60% modified food starch having a molecular weight in excess of 2,000, 30-60% malto-dextrin and flavorant. A typical fixed flavor can be about 40% chemically modified food starch, about 40% malto-dextrin and about 20% lemon oil is mixed with 40% "N-LOC" modified starch manufactured by National Starch and 40% "LODEX" hydrolyzed corn syrup supplied by Amaizo, American Maize Products, Hammond, Ind. When mixed in an aqueous suspension or solution and spray dried there is produced a lemon flavor with a water activity below 0.36, most preferably below 0.34. A dry mix composition may be prepared in the following manner. Minor ingredients such as vitamins, colors, buffers, sweetness enhancers and the anti-caking agent are added to the acid already placed in a ribbon mixer. The premix is blended for 20 minutes or more to obtain a uniform blend. Each ingredient is fed separately into the blender through a coarse screen which is used to distribute the material onto the surface of the acid. The premix is then added with the major ingredients of sucrose and fructose and flavor, using Merrick™ Scale Feeders, to a continuous mixing screw where the ingredients are homogeneously blended without excessive handling which would produce fines. The dry mix is stored in large containers and transported, when needed, to packaging. Rough treatment of the prepared mix is avoided and the temperature and humidity of the ambient atmosphere are controlled to reduce exposure of the mix to moisture. The mix is packaged in depending on the product and its serving size. The following examples which set forth several non-caking beverage mix formulations are intended to illustrate various embodiments of the invention but are not intended to limit the invention in any way. __________________________________________________________________________ Example No. 1 2 3 4 5 6 FlavorIngredients (wt. %) Lemonade Orange Punch Grape Lemon Cherry__________________________________________________________________________Crystalline Sucrose 77 77 81 81 79 81Coarse Fructose 14 14 14 16 17 16Flavor extruded in 1 1 -- -- -- --amorphous carbohydrate(Aw less than 0.34)Spray Dried Flavor -- -- 0.6 0.28 0.32 0.4(Aw less than 0.34)Crystallized 6.9 5.4 3.9 2.4 3.1 2.4Citric AcidAlkalineAnti-caking AgentMagnesium Oxide 0.3 -- 0.2 -- -- --Calcium Silicate -- -- 0.09 -- -- --Neutral or AcidicAnti-caking AgentTricalcium phosphate -- 0.3 -- 0.3 0.3 0.3Tricalcium citrate -- 0.15 -- -- -- --Buffer, color trace trace trace trace trace tracevitamins, cloud,flavor and enhancers__________________________________________________________________________ It can be seen that alkaline flow agents can be employed provided the acid level is maintained above 3.0% by weight. The spray dried flavors, which may contain 2-8% moisture, can contribute about one half the water content of the mix, were found to produce non-caking products on storage and use.
A sucrose and fructose-containing dry food mix and method of manufacture is disclosed. The fructose is crystalline fructose having less than 10% of its particles smaller than 150 microns, a flavor having a low water activity particularly spray dried in a modified starch and malto-dextrin matrix and an acidic or neutral anti-caking agent. The food mix does not cake over an extended period of time.
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RELATED APPLICATION [0001] This application is a divisional application of pending application Ser. No. 09/587,970 filed Jun. 8, 2000, which is hereby incorporated by reference in its entirety. BACKGROUND OF THE INVENTION [0002] This invention relates to photocatalytically active coated substrates, in particular, but not exclusively, it relates to a photocatalytically active coated glass. [0003] It is known to deposit thin coatings having one or more layers, with a variety of properties, on to substrates including on to glass substrates. One property of interest is photocatalytic activity which arises by the photogeneration, in a semiconductor, of a hole-electron pair when the semiconductor is illuminated by light of a particular frequency. The hole-electron pair can be generated in sunlight and can react in humid air to form hydroxy and peroxy radicals on the surface of the semiconductor. The radicals oxidise organic grime on the surface. This property has an application in self-cleaning substrates, especially in self-cleaning glass for windows. [0004] Titanium dioxide may be an efficient photocatalyst and may be deposited on to substrates to form a transparent coating with photocatalytic self-cleaning properties. Titanium oxide photocatalytic coatings are disclosed in EP 0 901 991 A2, WO 97/07069, WO 97/10186, WO 98/41480, in Abstract 735 of 187th Electrochemical Society Meeting (Reno, Nev., 95-1, p.1102) and in New Scientist magazine (Aug. 26, 1995, p.19). In WO 98/06675 a chemical vapor deposition process is described for depositing titanium oxide coatings on hot flat glass at high deposition rate using a precursor gas mixture of titanium chloride and an organic compound as source of oxygen for formation of the titanium oxide coating. [0005] It has been thought that relatively thick titanium oxide coatings need to be deposited to provide good photocatalytic activity. For example, in WO 98/41480 it is stated that a photocatalytically active self-cleaning coating must be sufficiently thick so as to provide an acceptable level of activity and it is preferred that such a coating is at least about 200 Å and However, a problem of relatively thick titanium oxide coatings is high visible light reflection and thus relatively low visible light transmission. This problem is recognized in the article in New Scientist magazine in relation to coated windscreens, where it is suggested that to reduce the effect of high reflection, dashboards might have to be coated in black velvet or some other material that does not reflect light into a coated windscreen. [0006] EP 0 901 991A2 referred to above, relates to photocatalytic glass panes with a coating of titanium oxide of a particular crystal structure characterised by the presence of particular peaks in its X-ray diffraction pattern. The specification contemplates a range of coating thickness (with the specific Examples all having thickness in the range 20 nm to 135 nm, the thinner coatings being less photocatalytically active than the thicker coatings). The specification also contemplates a range of deposition temperatures from as low as 300° C. to as high as 750° C., but prefers temperatures in the range 400° C. to 600° C., and in all the specific Examples of the invention the titanium dioxide layer is deposited at a temperature in or below this preferred range. [0007] The applicants have now found that by depositing the titanium oxide coatings at higher temperatures, especially temperatures above 600° C., they are able to achieve coatings with an enhanced photocatalytic activity for a given thickness, enabling the same photocatalytic performance to be achieved with thinner coatings. Such thinner coatings tend to have, advantageously, lower visible light reflection and, apparently in consequence of their higher deposition temperature, improved durability, especially to abrasion and temperature cycling in a humid atmosphere. SUMMARY OF THE INVENTION [0008] The present invention accordingly provides a process for the production of a photocatalytically active coated substrate which comprises depositing a titanium oxide coating on the surface of a substrate by contacting the surface of the substrate with a fluid mixture containing a source of titanium and a source of oxygen, said substrate being at a temperature of at least 600° C., whereby the coated surface of the substrate has a photocatalytic activity of greater than 5×10 −3 cm −1 min −1 and a visible light reflection measured on the coated side of 35% or lower. [0009] Preferably, the substrate is at a temperature in the range 625° C. to 720° C., more preferably the substrate is at a temperature in the range 645° C. to 720° C. [0010] Advantageously, the fluid mixture comprises titanium chloride as the source of titanium and an ester other than a methyl ester. Thus, in a preferred embodiment, the present invention provides a process for the production of a photocatalytically active coated substrate which comprises depositing a titanium oxide coating having a thickness of less than 40 nm on a substrate by contacting a surface of the substrate with a fluid mixture comprising titanium chloride and an ester other than a methyl ester. [0011] The process may be performed wherein the surface of the substrate is contacted with the fluid mixture when the substrate is at a temperature in the range 600° C. to 750° C. [0012] Preferably, the ester is an alkyl ester having an alkyl group with a β hydrogen (the alkyl group of an alkyl ester is the group derived from the alcohol in synthesis of an ester and a β hydrogen is a hydrogen bonded to a carbon atom β to the oxygen of the ether linkage in an ester). Preferably the ester is a carboxylate ester. [0013] Suitable esters may be alkyl esters having a C 2 to C 10 alkyl group, but preferably the ester is an alkyl ester having a C 2 to C 4 alkyl group. [0014] Preferably, the ester is a compound of formula: R—C(O)—O—C(X)(X′)—C(Y)(Y′)—R′ [0015] where R and R′ represent hydrogen or an alkyl group, X, X′, Y and Y′ represent monovalent substituents, preferably alkyl groups or hydrogen atoms and wherein at least one of Y and Y′ represents hydrogen. [0016] Suitable esters that may be used in the process of the present invention include: ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, n-propyl formate, n-propyl acetate, n-propyl propionate, n-propyl butyrate, isopropyl formate, isopropyl acetate, isopropyl propionate, isopropyl butyrate, n-butyl formate, n-butyl acetate and t-butyl acetate. [0017] Preferably, the ester comprises an ethyl ester, more preferably the ester comprises ethyl formate, ethyl acetate or ethyl propionate. Most preferably the ester comprises ethyl acetate. [0018] The fluid mixture may be in the form of a liquid, especially dispersed as a fine spray (a process often referred to as spray deposition), but preferably the fluid mixture is a gaseous mixture. A deposition process performed using a gaseous mixture as precursor is often referred to as chemical vapor deposition (CVD). The preferred form of CVD is laminar flow CVD, although turbulent flow CVD may also be used. [0019] The process may be performed on substrates of various dimensions including on sheet substrates, especially on cut sheets of glass, or preferably on-line during the float glass production process on a continuous ribbon of glass. Thus, preferably, the process is performed on-line during the float glass production process and the substrate is a glass ribbon. If the process is performed on line, it is preferably performed on the glass ribbon whilst it is in the float bath. [0020] An advantage of performing the process on-line is that coatings deposited on-line tend to be durable and in particular to have good abrasion and chemical resistance. [0021] An on-line deposition process is preferably, and other deposition processes may be, performed at substantially atmospheric pressure. [0022] In a particularly preferred embodiment there is provided a process for the production of a durable photocatalytically active coated glass which comprises depositing on the surface of a glass substrate a photocatalytically active titanium oxide layer by contacting the surface of the substrate, which is at a temperature in the range 645° C. to 720° C., preferably in the range 670° C. to 720° C. with a fluid mixture containing a source of titanium. [0023] As noted above, the applicants have found that by depositing the titanium oxide at high temperature, a coating of relatively high photocatalytic activity for its thickness may be produced and, as coatings of reduced thickness tend to have lower reflection, the invention also provides novel products having an advantageous combination of high photocatalytic activity with moderate or low light reflection. [0024] Thus, the present invention, in another aspect, provides a photocatalytically active coated substrate comprising a substrate having a photocatalytically active titanium oxide coating on one surface thereof, characterised in that the coated surface of the substrate has a photocatalytic activity of greater than 5×10 −3 cm −1 min −1 and in that the coated substrate has a visible light reflection measured on the coated side of 35% or lower. [0025] High photocatalytic activity is advantageous because the amount of contaminants (including dirt) on the coated surface of the photocatalytically active coated substrate will be reduced quicker than on substrates with relatively low photocatalytic activity. Also, relatively quick removal of surface contaminants will tend to occur at low levels of UV light intensity. [0026] Photocatalytic activity for the purposes of this specification is determined by measuring the rate of decrease of the integrated absorbance of the infra-red absorption peaks corresponding to the C—H stretches of a thin film of stearic acid, formed on the coated substrate, under illumination by UV light from a UVA lamp having an intensity of about 32 W/m 2 at the surface of the coated substrate and a peak wavelength of 351 nm. The stearic acid may be formed on the coated substrate by spin casting a solution of stearic acid in methanol as described below. [0027] Preferably, the coated surface of the substrate has a photocatalytic activity of greater than 1×10 −2 cm −1 min −1 , more preferably of greater than 3×10 −2 cm −1 min −1 . [0028] Low visible light reflection is advantageous because it is less distracting than high reflection and, especially for glass substrates, low visible light reflection corresponds to high visible transmission which is often required in architectural and especially automotive applications of glass. [0029] Preferably, the coated substrate has a visible reflection measured on the coated side of 20% or lower more preferably of 17% or lower and most preferably of 15% or lower. [0030] In most embodiments of the invention the substrate will be substantially transparent and in a preferred embodiment of the invention the substrate comprises a glass substrate. Usually the glass substrate will be a soda lime glass substrate. [0031] Where the substrate is a soda lime glass substrate or other alkali metal ion containing substrate, the coated substrate preferably has an alkali metal ion blocking underlayer between the surface of the substrate and the photocatalytically active titanium oxide coating. This reduces the tendency for alkali metal ions from the substrate to migrate into the photocatalytically active titanium oxide coating which is advantageous because of the well known tendency of alkali metal ions to poison semiconductor oxide coatings, reducing their activity. [0032] The alkali metal ion blocking underlayer may comprise a metal oxide but preferably the alkali metal ion blocking layer is a layer of silicon oxide. The silicon oxide may be silica but will not necessarily be stoichiometric and may comprise impurities such as carbon (often referred to as silicon oxycarbide and deposited as described in GB 2,199,848B) or nitrogen (often referred to as silicon oxynitride). [0033] It is advantageous if the alkali metal ion blocking underlayer is thin so that it has no significant effect on the optical properties of the coating, especially by reducing the transparency of a transparent coated substrate or causing interference colors in reflection or transmission. The suitable thickness range will depend on the properties of the material used to form the alkali metal ion blocking layer (especially its refractive index), but usually the alkali metal ion blocking underlayer has a thickness of less than 60 nm and preferably has a thickness of less than 40 nm. Where present, the alkali metal ion blocking underlayer should always be thick enough to reduce or block migration of alkali metal ions from the glass into the titanium oxide coating. [0034] An advantage of the present invention is that the photocatalytically active titanium oxide coating is thin (contributing to the low visible reflection of the coated substrate) but the coated substrate still has excellent photocatalytic activity. Preferably, the titanium oxide coating has a thickness of 30 nm or lower, more preferably the titanium oxide coating has a thickness of 20 nm or lower and most preferably the titanium oxide coating has a thickness in the range 2 nm to about 20 nm. [0035] The present invention is also advantageous because depositing thin titanium oxide coatings requires less precursor and the layers can be deposited in a relatively short time. A thin titanium oxide coating is also less likely to cause interference colors in reflection or transmission. However, a particular advantage is that the visible light reflection of a thin titanium oxide coating is low which is especially important when the coated substrate is coated glass. Usually the required visible light transmission of the coated glass will determine the thickness of the titanium oxide coating. [0036] Preferably, the coated surface of the substrate has a static water contact angle of 20° or lower. Freshly prepared or cleaned glass has a hydrophilic surface (a static water contact angle of lower than about 40° indicates a hydrophilic surface), but organic contaminants rapidly adhere to the surface increasing the contact angle. A particular benefit of coated substrates (and especially coated glasses) of the present invention is that even if the coated surface is soiled, irradiation of the coated surface by UV light of the right wavelength will reduce the contact angle by reducing or destroying those contaminants. A further advantage is that water will spread out over the low contact angle surface reducing the distracting effect of droplets of water on the surface (e.g. from rain) and tending to wash away any grime or other contaminants that have not been destroyed by the photocatalytic activity of the surface. The static water contact angle is the angle subtended by the meniscus of a water droplet on a glass surface and may be determined in a known manner by measuring the diameter of a water droplet of known volume on a glass surface and calculated using an iterative procedure. [0037] Preferably, the coated substrate has a haze of 1% or lower, which is beneficial because this allows clarity of view through a transparent coated substrate. [0038] In preferred embodiments, the coated surface of the substrate is durable to abrasion, such that the coated surface remains photocatalytically active after it has been subjected to 300 strokes of the European standard abrasion test. Preferably, the coated surface remains photocatalytically active after it has been subjected to 500 strokes of the European standard abrasion test, and more preferably the coated surface remains photocatalytically active after it has been subjected to 1000 strokes of the European standard abrasion test. [0039] This is advantageous because self-cleaning coated substrates of the present invention will often be used with the coated surface exposed to the outside (e.g. coated glasses with the coated surface of the glass as the outer surface of a window) where the coating is vulnerable to abrasion. [0040] The European standard abrasion test refers to the abrasion test described in European standard BS EN 1096 Part 2 (1999) and comprises the reciprocation of a felt pad at a set speed and pressure over the surface of the sample. [0041] In the present specification, a coated substrate is considered to remain photocatalytically active if, after being subjected to the European abrasion test, irradiation by UV light (e.g. of peak wavelength 351 nm) reduces the static water contact angle to below 15°. To achieve this contact angle after abrasion of the coated substrate will usually take less than 48 hours of irradiation at an intensity of about 32 W/m 2 at the surface of the coated substrate. [0042] Preferably, the haze of the coated substrate is 2% or lower after being subjected to the European standard abrasion test. [0043] Durable coated substrates according to the present invention may also be durable to humidity cycling (which is intended to have a similar effect to weathering). Thus, in preferred embodiments of the invention, the coated surface of the substrate is durable to humidity cycling such that the coated surface remains photocatalytically active after the coated substrate has been subjected to 200 cycles of the humidity cycling test. In the present specification, the humidity cycling test refers to a test wherein the coating is subjected to a temperature cycle of 35° C. to 75° C. to 35° C. in 4 hours at near 100% relative humidity. The coated substrate is considered to remain photocatalytically active, if, after the test, irradiation by UV light reduces the static water contact angle to below 15°. [0044] In a further preferred embodiment, the present invention provides a durable photocatalytically active coated glass comprising a glass substrate having a coating on one surface thereof, said coating comprising an alkali metal ion blocking underlayer and a photocatalytically active titanium oxide layer, wherein the coated surface of the substrate is durable to abrasion such that the coated surface remains photocatalytically active after it has been subjected to 300 strokes of the European standard abrasion test. In this embodiment, the coated glass preferably has a visible light reflection measured on the coated side of 35% or lower, and the photocatalytically active titanium oxide layer preferably has a thickness of 30 nm or lower. Thin coatings are durable to abrasion which is surprising because previously it has been thought that only relatively thick coatings would have good durability. [0045] In a still further embodiment, the present invention provides a coated glass comprising a glass substrate having a photocatalytically active titanium oxide coating on one surface thereof, characterised in that the coated surface of the glass has a photocatalytic activity of greater than 4×10 −2 cm −1 min −1 , preferably greater than 6×10 −2 cm −1 min −1 and more preferably greater than 8×10 −2 cm −1 min −1 and in that the coated glass has a visible light reflection measured on the coated side of less than 20%. [0046] Coated substrates according to the present invention have uses in many areas, for example as glazings in windows including in a multiple glazing unit comprising a first glazing pane of a coated substrate in spaced opposed relationship to a second glazing pane, or, when the coated substrate is coated glass, as laminated glass comprising a first glass ply of the coated glass, a polymer interlayer (of, for example, polyvinylbutyral) and a second glass ply. [0047] In addition to uses in self-cleaning substrates (especially self-cleaning glass for windows), coated substrates of the present invention may also be useful in reducing the concentration of atmospheric contaminants. For example, coated glass under irradiation by light of UV wavelengths (including UV wavelengths present in sunlight) may destroy atmospheric contaminants for example, nitrogen oxides, ozone and organic pollutants, adsorbed on the coated surface of the glass. This use is particularly advantageous in the open in built-up areas (for example, in city streets) where the concentration of organic contaminants may be relatively high (especially in intense sunlight), but where the available surface area of glass is also relatively high. Alternatively, the coated glass (with the coated surface on the inside) may be used to reduce the concentration of atmospheric contaminants inside buildings, especially in office buildings having a relatively high concentration of atmospheric contaminants. [0048] The invention is illustrated but not limited by the following drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0049] [0049]FIG. 1 is a graph of photocatalytic activity of coated glass produced by a process according to the invention as a function of the thickness of the titanium oxide layer. [0050] [0050]FIG. 2 illustrates apparatus for on line chemical vapor deposition of coatings according to the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0051] In FIG. 1 the coated glasses were produced using an on-line CVD process as described in the Examples, below. The open circles 1 relate to titanium oxide layers deposited using titanium tetrachloride as titanium precursor, and the crosses 2 relate to titanium oxide layers deposited using titanium tetraethoxide as titanium precursor. [0052] The layers of the coating may be applied on line onto the glass substrate by chemical vapor deposition during the glass manufacturing process. FIG. 2 illustrates an apparatus, indicated generally at 10 , useful for the on line production of the coated glass article of the present invention, comprising a float section 11 , a lehr 12 , and a cooling section 13 . The float section 11 has a bottom 14 which contains a molten tin bath 15 , a roof 16 , sidewalls (not shown), and end walls 17 , which together form a seal such that there is provided an enclosed zone 18 , wherein a non-oxidizing atmosphere is maintained to prevent oxidation of the tin bath 15 . During operation of the apparatus 10 , molten glass 19 is cast onto a hearth 20 , and flows therefrom under a metering wall 2 1 , then downwardly onto the surface of the tin bath 15 , forming a float glass ribbon 37 , which is removed by lift-out rolls 22 and conveyed through the lehr 12 , and thereafter through the cooling section 13 . [0053] A non-oxidizing atmosphere is maintained in the float section 11 by introducing a suitable gas, such as for example one comprising nitrogen and 2% by volume hydrogen, into the zone 18 , through conduits 23 which are operably connected to a manifold 24 . The non-oxidizing gas is introduced into the zone 18 from the conduits 23 at a rate sufficient to compensate for losses of the gas (some of the non-oxidizing atmosphere leaves the zone 18 by flowing under the end walls 17 ), and to maintain a slight positive pressure above ambient pressure. The tin bath 15 and the enclosed zone 18 are heated by radiant heat directed downwardly from heaters 25 . The heat zone 18 is generally maintained at a temperature of about 1330° F. to 1400° F. (721° C. to 760° C.). The atmosphere in the lehr 12 is typically air, and the cooling section 13 is not enclosed. Ambient air is blown onto the glass by fans 26 . [0054] The apparatus 10 also includes coaters 27 , 28 , 29 and 30 located in series in the float zone 11 above the float glass ribbon 37 . The precursor gaseous mixtures for the individual layers of the coating are supplied to the respective coaters, which in turn direct the precursor gaseous mixtures to the hot surface of the float glass ribbon 37 . The temperature of the float glass ribbon 37 is highest at the location of the coater 27 nearest the hearth 20 and lowest at the location of the coater 30 nearest the lehr 12 . [0055] The invention is further illustrated by the following Examples, in which coatings were applied by laminar flow chemical vapor deposition in the float bath on to a moving ribbon of float glass during the glass production process. In the Examples two layer coatings were applied to the glass ribbon. [0056] All gas volumes are measured at standard temperature and pressure unless otherwise stated. The thickness values quoted for the layers were determined using high resolution scanning electron microscopy and optical modelling of the reflection and transmission spectra of the coated glass. Thickness of the coatings was measured with an uncertainty of about 5%. The transmission and reflection properties of the coated glasses were determined using an Hitachi U-4000 spectrophotometer. The a, b and L* values mentioned herein of the transmission and/or reflection color of the glasses refer to the CIE Lab colors. The visible reflection and visible transmission of the coated glasses were determined using the D65 illuminant and the standard CIE 2° observer in accordance with the ISO 9050 standard (Parry Moon airmass 2) The haze of the coated glasses was measured using a WYK-Gardner Hazeguard+ haze meter. [0057] The photocatalytic activity of the coated glasses was determined from the rate of decrease of the area of the infrared peaks corresponding to C—H stretches of a stearic acid film on the coated surface of the glass under illumination by UVA light. The stearic acid film was formed on samples of the glasses, 7-8 cm square, by spin casting 20 μl of a solution of stearic acid in methanol (8.8×10 −3 mol dm 3 ) on the coated surface of the glass at 2000 rpm for 1 minute. Infra red spectra were measured in transmission, and the peak height of the peak corresponding to the C—H stretches (at about 2700 to 3000 cm −1 ) of the stearic acid film was measured and the corresponding peak area determined from a calibration curve of peak area against peak height. The coated side of the glass was illuminated with a UVA-351 lamp (obtained from the Q-Panel Co., Cleveland, Ohio, USA) having a peak wavelength of 351 nm and an intensity at the surface of the coated glass of approximately 32W/m 2 . The photocatalytic activity is expressed in this specification either as the rate of decrease of the area of the IR peaks (in units of cm −1 min −1 ) or as t 90% (in units of min) which is the time of UV exposure taken to reduce the peak height (absorption) of a peak in the wavelength area down to 10% of its initial value. [0058] The static water contact angle of the coated glasses was determined by measuring the diameter of a water droplet (volume in the range 1 to 5 μl) placed on the surface of the coated glass after irradiation of the coated glass using the UVA 351 lamp for about 2 hours (or as otherwise specified). EXAMPLES 1-15 [0059] A ribbon of 1 mm thick soda lime float glass advancing at a lehr speed of 300 m/hour was coated with a two-layer coating as the ribbon advanced over the float bath at a position where the glass temperature was in the range of about 650° C. to about 670° C. The float bath atmosphere comprised a flowing gaseous mixture of nitrogen and 9% hydrogen at a bath pressure of approximately 0.15 mbar. [0060] Layer 1 (the first layer to be deposited on the glass) was a layer of silicon oxide. Layer 1 was deposited by causing a gaseous mixture of monosilane (SiH 4 , 60 ml/min), oxygen (120 ml/min), ethylene (360 ml/min) and nitrogen (8 liters/min) to contact and flow parallel to the glass surface in the direction of movement of the glass using coating apparatus as described in GB patent specification 1 507 966 (referring in particular to FIG. 2 and the corresponding description on page 3 line 73 to page 4 line 75) with a path of travel of the gaseous mixture over the glass surface of approximately 0.15 m. Extraction was at approximately 0.9 to 1.2 mbar. The glass ribbon was coated across a width of approximately 10 cm at a point where its temperature was approximately 670° C. The thickness of the silica layer was about 20 to 25 m. [0061] Layer 2 (the second layer to be deposited) was a layer of titanium dioxide. Layer 2 was deposited by combining separate gas streams comprising titanium tetrachloride in flowing nitrogen carrier gas, ethyl acetate in flowing nitrogen carrier gas and a bulk flow of nitrogen of 8 l/min (flow rate measured at 20 psi) into a gaseous mixture and then delivering (through lines maintained at about 250° C.) the gaseous mixture to coating apparatus consisting of an oil cooled dual flow coater. The pressure of the nitrogen carrier and bulk nitrogen gases was approximately 20 pounds per square inch. The gaseous mixture contacted and flowed parallel to the glass surface both upstream and downstream along the glass ribbon. The path of travel of the gaseous mixture downstream was about 0.15 m and upstream was about 0.15 m with extraction of about 0.15 mbar. Titanium tetrachloride and ethyl acetate were entrained in separate streams of flowing nitrogen carrier gas by passing nitrogen through bubblers containing either titanium tetrachloride or ethyl acetate. The flow rates of the nitrogen carrier gases are described in Table 1 (the flow rates were measured at 20 psi). The titanium tetrachloride bubbler was maintained at a temperature of 69° C. and the ethyl acetate bubbler was maintained at a temperature of 42° C. The estimated flow rates of entrained titanium tetrachloride and entrained ethyl acetate are also described in Table 1 for each of the Examples 1 to 15. [0062] The properties of the two-layer coatings were measured. Values of the thickness of layer 2 (the titanium oxide layer), and values of the visible reflection measured on the coated side, L* and haze of the coated glasses are described in Table 2 for the Examples 1-15. The haze of each coated glass was below 0.2%. [0063] The photocatalytic activity and static water contact angle of the coated glasses were determined. The initial peak height and initial peak area of the IR peaks corresponding to the stearic acid C—H stretches, the photocatalytic activity, the static water contact angle and t 90% for the Examples 1-15 are described in Table 3. The thickness of the titanium oxide layer, surprisingly has little effect on photocatalytic activity. EXAMPLES 16-19 [0064] Examples 16-19 were conducted under the same conditions as Examples 1-15 except that the bath pressure was approximately 0.11 mbar, extraction for deposition of the silica undercoat (layer 1 ) was approximately 0.7 mbar, the titanium tetrachloride bubbler was maintained at a temperature of approximately 100° C., the ethyl acetate bubbler was maintained at a temperature of approximately 45° C. and the delivery lines were maintained at a temperature of approximately 220° C. [0065] The flow rates of nitrogen carrier gas, and the estimated flow rates of entrained titanium tetrachloride and entrained ethyl acetate are disclosed for each of the examples 16-19 in Table 1. [0066] Values of the estimated thickness of layer 2 (the titanium oxide layer), and values of visible reflection measured on the coated side, L* and haze of the coated glasses are described in Table 2 for each of the Examples 16-19. [0067] The initial peak height and initial peak area of the IR peaks corresponding to the stearic acid C—H stretches, the photocatalytic activity, t 90% and the static water contact angle and for each of the Examples 16-19 are described in Table 3. [0068] The photocatalytic activity of the Examples 16-19 was not substantially greater than that of the Examples 1-15 despite the thicker titanium oxide (and hence more reflective) coatings. TABLE 1 Nitrogen Carrier Gas Flow Rates to Bubblers Ethyl (1/min, measured at 20 psi) TiCl 4 Acetate TiCl 4 Ethyl Acetate flow rate flow rate Example Bubbler Bubbler (1/min) (1/min) 1 0.16 1 0.032 0.46 2 0.12 0.3 0.024 0.14 3 0.12 0.45 0.024 0.21 4 0.08 0.2 0.016 0.09 5 0.12 0.15 0.024 0.07 6 0.12 0.75 0.024 0.35 7 0.08 0.3 0.016 0.14 8 0.08 0.5 0.016 0.23 9 0.04 0.1 0.008 0.05 10 0.04 0.15 0.008 0.07 11 0.04 0.25 0.008 0.12 12 0.16 0.1 0.032 0.05 13 0.08 0.1 0.016 0.05 14 0.16 0.4 0.032 0.19 15 0.16 0.2 0.032 0.09 16 0.1 0.5 0.088 0.27 17 0.08 0.4 0.070 0.22 18 0.06 0.3 0.053 0.16 19 0.04 0.2 0.035 0.11 [0069] [0069] TABLE 2 Thickness of titanium oxide Visible L* value of layer reflection of coated glass Haze Example (nm) coated glass (%) (%) (%) 1 15 14.1 44 0.12 2 14.3 13.9 44 0.07 3 14.2 13.2 43 0.12 4 11.3 11.4 40 0.08 5 12.1 12.1 41 0.08 6 11.0 a a 0.07 7 8 a a 0.11 8 7.2 9.7 37 0.04 9 6.1 9.1 36 0.05 10 5.6 9 36 0.07 11 4.6 8.7 35 0.06 12 15.6 15.4 46 0.1 13 16.0 a a 0.13 14 17.5 16.2 47 0.14 15 20.3 19.5 51 0.1 16 a 28.4 47.8 0.3 17 ca 68 29.1 58.4 0.37 18 ca 32 25.9 55.6 0.24 19 ca 27 20.5 50.2 0.2 [0070] [0070] TABLE 3 IR Peaks corresponding to stearic acid film C—H stretches (2700-3000 cm −1 ) Static Initial Peak Photocatalytic Water Height Activity Contact (arbitrary Initial Peak (× 10 −2 cm −1 Angle t 90% Example units) Area (cm −1 ) min −1 ) (°) (min) 1 0.030 1.04 9.4 17 ± 5 10 2 0.0331 1.15 10.4 15 ± 1 10 3 0.0311 1.08 12.2 13 ± 2 8 4 0.0324 1.13 6.8 14 ± 1 15 5 0.0287 1.00 8.2 16 ± 3 11 6 0.028 0.98 8.8 15 ± 1 10 7 0.0343 1.20 10.8 15 ± 1 10 8 0.0289 1.03 6.6 16 ± 1 14 9 0.0289 1.01 6.5 14 ± 2 14 10 0.0278 0.97 6.2 18 ± 2 14 11 0.0344 1.20 5.4 18 ± 1 20 12 0.0291 1.02 10.2 12 ± 1 9 13 0.0289 1.01 9.1 14 ± 2 10 14 0.0269 0.94 9.4 15 ± 2 9 15 0.0331 1.15 8.7 15 ± 2 12 16 0.0227 0.79 17.8 12 4 17 0.026 0.91 10.2 12 8 18 0.0225 0.79 10.1 13 7 19 0.0258 0.90 10.1 16 8 EXAMPLES 20-27 [0071] The Examples 20-27 were conducted under the same conditions as Examples 1-15 except that layer 2 was deposited from a gaseous mixture comprising titanium tetraethoxide entrained in nitrogen carrier gas by passing the carrier gas through a bubbler containing titanium tetraethoxide maintained at a temperature of 170° C. The flow rates of nitrogen carrier gas (measured at 20 psi) and titanium tetraethoxide are described in Table 4 for each of the Examples 20-27. The flow rate of bulk nitrogen gas was 8.5 l/min (measured at 20 psi). [0072] The properties of the two-layer coatings were measured. Values of the thickness of layer 2 (the titanium oxide layer), and values of the visible reflection measured on the coated side and haze of the coated glasses are described in Table 5 for the Examples 20-27. The haze of each coated glass was below 0.7%. [0073] The photocatalytic activity and static water contact angle of the coated glasses were determined. The initial peak height and initial peak area of the IR peaks corresponding to the stearic acid C—H stretches, the photocatalytic activity and t 90% , and the static water contact angle for each of the Examples 20-27 are described in Table 6. EXAMPLES 28 AND 29 [0074] The Examples 28 and 29 were conducted under the same conditions as Examples 20-27 except that the titanium tetraethoxide bubbler was maintained at a temperature of 168° C. and the bath pressure was 0.11 mbar. Data relating to Examples 28-29 equivalent to data for Examples 20-27 are described in Tables 4, 5 and 6. TABLE 4 Nitrogen Carrier Gas Flow Rates to Titanium ethoxide flow Titanium tetraethoxide bubbler (1/ rate Example min, measured at 20 psi) (1/min) 20 0.25 0.014 21 0.15 0.008 22 0.2 0.011 23 0.25 0.014 24 0.3 0.017 25 0.35 0.019 26 0.2 0.011 27 0.1 0.006 28 0.6 0.030 29 0.4 0.020 [0075] [0075] TABLE 5 Thickness of titanium oxide layer Visible reflection of Haze Example (nm) coated glass (%) (%) 20 13 a 0.4 21 13 a 0.29 22 16 15.7 0.29 23 18 a 0.28 24 24 a a 25 26 a 0.61 26 9.9 10.9 0.19 27 4.7 8.8 0.29 28 38.3 35.2 0.29 29 31.9 28.4 0.22 [0076] [0076] TABLE 6 IR Peaks corresponding to stearic acid film C—H stretches (2700-3000 cm −1 ) Static Initial Peak Photocatalytic Water Height Activity Contact (arbitrary Initial Peak (× 10 −2 cm −1 Angle t 90% Example units) Area (cm −1 ) min −1 ) (°) (min) 20 0.027 0.953 5.7 19 ± 5 15 21 0.031 1.095 5.7 a 17 22 0.024 0.838 3.6 15 ± 2 21 23 0.030 1.029 7.1 11 ± 3 13 24 0.029 1.015 7 17 ± 3 13 25 0.031 1.071 7.4 13 ± 4 13 26 0.031 1.085 4.4 21 ± 3 22 27 0.029 0.998 3.2 16 ± 5 28 28 0.021 0.733 3.6 13 18 29 0.024 0.848 3.3 14 23 EXAMPLES 30-42 [0077] In Examples 30 to 42, two-layer coatings were applied by on line CVD to a float glass ribbon across the full width of approximately 132 inches (3.35 m) in the float bath during the float glass production process. The apparatus used to deposit the coating is illustrated in FIG. 2. The float bath atmosphere comprised nitrogen and 2% by volume hydrogen. Bath pressure was 0.15 mbar. [0078] The two layer coating consisted of a silicon oxide layer deposited first on the float glass ribbon and titanium oxide layer deposited on to the silicon oxide layer. The precursor chemistry of the gaseous mixtures used to deposit the coating was the same as that used in Examples 1-15. The temperature of deposition of the layers was varied by using different coaters 27 , 28 , 29 or 30 (referring to FIG. 2). Coater 27 located nearest the hearth being hottest and coater 30 being located nearest the lehr being coolest. In Examples 30-33 and 42 two coaters ( 28 and 29 in Examples 30-33 and coaters 27 and 28 in Example 42) were used to deposit the silicon oxide coating. The benefit of using two coaters to deposit the silicon oxide layer is that longer production run times are possible. [0079] The gaseous mixture used to deposit the silicon oxide layer for Examples 30 to 41 consisted of the following gases at the following flow rates: helium (250 l/min), nitrogen (285 l/min), monosilane (2.5 l/min), ethylene (15 l/min) and oxygen (10 l/min). For Example 42, the same gases and flow rates were used except for monosilane (2.3 l/min), ethylene (13.8 l/min) and oxygen (9.2 l/min). Where two coaters were used to deposit the silicon oxide layer in Examples 30 to 42, the above flow rates were used for each coater. [0080] In Examples 30-42 the deposition temperatures (i.e. the temperature of the float glass ribbon under the coater responding to each of the coaters 27 - 30 ) was as indicated in Table 7. The temperatures in Table 7 have an uncertainty of about ±50° F. (±28° C.). The extraction for each coater was at approximately 2 mbar. TABLE 7 Coater Approx. Temperature of Glass Ribbon 27 1330° F. (721° C.) 28 1275° F. (690° C.) 29 1250° F. (677° C.) 30 1150° F. (621° C.) [0081] Titanium tetrachloride (TiCl 4 ) and ethyl acetate were entrained in separate nitrogen/helium carrier gas streams. For the evaporation of TiCl 4 a thin film evaporator was used. The liquid TiCl 4 was held in a pressurised container (head pressure approx 5 psi). This was used to deliver the liquid to a metering pump and Coriolis force flow measurement system. The metered flow of the precursor was then fed into a thin film evaporator at a temperature of 110° F. (43° C.). The TiCl 4 was then entrained in the carrier gas (helium) and delivered to the mixing point down lines held at 250° F. (121° C.). The ethyl acetate was delivered in a similar way. The liquid ethyl acetate was held in a pressurised container (head pressure approx 5 psi). This was used to deliver the liquid to a metering pump and Coriolis force flow measurement system. The metered flow of the precursor was then fed into a thin film evaporator at a temperature of 268° F. (131° C.). The evaporated ethyl acetate was then entrained in the carrier gas (helium/nitrogen mixture) and delivered to the mixing point down lines held at approximately 250° F. (121° C.). [0082] The TiCl 4 and ethyl acetate gas streams were combined to form the gaseous mixture used to deposit the titanium oxide layer. This mixing point was just prior to the coater. [0083] The line speed of the float glass ribbon, the temperature of deposition of the silicon oxide and temperature of deposition of the titanium oxide layers and the flow rates of the He/N 2 bulk carrier gas and the flow rate of TiCl 4 and ethyl acetate are described for Examples 30-42 in Table 8. [0084] The coated float glass ribbon was cooled and cut and the optical properties and photocatalytic activity of samples determined. Table 9 describes the haze, optical properties in transmission and reflection (visible percent transmission/reflection and color co-ordinates using the LAB system) of the samples. The coated glasses were subjected to abrasion testing in accordance with BS EN 1096, in which a sample of size 300 mm×300 mm is fixed rigidly, at the four comers, to the test bed ensuring that no movement of the sample is possible. An unused felt pad cut to the dimensions stated in the standard (BS EN 1096 Part 2 (1999)) is then mounted in the test finger and the finger lowered to the glass surface. A load pressure on the test finger of 4N is then set and the test started. The finger is allowed to reciprocate across the sample for 500 strokes at a speed of 60 strokes/min±6 strokes/min. Upon completion of this abrasion the sample is removed and inspected optically and in terms of photocatalytic activity. The sample is deemed to have passed the test if the abrasion results in a change in transmission of no more than ±5% when measured at 550 nm and the coated substrate remains photocatalytically active which means that, after the test irradiation by UV light for 2 hours reduces the static water contact angle to below 15°. [0085] The glasses were also subjected to a humidity cycling test in which the coating is subjected to a temperature cycle of 35° C. to 75° C. to 35° C. in 4 hours at near 100% relative humidity. [0086] The static water contact angle of the coated glasses as produced and after 130 minutes of UV irradiation (UVA 351 mm lamp at approximately 32 W/m 2 ) and after 300, 500 and/or 1000 strokes of the European standard abrasion test described in Table 10. The contact angle of the abraded samples was determined after irradiation for 2 hours. [0087] The samples deposited at the higher temperatures of 1330-1250° F. (721° C. to 677° C.) were photocatalytically active even after 1000 European standard abrasion strokes or after 200 humidity cycles. The photocatalytic activity in terms of t 90% of the coated glasses as produced and after 300, 500 and/or 1000 strokes of the European standard abrasion test and after 200 humidity testing cycles are described in Table 11. In Table 11, the term Active indicates that the coated glasses were photocatalytically active but that t 90% was not determined. [0088] The photocatalytically active coated substrates of the invention have been illustrated and described in their preferred embodiments, however, it will be appreciated that modifications to these embodiments can be made without departing from the spirit and scope of the attached claims. TABLE 8 Titanium Oxide Layer Flow Rates of Precursors Line-Speed Silica layer Deposition Deposition Flow Rates of Carrier Gases Ethyl Acetate Example (m/min) Temperature/° C. Temperature/° C. He L/min N 2 L/min TiCl 4 cc/min cc/min 30 10.9 690 & 677 621 300 300 6.3 16.3 31 10.9 690 & 677 621 300 300 6.3 16.3 32 10.9 690 & 677 621 300 300 6.3 16.3 33 10.9 690 & 677 621 300 300 6.3 16.3 34 10.9 690 621 300 300 6 16 35 10.9 690 621 300 300 6 16 36 10.9 690 621 300 300 6 16 37 10.9 690 677 300 300 5.5 14.7 38 10.9 690 677 300 300 5.5 14.7 39 10.9 690 677 300 300 5.5 14.7 40 10.9 690 677 300 300 5.5 14.7 41 6.5 721 690 300 300 4 10.7 42 12.1 721 & 690 677 300 300 9.5 25.4 [0089] [0089] TABLE 9 Film Side Reflection Transmission Haze Example R(%) L* a b T(%) L* a b (%) 30 14.2 44.5 0.3 −10.3 84.3 93.6 −1.2 3.6 0.11 31 14.6 45.1 0.3 −10.4 84.5 93.7 −1.1 3.4 0.30 32 14.6 45.1 0.3 −10.5 84.3 93.6 −1.1 3.6 0.12 33 13.8 44.0 0.3 −9.8 85.5 94.1 −1.1 2.9 0.15 34 13.6 43.7 0.1 −8.7 84.8 93.8 −1.1 2.7 0.12 35 13.8 43.9 0.1 −8.8 85.4 94.1 −1.1 2.6 0.11 36 12.9 42.6 0.1 −8.2 85.8 94.2 −1.1 2.5 0.14 37 12.6 42.2 0.1 −7.9 86.1 94.4 −1.1 2.3 0.08 38 11.9 41.0 0.1 −6.9 87.1 94.8 −1.1 1.7 0.07 39 11.5 40.4 0.0 −6.5 87.2 94.8 −1.1 1.8 0.10 40 11.6 40.6 0.0 −6.6 86.9 94.7 −1.1 1.8 0.08 41 a a a a a a a a a 42 14   44.3 0.1 −9.9 84.8 93.8 −1.1 3.1 0.14 [0090] [0090] TABLE 10 Static Water Contact Angle (°) after Number of Abrasion Strokes 0 (after irradiation Example 0 130 min UV) 300 500 1000 30 2.3 3.3 failed 31 2.0 3.2 failed 32 a a failed 33 2.0 3.2 failed 34 a a failed 35 2.0 3.2 failed 36 2.1 3.4 failed 37 2.2 3.3 <15 38 2.0 3.1 <15 39 1.9 3.1 <15 40 2.2 3.2 <15 41 7.8 7.8 10.1 42 4.7-5.3 4.7-5.3 5.6-9.8 [0091] [0091] TABLE 11 t 90% (min) after Number of Abrasion Strokes t 90% (min) after 200 Example 0 300 500 1000 Humidity Cycles 30 7.5 failed failed 31 18.5 failed failed 32 8.5 failed failed 33 8 failed failed 34 21 failed failed 35 4 failed failed 36 8.5 failed failed 37 15.5 Ca. 2160 Active 38 18.5 Ca. 2160 Active 39 17 Ca. 2160 Active 40 18.5 Ca. 2160 Active 41 a ca. 2160 Active 42 45 2800 Active
A coated substrate, especially a glass substrate, such coated substrate having high photocatalytic activity and low visible light reflection as well as being highly abrasion resistant. Preferably, the coating is a titanium oxide coating, the photolytic activity is greater than 5×10 −3 cm −1 min −1 , and coating side visible light reflection is 35% or lower.
2
FIELD OF THE INVENTION [0001] The present invention relates to a preparation of perylene or perinone pigments using certain metallic catalysts. BACKGROUND OF THE INVENTION [0002] Current technologies involving the condensation of amines with perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) require high-boiling point solvents, such as nitrobenzene, trichlorobenzene, N-methylpyrrolidone, benzyl alcohol, lauryl alcohol, quinoline, and the like (e.g., GB 859,288; and WO 2005/078023), and high temperatures, as high as 150°-250° C. (e.g., U.S. Pat. No. 5,225,307; WO 2005/078023; and GB 859,288), to form the condensation products. To lower the reaction temperature, the reaction may be conducted under pressure using a lower boiling point solvent, such as water, chlorobenzenes, and the like. Also, certain catalysts can be used to lower the reaction temperature. [0003] Commonly used catalysts for the condensation reactions include zinc salts, such as anhydrous zinc chloride, anhydrous zinc acetate, zinc oxide, and the like, and acids, such as sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid, p-toluene sulfonic acid, and the like (see, for example, U.S. Pat. No. 4,587,189; and GB 859,288). When zinc salts are used for the condensation reactions, it is necessary to use a large amount of the zinc salts in order to drive the reaction at a reasonable rate and to attain high yields, for example, above 90%. This typically results in the formation of high amount of insoluble sludge in the reaction mixture. To avoid this, the zinc salts need to be highly diluted with a solvent. The lower the dilutions of zinc salt, the more the formation of insoluble sludge, and the harder the agitation and, therefore, the heat transfer during the process. The high amount of insoluble sludge moreover renders the removal thereof from the reaction vessel difficult. [0004] Other solvents such as aluminum chloride and p-toluene sulfonic acid (e.g., WO 2005/078023) have been used to solve the problem, but yields are low and not satisfactory. In addition, the requirement for high levels of zinc salts also leads to the production of the high amount of hazardous wastes containing heavy metal zinc. Thus, the need exists for an alternative catalyst to resolve these problems encountered in condensation reactions. SUMMARY OF THE INVENTION [0005] The present invention provides a method for preparing a condensation product using certain metallic catalysts. In particular, the present invention provides a method for preparing perylene and perinone pigments by condensation reactions between amines and perylene or naphthalene tetracarboxylic acid or their anhydrides or imides in the presence of certain metallic catalysts, such as ammonium molybdate, molybdenum oxide, and carbonyl compounds of molybdenum, titanium or iron (collectively “metal carbonyls”). The use of these catalysts is advantageous as it requires a small amount of the catalyst compared to typical catalysts conventionally used for the production of perylene or perinone pigments, and yet attain high yields comparable to the conventional catalysts. Furthermore, the condensation reactions using these catalysts produce less amount of insoluble sludge, thereby making the production process much easier and the disposal of the waste water easier and more economical. [0006] In one embodiment, the starting materials for the condensation reaction are an amine and a compound selected from the group consisting of a perylene-3,4,9,10-tetracarboxylic acid, its anhydrides and imides (collectively “PTCDA”), optionally substituted, to obtain perylenes. In another embodiment, the starting materials for the condensation reaction are an amine and a compound selected from the group consisting of a 1,4,5,8-naphthalene-tetracarboxylic acid, its anhydrides and imides (collectively “NTCDA”), optionally substituted, to obtain perinones. In both embodiments, the reactant may be a monoanhydride, dianhydride, or monoimide monoanhydride. The imide optional substituents include alkyl and aromatic groups. The amine to be used in the present method can be primary aliphatic or aromatic monoamines or diamines. [0007] Thus, the present invention provides a method for preparing a condensation product comprising reacting a PTCDA or NTCDA and an amine in the presence of a catalyst selected from the group consisting of ammonium molybdate, molybdenum oxide and the aforementioned metal carbonyls, and a solvent. In a specific embodiment, the condensation product is a perylene pigment. In another specific embodiment, the condensation product is a perinone pigment. DETAILED DESCRIPTION OF THE INVENTION [0008] The present invention generally relates to a method for preparing a condensation product between PCTDA or NTCDA and an amine using certain metallic catalysts. The present invention is based, partly, on the discovery that the use of certain catalysts for a condensation reaction between o-phenylene diamine and PTCDA results in more efficient and economical production of the condensation products, i.e., o-phenylenediamine pigments. [0009] Previously, problems were encountered when an attempt was made, for economical purposes, to reduce the amount of the solvent (e.g., N-methylpyrrolidone) in the condensation reaction using zinc salts as catalysts. The reduction of the amount of the solvent to 6-7 parts based on the amount of PTCDA resulted in the formation of a large amount of insoluble sludge, which hindered the agitation and the removal of the reaction mass from the vessel during the process. [0010] A surprising result was obtained by replacing zinc salts with, for instance, ammonium molybdate, because the condensation reaction required much less amount of ammonium molybdate than that of zinc salts and yet achieved the same yield as the latter with more ease and efficiency. Although the ammonium molybdate is more expensive than zinc salts, the overall cost for the condensation reaction using the former is about the same as using the latter. Furthermore, the use of ammonium molybdate also results in the reduction of the wastes containing hazardous metals and is beneficial for the environment. [0011] Thus, the present invention provides a method for preparing a condensation product comprising reacting PTCDA or NTCDA with an amine in the presence of a specific metallic catalyst and an appropriate solvent. The condensation product is a perylene pigment or a perinone pigment depending on the starting materials. [0012] The condensation reaction can be carried out under typical conditions well known in the art, except for using a specific metallic catalyst in the place of conventional catalysts and the type and amount of solvent. [0013] The starting materials for preparing perylene pigments include a perylene-3,4,9,10-tetracarboxylic acid or its monoanhydride (i.e., perylene-3,4-dicarobxylic acid monoanhydride) or dianhydride (collectively “PTCDA”), or a perylene monoimide monoanhydride, whose monoimide portion being optionally substituted with a hydrogen, or an alkyl or aromatic group, and derivatives thereof, including, but are not limited to, halogen derivatives, such as dichloroperylene-3,4,9,10-tetracarboxylic anhydride; tetrachloroperylene-3,4,9,10-tetracarboxylic anhydride; and bromoperylene-3,4,9,10-tetracarboxylic anhydride, and the like, and corresponding sulfonated or nitrated PTCDA or perylene monoimide monoanhydride, and the like. [0014] The starting materials for preparing perinone pigments include a 1,4,5,8-naphthalene-tetracarboxylic acid or its mono- (i.e., 1,8-naphthalene-dicarboxylic acid monoanhydride) or dianhydride (collectively “NTCDA”), or a naphthalene monoimide monoanhydride, whose monoimide portion being optionally substituted with a hydrogen, or an alkyl or aromatic group, and derivatives thereof, including, but are not limited to, halogenated, sulfonated, or nitrated NTCDA or naphthalene monoimide monoanhydride. [0015] Suitable amines to be used in the condensation reaction to obtain perylene or perinone pigments include, but not by way of limitation, primary aliphatic monoamines, including alkylamine and alcoholamine, such as methylamine, ethanolamine, and the like; primary aliphatic diamines, such as 1,4-diaminobutane, ethylenediamine, trimethylenediamine, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, and the like; primary aromatic monoamines, such as 2-methylaminopyridine, 3-methylaminopyridine, 5-methylpyridin-3-ylamine, 2-amino-4-methyl-pyridine, 2-amino-3-methyl-pyridine, 2-amino-6-methyl-pyridine, aniline, dimethylanilines, p-toluidine and the like; primary aromatic diamines, such as benzidine, o-phenylenediamine, meta-phenylenediamine, para-phenylenediamine, 1,2-diamino-4-methylbenzene, 1,2-diamino-4-methoxybenzene, 1,2-diamino-4-chlorbenzene, 2,3-diaminonaphthalene, 2,3-diamino pyridine, 3,4-diamino pyridine, 5,6-diamino pyrimidene, 9,10-diamino phenanthrene, 1,8-diamino naphthalene, 4,4′-oxydianiline, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 2,4′-diaminodiphenylether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylsulphone, 3,3′-diaminodiphenylsulphone, 4,4′-diaminodiphenylethane-1,1, 4,4′-diaminodiphenylpropane-2,2, 4,4′-bis(4-aminophenoxy)-diphenylsulphone, and the like. [0016] The molar ratio of an amine and PTCDA, NTCDA, or monoimide monoanhydride thereof, is typically about 2:1 to about 10:1, preferably about 2:1 to about 3:1, and most preferably about 2.2:1 to about 2.4:1. [0017] The catalyst to be used in the present invention can be selected from the group consisting of ammonium molybdate [(NH 4 ) 2 MoO 4 ], molybdenum oxide (MoO 2 ), and metal carbonyls. The metal carbonyls suitable for the present invention include, but are not limited to, hexacarbonylmolybdenum [Mo(CO) 6 ], carbonyl titanium [Ti(CO) 6 ], iron carbonyls, such as [Fe(CO) ] and [Fe 2 (CO) 9 ], and the like. These catalysts are commercially available. The amount of the catalyst in the present method should be at least about 0.01 mole, based on 1 mole of PTCDA or NTCDA, and is only limited by cost and the amount of the resulting insoluble sludge generated in the reaction mixture. Preferably the amount of the catalyst is in the range of about 0.01 to about 1 mole, more preferably in the range of about 0.02 to about 0.5 mole, and most preferably in the range of about 0.03 to about 0.1 mole, based on 1 mole of PTCDA or NTCDA. [0018] The solvent for the condensation reaction can be any solvent typically used for the reaction and include, but are not limited to, high-boiling point solvents, such as nitrobenzene, trichlorobenzene, N-methylpyrrolidone, cyclo-hexylpyrrolidone, benzyl alcohol, lauryl alcohol, quinoline, dimethylsulfoxide, dimethylformimide, and the like; and low-boiling point solvents, such as chlorobenzene, glacial acetic acid, water, and the like. The solvent can be reduced or replaced by use of an excess amount of the amine to be reacted with PTCDA, NTCDA, or monoimide monoanhydride thereof. In general, about 1 to about 20 parts by weight, preferably about 5 to about 15 parts by weight, and most preferably about 6 to about 10 parts by weight, of the solvent for each part of PTCDA or NTCDA have been found particularly advantageous to use. [0019] The condensation reaction to prepare a perylene pigment can be carried out at a temperature determined by the type of solvent used but, in general, in the range of about 140° C. to about 300° C., preferably about 180° C. to about 225° C. For preparing a perinone pigment, the reaction temperature can be in the range of about 80° C. to about 300° C., preferably about 90° C. to about 220° C. The reaction time depends on the reaction temperature, but typically is several minutes at the highest temperatures to several hours at the lower temperatures. [0020] Upon completion of the reaction, typically, the reaction mixture is cooled and filtered to remove the solvent. The resulting presscake is washed with the solvent. [0021] The thus prepared condensation product can be used as crude pigments that have not been modified after chemical synthesis, but also can be modified by, for example, halogenation, sulfonation, or nitration. Furthermore, the pigments can be conditioned or otherwise treated by any methods well known in the art. Such conditioning or treatment may include, but not by way of limitation, various types of milling, including milling with bead mill, media mill, three roll mill, and the like. Although the particular milling apparatus is generally not critical, suitable mills include horizontal mills (for example, Eiger mills, Netzsch mills, and Super mills), vertical mills, ball mills, three roll mills, attritors, vibratory mills, and the like containing various grinding media. Suitable grinding media include salt; sand; glass beads, such as barium titanate, soda lime, or borosilicate; ceramic beads, such as zirconia, zirconium silicate, and alumina beads; metal beads, such as stainless steel, carbon steel, and tungsten carbide beads; and so forth. [0022] Other suitable conditioning or treatment methods well known in the art may be also used to prepare a pigment prepared by the present process; such conditioning or treatment methods include acid pasting and mixing (for example, by stirring) with a conditioning solvent mixture comprising water and an aromatic carboxylic acid ester, optionally in the presence of a particle size dispersant, such as homopolymers or copolymers of ethylenically unsaturated monomers, such as (meth)acrylic acids or corresponding alkyl or hydroxyalkyl esters, polyester, polyurethane, styrene-maleic anhydride copolymers (e.g., SMA® Resins), various forms of rosin or polymerized rosin, alkali metal salts of sulfosuccinate esters, alkylene oxide polymers or copolymers, and so forth. [0023] The conditioned or otherwise treated pigment can be collected as a presscake by methods known in the art, for example, by filtration and centrifugation, but most preferably by filtration. The presscake obtained can be dried using conventional drying methods, such as spray drying, tray drying, drum drying, and the like. EXAMPLES [0024] The following examples illustrate the condensation reaction according to the method provided by the present invention and those according to the conventional method. All parts and percentages are by weight and temperatures are by centigrade (° C.), unless otherwise indicated. These examples should not be construed as limiting. Comparative Example 1 [0025] To a glass reaction flask equipped with an agitator, thermometer, Dean Stark trap and condenser, were added 13 parts N-methylpyrrolidone (NMP) based on the amount of PTCDA, 0.23 mole perylene tetracarboxylic dianhydride (PTCDA) (98% purity), 0.53 mole o-phenylene diamine, and 0.01 mole zinc sulfate monohydrate. With agitation, the reaction mass was heated to 200° C. and held 21 hours at 200-2° C. The reaction mixture was cooled and filtered from the solvent. The presscake was washed with NMP and then purified by heating to 90° in dilute sulfuric acid. After filtering and washing, the cake was reslurried in diluted caustic potash and heated to 90° C. The slurry was filtered and washed. This cake was reslurried and the pH was adjusted to neutral with dilute caustic potash. The slurry was filtered, washed, and dried at 70° C. The yield was 85.9% at 92.3% purity and an overall yield was 79.2%. Comparative Example 2 [0026] Comparative Example 1 was repeated using 0.12 mole of zinc sulfate monohydrate. The yield was 96.7% with a purity of 94.4% and an overall yield was 91.2%. Example 1 [0027] Comparative Example 1 was repeated except that 0.007 mole ammonium molybdate was used as the catalyst instead of the zinc salt. The yield was 96.2% at 96.6% purity and an overall yield was 92.9%. Example 2 [0028] Comparative Example 1 was repeated using 0.037 mole perylene tetracarboxylic dianhydride, 0.271 mole p-toluidine, and 0.003 mole ammonium molybdate. The as-is yield was 19.2 grams or 89.8% yield. [0029] The results are summarized in Table 1. [0000] TABLE 1 Catalyst/ PTCDA PTCDA As is Pure Example (moles) Catalyst Molar ratio Yield % Yield % Comparative 1 ZnSO 4 •H 2 0 0.04 85.9 79.02 Example 1 Comparative 1 ZnSO 4 •H 2 0 0.52 96.7 91.2 Example 2 Example 3 1 (NH 4 ) 2 MoO 4 0.03 96.2 92.9 Example 4 1 (NH 4 ) 2 MoO 4 0.08 89.8 — Example 3 [0030] Example 1 is repeated using 0.01 mole molybdenum oxide in place of the ammonium molybdate. Example 4 [0031] Example 1 is repeated using 0.02 moles hexacarbonylmolybdenum in place of the ammonium molybdate. Example 5 [0032] Example 2 is repeated using 0.003 moles of carbonyl titanium in place of the ammonium molybdate. Example 6 [0033] Example 2 is repeated using 0.004 moles of carbonyl iron [Fe(CO) 5 ] in place of the ammonium molybdate.
A method for preparing a perylene pigment or perinone pigment involves a condensation reaction between perylene tetracarboxylic acid or naphthalene tetracarboxylic acid, or anhydrides or imides thereof, and amines in the presence of certain metal catalysts, such as ammonium molybdate, molybdenum oxide, and metal carbonyls, such as hexacarbonylmolybdenum, titanium carbonyl, iron carbonyls, and the like. The use of these catalysts provides various advantages, including the reduction of the amount of the catalyst, while achieves high yields, the lowering of reaction temperatures, and the reduction of insoluble sludge in the reaction mixture, thereby making the reaction operation easier and reducing the amounts of hazardous wastes containing heavy metals.
2
This is a divisional of co-pending application Ser. No. 784,739, filed on 10/7/85, now U.S. Pat. No. 4,654,509, issued 1/30/87. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates generally to epitaxial deposition of materials on a substrate and, more particularly, to epitaxial deposition of materials on a substrate in an axially symmetric configuration. Because of the axially symmetric configuration, the deposition chamber must be specifically designed to provide for uniform heating of substrate. 2. Description of the Related Art It is known that the quality of the deposited material in an epitaxial deposition chamber can depend, among other things, on the uniformity of the temperature of the substrate and the uniformity of deposition material in the carrier gas. Recently, the advantages of epitaxial deposition in an axially symmetric configuration have been identified. The full advantage of this configuration in a commercial environment can be realized only with rapid, uniform heating of the substrate. In the prior art, massive susceptors have been heated by arrays of linear lamps or by RF fields, with temperature uniformity provided in part by the large thermal mass and high thermal conductivity of a susceptor associated with the substrate. However, the high thermal mass of the susceptor provides a thermal inertia that prolongs the heating and cooling cycles associated with the epitaxial deposition process. A need has therefore been felt for apparatus and for a method that can rapidly and uniformly heat a wafer and, more particularly, can uniformly heat a susceptor and/or wafer of low thermal mass in an axially symmetric environment. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an improved apparatus and method for use with epitaxial deposition process. It is another object of the present invention to provide heating apparatus and method in an epitaxial deposition environment utilizing an axially symmetric gas flow. It is yet another object of the present invention to provide method and apparatus for uniform heating of a semiconductor substrate in a epitaxial deposition apparatus in which the gas flow and the substrate have axial symmetry. It is a more particular object of the present invention to provide uniform heating of a semiconductor substate and associated susceptor combination utilizing heating lamps above and below the combination, wherein the two sets of heat lamps are at substantially right angles to each other. It is yet another object of the present invention to provide a uniform heating of the semiconductor substrate-susceptor combination using a first chamber having a group of heating lamps and a second chamber in which the reflectivity of the chamber on the reverse side of the combination has a predetermined configuration and includes at least two regions with different reflectivity coefficients. It is still another object of the present invention to provide a substrate-susceptor combination enclosed by two generally square heating chambers. It is a more particular object of the present invention to enclose a substrate-susceptor combination with two generally square heating chambers, the heating chambers having heat lamps with radiation focused by parabolic reflectors positioned at approximately 90° with respect to heat lamps in the other chamber. It is another particular object of the present invention to enclose a substrate-susceptor combination with two chambers having radiation from heat lamps focused by parabolic reflectors, the heat lamps in each chamber positioned at approximately 90° to the heat lamps in the other chamber, wherein a plurality of interior heat lamps in at least one chamber have a flat reflecting surface associated therewith. The aforementioned and other features are accomplished, according to the present invention, by an epitaxial reactor device generally comprised of an upper chamber and a lower chamber substantially enclosing a substrate-susceptor combination. In the upper chamber, a series of heat lamps extend through the interior of the chamber generating at least a portion of the thermal energy for the semiconductor substrate-susceptor combination. The heat lamps are generally parallel and can be equally spaced, and when a circular chamber is used, can have varying portions of the lamps extending through the circular chamber. The reflectivity of the chamber walls is chosen to complement the heat lamps and to provide a uniform distribution of heating radiation within the reactor. According to one embodiment of the invention, a circular lower chamber of the reactor is designed similarly to a circular upper portion. However, the heat lamps in the lower chamber are positioned generally at right angles to the heat lamps of the upper chamber. According to another second embodiment of the present invention, a lower chamber of the reactor comprises a circular chamber in which reflected energy from a circular upper chamber is used to provide thermal energy to the lower portion of the substrate-susceptor combination. A center portion of the lower chamber wall has a reflectivity chosen to provide uniform heating of the substrate-susceptor combination by having reflectivity different from that of the remainder of the chamber. According to yet another embodiment of the present invention, heat lamps in upper and lower chambers have parabolic reflectors associated therewith for providing generally parallel radiation impinging on the substrate-susceptor combination. In this embodiment, the chambers preferably have a square configuration. According to yet another embodiment, at least one of the chambers can have the parabolic reflectors replaced by a flat reflecting surface for selected heat lamps. The walls of the reflectors have deposited thereon a suitable reflecting medium. To provide further the uniformity of heating of the susceptor-substrate combination, the heating lamps can have a higher excitation energy or a smaller inter-lamp spacing, as the distance from the center lamps is increased to compensate, for example, for heat losses through ports necessary, for example, to introduce gas components into the reactor. These and other features of the present invention will be understood by reading the following description along with the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing the flow of gas toward a substrate to produce an axially symmetric flow. FIG. 2 is a perspective view of one chamber of the reactor having heating lamps passing therethrough. FIG. 3 is a schematic cross-section diagram of a configuration for uniformly heating a substrate-susceptor combination utilizing heat lamps above and below the combination. FIG. 4 is a schematic cross-section diagram showing the configuration in which a substrate-susceptor combination is heated by a group of lamps above the combination and is heated by reflected energy from the other side of the combination. FIG. 5 is a perspective view of a different configuration of a heating chamber with a heating lamp extending therethrough. FIG. 6 is a schematic cross-section diagram showing the configuration in which a substrate susceptor combination is heated by a plurality of lamps with associated parabolic and planar reflectors. DESCRIPTION OF THE PREFERRED EMBODIMENT Detailed Description of the Figures Referring now to FIG. 1, the general configuration for axially symmetric epitaxial deposition is shown. In the preferred embodiment, the technique consists of projecting a gas carrying the deposition materials with a uniform velocity perpendicular to the substrate 10 and susceptor 15 combination. With apparatus not shown, the gas is conducted from the edge of the circular substrate-susceptor combination, and the result is a configuration for a chemical reaction generally referred to as the stagnation point flow configuration. By stagnation point flow is meant a flow of gas toward a circular substrate that has a uniform temperature and a uniform component of velocity toward the substrate at a predetermined distance. Referring to FIG. 2, a perspective view of one chamber 49 of a reactor is shown with the heating lamps 50 passing therethrough. In this embodiment, the heating chamber 49 is circular. Referring next to FIG. 3, the general structure of the reactor for heating the substrate 10 and the associated susceptor 15 is shown. The apparatus shown in this cross-section is not complete. For example, the apparatus for generating the uniform flow of gas toward the substrate is missing as well as structures necessary to support the substrate. However, the essential portions of the apparatus relating to heating of the susceptor 15 and the substrate 10 are shown. The reactor is comprised of two circular chambers 49, one above and one below the substrate-susceptor combination. The purpose of the reactor configuration is to provide an environment that, to the extent possible, provides uniform radiation for the substrate and the associated susceptor. When the radiation is uniform, the temperature of the substrate-susceptor combination will be uniform to the extent that thermal losses are also uniform. The top portion has a circular surface area with a cylindrical side portion. Inserted through the cylinder portion of the chamber 49 are a series of parallel heat lamps 50. The surface of the upper chamber is coated with a diffuse reflecting material, such as a gold plating, and the sides of the chamber are coated with a diffuse or a specular reflecting material. The bottom chamber 49, in this embodiment, is similar to the upper chamber with the exception that the lamps 50 are positioned generally at right angles to the lamps in the upper chamber. The bottom and the side surfaces of the chamber 60 have coatings similar to those described for the upper chamber. Openings 71 between the two chambers, used for introducing gas into the cavity as well as other functions, is important because this region is thermally cool, and tends to produce non-uniform heat losses from the circumference of the substrate. Referring next to FIG. 4, the upper chamber 49 of this embodiment has a similar configuration to the upper chamber shown in the embodiment in FIG. 2. The lamps 50 of the upper chamber are present, the diffuse reflecting material 52 is coated on the upper surface, and the side surfaces can have either a diffuse or a specular reflecting coating 53. Below the upper chamber is a second chamber 61. Chamber 61 has a surface 54 that is coated on the side and a portion of the bottom floor with a diffuse reflector material having, for example, reflectivity of the order of 0.95. In the center of the circular floor portion of the chamber, a circular area 55 has a diffuse reflective coating with a reflectivity lower than that of the other portions, the reflectivity being of the order of 0.8 in the specific configuration described. The lower chamber 61 is used to heat the substrate-susceptor combination using radiation from the upper chamber. Again, aperture 71 is present resulting in a non-uniform radiation field. Referring next to FIG. 5, a different configuration for for the heating chambers is shown. In this embodiment, the chamber 49 is generally square in nature. Again, heating lamps 50 are inserted therethrough to provide for radiant heating of the substrate-susceptor combination. This configuration has the disadvantage that the symmetry of the substrate-susceptor combination is not present in the chamber configuration. Despite the lack of axial symmetry, it is found that this configuration can result in a uniform substrate-susceptor combination heating. Referring to FIG. 6, an embodiment for heating a substrate-susceptor combination that employs the chamber configuration of FIG. 5. In addition, the heating lamps 50 have the emitted radiation reflected by parabolic reflectors 53. In practice, the parabolic reflectors can be approximated by other geometric surface configurations. The parabolic reflector causes the reflected radiation to be parallel thereby increasing the uniformity of the radiation impinging on selected areas the substrate-susceptor combination. As with the configuration shown in FIG. 3, the heating lamps in the lower chamber are generally disposed at right angles to the heating lamps of the upper chamber to average some of the structure imposed on the radiation impinging on the substrate-susceptor combination because of the use of discrete heat sources. Thermal aperture 71 is present as in previous configurations and compromises the uniformity of the radiation field. As shown in the upper chamber, the parabolic reflectors can be replaced by a plane for interior heat lamps of the chamber. In addition, the exterior parabolic reflector of the group of reflectors can be implemented so that the reflectors can be tilted, thereby providing additional control for environment of the substrate-susceptor combination. Operation of the Preferred Embodiment The function of the chambers of the epitaxial reactor is to provide, from the perspective of the substrate and associated susceptor, a cavity having uniform radiation field for heating the substrate-susceptor combination. Because of the necessity for introducing and removing the gas with the deposition materials, as well as the necessity for introducing and removing the substrate-susceptor combination itself, the reactor cannot have a truly uniform source of radiation because of requisite apertures for accomplishing the associated functions. The aperture 71 can therefore be critical in any effort to provide a uniform temperature environment for the substrate/susceptor combination because the thermal losses through the aperture cool the combination non-uniformity. However, the regions that do not contain a source of radiation can be made relatively small. The regions that lack a source of radiation are closest to the circumference of the substrate-susceptor combination. In order to correct for this non-uniformity in the radiation field, the end lamps of the array 50 can be operated at elevated power levels producing a higher temperature, and therefore higher radiation intensity, than the other heating lamps. This additional heating can compensate for the otherwise lower radiation intensity at the circumference of the substrate. To further provide axially uniform radiation, the heat lamps in the bottom chamber are placed at a large angle, approximately 90°, with respect to the lamps in the upper chamber. In addition, to provide more uniform thermal environment, a diffuse reflector is deposited on the various portions of the chamber other than the parabolic reflectors to simulate as nearly as possible a constant temperature region as viewed from any region of the substrate. In addition, by apparatus not shown, the substrate-susceptor combination can be rotated to further average any departures from the observance of a uniform temperature environment for the substrate-susceptor combination. Referring once again to FIG. 4, only the upper chamber is provided with a heat generating lamp configuration. In this embodiment, the lower chamber does not produce power directly, but reflects power from the upper heating chamber. It has been found by computer simulation that, in order to achieve a uniform temperature in this configuration, it is necessary to have a region 55 with an intermediate magnitude reflectivity. Region 55 causes the center of the substrate-susceptor combination to receive a lower intensity of reflected radiation compared with the circumference, thus compensating for the nonuniform radiation discussed previously. As indicated above, the areas 54 include a diffuse reflector with a reflectivity on the order of 0.95, while the area 55 includes a diffuse reflector with a reflectivity of about 0.8. The diameter of area 55 is approximately two-thirds the diameter of the susceptor-substrate combination. However, this relationship is a function of size of the substrate, distance between the substrate and the reflecting surface, and the other structural dimensions. It will be clear that additional thermal energy in the exterior regions of the chamber can be achieved by a higher density of lamps at the external region. In addition, the dimension of the chamber can be expanded so that the aperture 71 has a smaller influence on the non-uniform field experienced by the substrate/susceptor combination. The use of square heating chambers provides a situation where the corners of the heating chamber provide a larger effective chamber and can minimize the influence of aperture 71. It will be clear to those skilled in the art that various gases interacting with the substrate must generally be confined while flowing in the vicinity of the substrate. The confinement can be performed by materials such as quartz, that permit a large portion of the radiation to be transmitted therethrough. However, the properties of the quartz or other enclosing material, such as the absorption or emission characteristic, must be considered in determining the thermal environment of the substrate/susceptor combination. The above description is included to illustrate to operation of the preferred embodiment and is not meant to limit the scope of the invention. The scope of the invention is to be limited only by the following claims. From the above description, many variations will be apparent to those skilled in the art that would yet be encompassed by the spirit and scope of the invention.
An apparatus and method for heating a substrate and associated rotatable susceptor in an epitaxial deposition reactor with an axially symmetric gas flow carrying deposition material include at least one chamber having a plurality of heat lamps. The chamber is generally symmetric with respect to an axis of the substrate. The chamber walls are coated to reflect light from the heat lamps. The outermost heat lamps can be energized to produce a higher temperature than the centrally located lamps to compensate for regions of the reactor which provide access to the substrate and, therefore, promote thermal losses. The spacing of the heat lamps may be varied to compensate for thermal non-uniformity of the heating cavity. The substrate may be rotated, on the rotatable susceptor, to average the thermal environment to which the substrate is exposed.
2
BACKGROUND [0001] 1. Technical Field [0002] This disclosure relates in general to step-down DC-DC switching converters and in particular to self powering techniques of the control circuits of the converter through an internal linear voltage regulator that is connected to the output voltage node of the converter, disconnecting it from the input voltage node thereof, in order to reduce power absorption. [0003] 2. Description of the Related Art [0004] By using the output voltage of the converter itself for supplying the controller of a power switch adapted to intermittently transfer electrical power from the input node to the output node and an external electrical load, power consumption within the controller may be reduced by a factor equal to the ratio between the output voltage and the input voltage. [0005] Possible solutions have been sought and circuital embodiments proposed for exploiting this opportunity when work conditions of the converter may consent it, but they have shortcomings of non-fully optimal management of the energy saving and/or of being applicable only to restricted types of applications. [0006] The document U.S. Pat. No. 5,528,132-A describes a method and related circuit wherein an internal voltage regulator of the DC-DC converter is coupled to the output voltage node when the output voltage becomes greater than the nominal (design) voltage of the linear regulator. The proposed circuit architecture is depicted in FIG. 1 . Clearly, the output voltage values must be compatible with the admissible maximum supply voltage of the internal circuitry on the chip. Wherever a broader variability of the output voltage (beyond said compatibility limit) is desired, this solution is inapplicable because of the risk of destroying the chip if the output voltage should overcome said safe operation voltage of the control circuit components. [0007] The published patent application US2006001409-A1, describes a circuit the architecture of which is depicted in FIG. 2 . The linear voltage regulator internal to the DC-DC converter has two distinct output stages, one connected to the input voltage node of the converter and the other to the output voltage node, which are selectively driven by the linear regulator depending on whether the output voltage is lower or greater than a reference voltage. Though compatible with any level of output voltage of the converter, the absorption of the linear regulator persists in every functioning condition. BRIEF SUMMARY [0008] One embodiment of the present disclosure overcomes the above-mentioned limitations and persisting inefficiencies of known solutions, allowing to power the controller of the power switch of the step-down converter for a broad range of values of the output voltage and achieves a greater energy-saving under low load conditions. [0009] One embodiment of the present disclosure is a method that includes defining two discrimination thresholds (VREF2/KDIV1, VREF2/KDIV2) of the output voltage (VOUT), which are compared to a reference voltage (VREF2), for generating two respective control signals (VCTRL1, VCTRL2), and identifying through logic combinations of the two control signals three distinctive operation regions of the converter upon the variation of electrical parameters, respectively identified by the logic combinations of the logic values of a pair of enable signals (EN1, EN2). [0010] The pair of enabling logic values is thus exploited for: [0011] enabling a first linear regulator LDO1 that regulates the supply voltage VCC of the controller by selectively connecting the input voltage VIN with an internal supply node VCC, disabling, and placing in a high impedance state an output stage DMOS2 of a second linear regulator LDO2 that regulates the supply voltage VCC by selectively connecting the output voltage VOUT with an output node of the second regulator LDO2, and disabling a connection device CONN_DEV that, when enabled, connects the output node of the second linear regulator LDO2 with the VCC node, as long as the output voltage is below a first one VREF2/KDIV1 of said two thresholds; [0012] disabling, and placing in a high impedance state an output stage DMOS1 of the first linear regulator LDO1, enabling the second linear regulator LDO2, and enabling the connection device CONN_DEV to connect the output node of the second linear regulator LDO2 with the VCC node, when the output voltage is greater than the second one VREF2/KDIV2 of said two thresholds; and [0013] disabling both linear regulators LDO1, LDO2 while forcing into a conduction state the output stage DMOS2 of said second linear regulator LDO2, which directly couples the output VOUT of the controller with the output node of the second regulator LDO2, and enabling the connection device CONN_DEV, connecting the controller output VOUT to the internal supply node VCC, when the output voltage is equal to or greater than the first threshold VREF2/KDIV1 and lower than or equal to the second one VREF2/KDIV2 of said two thresholds. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS [0014] FIG. 1 shows a known circuit diagram as previously commented. [0015] FIG. 2 shows another known circuit diagram as previously commented. [0016] FIG. 3 shows the general circuit architecture of the novel converter of this disclosure. [0017] FIG. 4 shows the functional block diagram of the circuit that analyzes the output voltage, on which the novel architecture is founded. [0018] FIG. 5 is a sample embodiment of the power supply circuit of the internal control circuitry of the converter. [0019] FIG. 6 shows a diagram representative of the way the novel mechanism of power supplying of the internal circuitry functions upon variations of the output voltage of the converter. DETAILED DESCRIPTION [0020] An exemplary embodiment of a step-down DC-DC switching converter 100 is depicted in the basic diagram of FIG. 3 . [0021] The switching converter 100 includes a functional circuit block, VOUT Monitoring 102 , for assessing the level of the output voltage VOUT of the step-down DC-DC converter 100 , relative to two distinct discrimination threshold values VREF2/KDIV1 and VREF2/KDIV2. Based on the level of the output voltage VOUT provided to a load LOAD, a control logic block 104 generates a set of signals adapted to selectively configure a supply circuit 106 in any of three different ways. The supply circuit 106 provides a regulated voltage supply VCC to power a common dedicated integrated circuit controller 108 and a driver 109 . The controller 108 includes a number of analog and digital circuits that are powered by the regulated voltage supply Vcc and generally implements a feedback control of the driver 109 , which drives the power switch HS Switch of the DC-DC converter 100 , in order to achieve efficient performance from the point of view of energy savings (i.e., reduction of power absorption from the source VIN, relative to known devices). [0022] A diagram of the VOUT-monitoring block 102 , is depicted in FIG. 4 , according to an embodiment. In this embodiment, a two-threshold, two output comparator 110 and a voltage divider 112 are used in order to generate a pair of control signals VCTRL1 and VCTRL2. The voltage divider 112 divides the output voltage VOUT of the converter according to divider ratios KDIV1 and KDIV2 to produce respective voltage values KDIV1·VOUT and KDIV2·VOUT for comparison with the reference voltage VREF2. Effectively, these comparisons are equivalent to comparing the output voltage VOUT with threshold values VREF2/KDIV1 and VREF2/KDIV2. The control logic block 104 produces first and second enabling logic signals EN1, EN2 according to the states of the control signals VCTRL1 and VCTRL2. [0023] A diagram of the supply circuit 106 is depicted in FIG. 5 , according to an embodiment. In this embodiment, the supply circuit 106 includes two distinct linear drop out (LDO) voltage regulators 114 , 116 , first and second resistors 118 , 120 , and a connecting device CONN_DEV. The output of the first LDO regulator 114 is coupled to an input of the connecting device CONN_DEV at a node configured to supply a regulated output voltage Vcc. The first and second resistors 118 , 120 are connected to each other at an intermediate node configured to supply a feedback voltage VFB that is proportional to the regulated output voltage Vcc. The connecting device CONN_DEV is connected in the electric current path between the second DMOS transistor 128 of the second LDO regulator 116 towards the output node configured to provide the regulated supply voltage VCC to the controller 108 . [0024] The LDO regulators 114 , 116 include respective differential amplifiers (error amplifiers) 122 , 124 and respective output stages implemented respectively by double-diffused metal-oxide-semiconductor (DMOS) transistors 126 , 128 . The differential amplifiers 122 , 124 have respective inverting and non-inverting inputs coupled to receive the reference voltage VREF1 and the feedback voltage VFB, respective supply terminals, and respective output terminals coupled respectively to the gates of the DMOS transistors 126 , 128 . The supply terminal of the first differential amplifier 122 is connected to the input voltage VIN and the supply terminal of the second differential amplifier 124 is connected to the output voltage VOUT. In addition, the first differential amplifier 122 has an enable terminal configured to receive a first enable signal EN1 from the control logic 104 and the second differential amplifier 124 has first and second enable terminals respectively configured to receive the first enable signal EN1 and a second enable signal EN2 from the control logic 104 . [0025] In the example considered, the connection device CONN_DEV includes a third DMOS transistor 130 and an NMOS transistor 132 . The third DMOS transistor 130 has a drain connected to the drain of the second DMOS transistor 128 of the output stage of the second LDO regulator 116 , and a source connected to the supply node VCC. The NMOS transistor 132 also has its drain connected to the drain of the second DMOS transistor 128 and its source connected to ground. Both transistors 130 , 132 are controlled by the first enabling logic signal EN1. [0026] The first regulator LDO1 operates in one of two operating states, as controlled by the first enable signal EN1. In the first state, the differential amplifier 122 of the first LDO regulator 114 is enabled by the first enable signal EN1 to control the gate voltage of the first DMOS transistor 126 based on a comparison of the feedback signal VFB with the first reference voltage VREF1. In the second state, operation of the first differential amplifier 122 and the first LDO regulator 114 are disabled by the first enable signal EN1 and the first DMOS transistor 126 is locked in a high impedance (non-conducting) condition. [0027] The second regulator LDO2 operates in one of three operating states, as controlled by the combined first and second enable signals EN1 and EN2. In the first operating state, the second differential amplifier 124 of the second LDO regulator 116 is enabled to control the gate voltage of the second DMOS transistor 128 based on a comparison of the feedback signal VFB with the first reference value VREF1. In the second operating state, operation of the second differential amplifier 124 and the second LDO regulator 116 are disabled and the second DMOS transistor 128 is locked in a high impedance (non-conducting) condition. In the third operating state, the second DMOS transistor 128 is locked in a low impedance (conducting) condition. [0028] The connecting device CONN_DEV operates in one of two operating states, as controlled by the first enabling logic signal EN1. In the first state, the third DMOS transistor 130 is controlled to be closed, i.e., to electrically couple the drain of the second DMOS transistor 128 with the supply node VCC, while the NMOS transistor 132 is concurrently controlled to be open, i.e., to electrically isolate the drain of the second DMOS transistor 128 from ground. In the second state, the conditions of the transistors 130 , 132 are reversed: the third DMOS transistor 130 is controlled to be open while the NMOS transistor 132 is controlled to be closed. [0029] The two control signals VCTRL1 and VCTRL2, combined by the control logic 104 to produce the enabling logic signals EN1 and EN2, define three distinct regions of operation of the supply circuit 106 , to which correspond three different topologies of the power supply circuit of the internal control circuitry, to which, in turn, correspond different levels of power consumption, as indicated in the following table. [0000] TABLE 1 Region Operating mode Output voltage condition 1 VCC generated by LDO1 VOUT < VREF2/KDIV1 (VIN powered) 2 VCC directly connected to VREF2/KDIV1 < VOUT < VOUT via DMOS2 and VREF2/KDIV2 DMOS3 3 VCC generated by LDO2 VREF2/KDIV2 < VOUT (VOUT-powered) [0030] The three logical combinations of the two control signals VCTRL1 and VCTRL2 and the corresponding logical combinations of the pair of enabling signals EN1 and EN2 of the two linear voltage regulators, LDO1 and LDO2, and of the connection device CONN_DEV, and the three consequent configurations of the supply circuit 106 that they implement through the gate signals GATE1, GATE2, applied to the devices DMOS1 and DMOS2, respectively, are indicated in the following table. [0000] TABLE 2 Region VCTRL1 VCTRL2 EN1 EN2 GATE1 GATE2 1 0 0 1 0 Con- VOUT trolled by LDO 114 2 1 0 0 0 VIN VOUT − V GS, MAX 3 1 1 0 1 VIN Con- trolled by LDO 116 [0031] In the operating region 1, the behavior of the internal supply circuit 106 is that of the linear voltage regulator: In this region, the power consumption by the internal circuitry is the greatest. The first LDO regulator 114 is in its first operating state, the second LDO regulator 116 is in its second operating state, and the connection device CONN_DEV is in its second operation state. Accordingly, the VCC voltage is determined solely by the first LDO regulator 114 , with the second LDO regulator 116 disabled and with the second DMOS transistor 128 in a high impedance, non-conducting state. The third DMOS transistor 130 of the connection device CONN_DEV, between the supply node VCC and the second LDO regulator 116 , is open and non-conducting, while the NMOS transistor 132 is closed, grounding the second DMOS transistor 128 . [0032] In the operating region 3, the first LDO regulator 114 is in its second operating state, the the second LDO regulator 116 is in its first operating state, and the connection device CONN_DEV is in its first operation state. Thus, the first LDO regulator 114 , powered by VIN, is switched off and the second LDO regulator 116 , powered by VOUT, is switched on. In this way, the current to power the whole control circuitry, i:e, the supply circuit 106 and the controller 108 , is no longer drawn from the input source (VIN), on the contrary it is drawn from the output node (at the voltage VOUT) of the switching converter (which is lower than VIN in view of the fact that the converter is of step-down type) and as a consequence, the internally consumed power decreases by a factor equal to VOUT/VIN. The voltage VCC is solely provided by the second LDO regulator 116 , with the first LDO regulator 114 disabled and its output DMOS transistor 126 in a high impedance state. In this region, the connection device CONN_DEV is enabled to couple the output DMOS transistor 128 of the second LDO regulator 116 with the VCC node. [0033] In the operating region 2, besides achieving the above described result, a further reduction of current absorption is obtained because none of the two linear regulators is active. The first LDO regulator 114 is in its second operating state, the second LDO regulator 116 is in its third operating state, and the connection device CONN_DEV is in its first operation state. Thus, VCC voltage is more or less equal to VOUT (less the voltage drop on the second and third DMOS transistors 128 , 130 ), LDO 1 is disabled, with its output DMOS transistor 126 in a high impedance state, and the second LDO regulator 116 is also disabled, with the gate of the second DMOS transistor 128 forced to VOUT-V GS,max . The third DMOS transistor 130 of the connection device CONN_DEV is enabled in order to ensure the minimum connection resistance between VOUT and VCC. [0034] In view of the fact that the DC-DC converter is of the step-down type, the output voltage VOUT being, by definition, lower than the input supply voltage VIN, it is evident that the power consumption in regions 2 and 3 is less than that consumed in region 1. Furthermore, because neither of the linear regulators 114 , 116 is in operation while the output voltage VOUT is in the operating region 2, which corresponds to the nominal output voltage of the converter, they consume almost no power while the converter is able to maintain the output voltage VOUT near its target value. [0035] The results in terms of reduction of the power consumption in the internal circuitry using the novel architecture of the applicant are summarized in the following table in which are also indicated the values taken by the ratio K P =P INT /P OUT , the trend of which is a determining factor in evaluating the efficiency (in view of the fact that the efficiency η=1(1+K P )). [0000] TABLE 3 Region P INT K P = P INT /P OUT 1 VIN * (I CTRL + I LDO ) VIN/VOUT * (I CTRL + I LDO )/I OUT 2 VOUT * I CTRL I CTRL /I OUT 3 VOUT * (I CTRL + I LDO ) (I CTRL + I LDO )/I OUT [0036] As may be deduced from Table 3, the novel DC-DC converter of the applicant achieves a reduction of power consumption that is greater or equal to the conversion ratio of operation of the converter, and such a result is obtained also in applications wherein the output voltage may undergo large variations. [0037] Preferably, the VOUT monitoring block 102 , as schematically exemplified in FIG. 4 , is designed in a way to introduce an adequate hysteresis in both of the two triggering thresholds, in order to eliminate the risk of oscillation between adjacent regions of operation that could be caused by disturbances or noise. [0038] In an application wherein the output voltage may cross or stay for long periods of time in the operation region 2 of the converter, the increment of efficiency compared to prior art converters is remarkable, because the power consumption of a linear voltage regulator that, in applications designed for extremely low power consumption, represents one of the dominant items of current absorption, may be practically eliminated. [0039] The behavior of the proposed architecture is diagrammatically illustrated in FIG. 6 , wherein the states of the control signals VCTRL1 and VCTRL2, which define the functioning region corresponding to the value of VOUT may be observed. Moreover, it is possible to observe as, in region 2, the VCC is identical to VOUT because of the direct strapping obtained by switching on with fullest VGS the second DMOS transistor 128 and the connection device CONN_DEV, and how the VCC is constant in the operating regions 1 and 3 because of the switching on of the first and second LDO regulators 114 , 116 , respectively. The vertical dashed lines T1 and T2 in the graph of FIG. 6 correspond to the points at which the rising slope of the output voltage VOUT crosses the threshold values VREF2/KDIV1 and VREF2/KDIV2, respectively. The various embodiments described above can be combined to provide further embodiments. These and other changes can be made to the embodiments in light of the above-detailed description. In general, in the following claims, the terms used should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by the disclosure.
Powering the internal circuitry, that is the controller of the power switch of a step-down DC-DC converter for a broad range of values of output voltage and achieving an enhanced energy saving in a low load conditions of operation is made possible by a method and implementing circuit based on defining two distinct thresholds of discrimination of the output voltage, both tied to a reference voltage, for generating two respective control signals and defining, from logical combinations of said two control signals, three distinct regions of operation of the converter upon the varying of electrical parameters, respectively identified by logical combinations of a pair of enabling signals.
8
TECHNICAL FIELD [0001] This disclosure relates to fractional-order proportional-resonant controllers for sinusoidal references. BACKGROUND [0002] Various types of electric vehicles or power systems draw power from a battery bank or direct current source (e.g., photovoltaic cells, fuel cells, capacitors). Direct current from the battery is fed into an inverter to generate alternating current, which is received by an electric machine or power grid. An error may develop between the demand (reference) and output, commonly referred to as steady-state error. A controller may be used to ensure the output tracks the reference such that the steady-state error is as close to zero as possible. Numerous strategies have been implemented to reduce steady-state error, but generally have drawbacks. The drawbacks may be related to the amount of processing required to control the signal or limited degrees of freedom to properly tune the control system transfer functions. SUMMARY [0003] A closed-loop system may include a plant (e.g., an electric machine requiring control) and a fractional-order proportional-resonant controller. The fractional-order proportional-resonant controller may have an order greater than zero and less than or equal to one. The order for the fractional-order proportional-resonant controller may be selected to yield a target amplitude and target slope for frequency response. The frequency response may be such that a steady-state error associated with a speed of the electric machine is inversely proportional to the target amplitude and less than a predetermined threshold. The order of the controller may be 0.9. The bandwidth about the natural frequency or resonant frequency of the controller may be one radian per second. The natural frequency of the controller may be 120π Hz. The proportional gain of the controller may be four. The integral gain of the controller may be 300. The controller may have a gain of at least 50 dB at 60 Hz. [0004] A vehicle may include an inverter for an electric machine and a fractional-order proportional-resonant controller. The fractional-order proportional-resonant controller may have at least three degrees of freedom and an order, greater than zero and less than or equal to one, selected to yield a target amplitude and target slope for frequency response such that a steady-state error associated with an output signal of the electric machine is inversely proportional to the target amplitude and less than a predetermined threshold. The order of the controller may be 0.9. The bandwidth about the natural frequency may be one. The natural frequency of the system may be 120n Hz. The proportional gain may be four. The integral gain may be 300. The controller may have a gain of at least 50 dB at 60 Hz. BRIEF DESCRIPTION OF THE DRAWINGS [0005] FIG. 1 depicts an electric vehicle or plant. [0006] FIG. 2 depicts a FO-PR controller for an electric vehicle or three-phase inverter. [0007] FIGS. 3A and 3B depict the system response at a 120π natural frequency. DETAILED DESCRIPTION [0008] Embodiments of the present disclosure are described herein. It is to be understood, however, that the disclosed embodiments are merely examples and other embodiments may take various and alternative forms. The figures are not necessarily to scale; some features could be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention. As those of ordinary skill in the art will understand, various features illustrated and described with reference to any one of the figures may be combined with features illustrated in one or more other figures to produce embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. Various combinations and modifications of the features consistent with the teachings of this disclosure, however, could be desired for particular applications or implementations. [0009] Controllers are used to achieve an objective output from a particular plant or system. The controller may be implemented as an interconnected system of parts having assigned functions. Some control systems are used to minimize steady state error and ensure proper system response. Typically, these systems employ feedback loops to create a closed-loop system, which reduces steady state error. Resonant systems provide particular challenges to controllers because of their continuously oscillating output. [0010] Closed-loop proportional integral (PI) controllers may be implemented to reduce steady state error of resonant systems. A closed-loop PI controller includes a proportional gain and integral gain. Typically, proportional integral controllers have a transfer function similar to Equation 1 below. [0000] G PI  ( s ) = K P + K I s ( 1 ) [0000] where K P is the proportional gain and K I is the integral gain. The PI controller can be used to controller resonant systems by transforming the resonant components of the input signal using Park's transformation or direct-quadrature-zero transformation. PI controllers also require additional feedfoward loops to control resonant systems. [0011] Closed-loop proportional-resonant (PR) controllers may be implemented to reduce steady state error of resonant systems. PR controllers also include proportional gain and integral gain. Typically, second-order PR controllers have a transfer function similar to Equation 2 below. [0000] G PR  ( s ) = K P + K I  s s 2 + ω n 2 ( 2 ) [0000] where K P is the proportional gain, K I is the integral gain, and ω n is the natural frequency. The PR controller above is an ideal PR controller. The controller is said to have “second-order” because the Laplace operator, s, is raised to the second power. The ideal PR controller has infinite gain but may cause stability problems due to practical limitations for implementing the signal processing systems. [0012] For these reasons, a non-ideal PR transfer function is used instead. The transfer function for a practical, non-ideal, second-order PR controller is shown in Equation 3 below. [0000] G PR  ( s ) = K P + K I  ω c  s s 2 + 2   ω c  s + ω n 2 ( 3 ) [0000] where K P is the proportional gain, K I is the integral gain, and ω n is the natural frequency. The resonant frequency may be adjusted to appropriately widen the bandwidth of the controller. Widening of the controller bandwidth may decrease the maximum gain of the controller. The second-order PR controller is said to have three degrees of freedom because the controller may be tuned using K P , K I , and ω C . Proportional-resonant controllers can operate on a stationary frame signal derived from a Clarke transformation. Proportional-resonant controllers do not require feedforward [0013] A fractional-order or arbitrary order controllers may be implemented using fractional-orders integrators and differentiators to enhance an engineer's ability to tune the controller. A fractional-order PID controller is said to increase the degrees of freedom of a PID controller, which has three degrees of freedom, to five degrees of freedom. The fractional-order PID controller, as depicted in Equation 4, includes five degrees of freedom (i.e., K P , K I , α, K D , β). [0000] G  ( s ) = K P + K I s α + K D  s β ( 4 ) [0000] where K P is the proportional gain, K I is the integral gain, α is the fractional-order of the integral component, K D is the derivative gain, and β is the fractional-order of the derivative component. [0014] As discussed above, PI controllers are poorly situated to control resonant systems and PR controllers lack sufficient degrees of freedom to provide fine tuning of the controller. A fractional-order, proportional-resonant (FO-PR) controller can provide additional degrees of freedom and avoid drawbacks related to the implementation of a PI controller on a resonant system. One such FO-PR controller is described in Equation 5. [0000] G FO - PR  ( s ) = K P + K I  s α s 2  α - 2   cos  ( απ 2 )  ω n α  s α + ω n 2  α ( 5 ) [0000] where K P is the proportional gain, K I is the integral gain, α is the fractional-order of the integral component, and ω n is the natural frequency at frequency (2πf). The controller may be adjusted for different frequencies and added in parallel using a similar reference and feedback system as disclosed in FIG. 2 , as shown in Equation 6. [0000] G FO - PR  ( s ) = ∑ j = 1 ∞   K Pj + K Ij  s α s 2  α - 2   cos  ( απ 2 )  ω nj α  s α + ω nj 2  α ( 6 ) [0015] Adding all of the frequencies in parallel allows for an FO-PR controller to control all of the frequencies anticipated when designing the controller for a particular plant. For example, a vehicle may demand various frequencies for given conditions. The FO-PR controller can provide accurate control of the resonant signal at each of those frequency demands with a smaller steady-state error and higher gain than other controllers. The coefficients, K Pj is the proportional gain, K Ij is the integral gain, α j is the fractional-order of the integral component, and ω nj , of the FO-PR controller of Equation 6 may be adjusted independently for each frequency. This tuning provides separate controllers with new sets of parameters, which are then paralleled, to address each frequency required. [0016] PI controllers are generally limited to operate on a rotating dq reference frame. The three-phase reference signal, as required by most electric machines and utility grids, is converted into the rotating dq reference frame by a Park transformation. PR controllers are capable of controlling a stationary reference frame on an α-β or x-y plane. A stationary reference frame is generally derived using a Clarke transformation of a three-phase reference signal. [0017] An example vehicle having an electric machine is depicted in FIG. 1 and referred to generally as a vehicle 16 . It is noted that a vehicle's electric machine and inverter is only one example of a plant that may be controlled by a fractional-order proportional-resonant controller. For example, a universal power supply could also be a plant controlled using a similar method. Continuing, the vehicle 16 includes a transmission 12 and is propelled by at least one electric machine 18 and may have selective assistance from an internal combustion engine (not shown). The electric machine 18 may be an alternating current (AC) electric motor depicted as “motor” 18 in FIG. 1 . The electric machine 18 receives electrical power and provides torque for vehicle propulsion. The electric machine 18 also functions as a generator for converting mechanical power into electrical power through regenerative braking. [0018] The vehicle 16 includes an energy storage device, such as a traction battery 52 for storing electrical energy. The battery 52 is a high-voltage battery that is capable of outputting electrical power to operate the electric machine 18 . The battery 52 also receives electrical power from the electric machine 18 and the second electric machine 24 when they are operating as generators. The battery 52 is a battery pack made up of several battery modules (not shown), where each battery module contains a plurality of battery cells (not shown). Other embodiments of the vehicle 16 contemplate different types of energy storage devices, such as capacitors and fuel cells (not shown) that supplement or replace the battery 52 . A high-voltage bus electrically connects the battery 52 to the electric machine 18 and to the second electric machine 24 . [0019] The vehicle includes a battery energy control module (BECM) 54 for controlling the battery 52 . The BECM 54 receives input that is indicative of vehicle conditions and battery conditions, such as battery temperature, voltage and current. The BECM 54 calculates and estimates battery parameters, such as battery state of charge and the battery power capability. The BECM 54 provides output (BSOC, P cap ) that is indicative of a battery state of charge (BSOC) and a battery power capability (P cap ) to other vehicle systems and controllers. [0020] The vehicle 16 includes a DC-DC converter or variable voltage converter (VVC) 10 and an inverter 56 . The VVC 10 and the inverter 56 are electrically connected between the traction battery 52 and the electric machine 18 . The VVC 10 “boosts” or increases the voltage potential of the electrical power provided by the battery 52 . The VVC 10 also “bucks” or decreases the voltage potential of the electrical power provided to the battery 52 , according to one or more embodiments. The inverter 56 inverts the DC power supplied by the main battery 52 (through the VVC 10 ) to AC power for operating the electric machine 18 . The inverter 56 also rectifies AC power provided by the electric machine 18 to DC for charging the traction battery 52 . Other embodiments of the transmission 12 include multiple inverters (not shown), such as one invertor associated with each electric machine 18 . The VVC 10 includes an inductor assembly 14 . [0021] The transmission 12 includes a transmission control module (TCM) 58 for controlling the electric machine 18 , the VVC 10 , and the inverter 56 . The TCM 58 is configured to monitor, among other things, the position, speed, and power consumption of the electric machine 18 . The TCM 58 also monitors electrical parameters (e.g., voltage and current) at various locations within the VVC 10 and the inverter 56 . The TCM 58 provides output signals corresponding to this information to other vehicle systems. [0022] The vehicle 16 includes a vehicle system controller (VSC) 60 that communicates with other vehicle systems and controllers for coordinating their function. Although it is shown as a single controller, the VSC 60 may include multiple controllers that may be used to control multiple vehicle systems according to an overall vehicle control logic, or software. [0023] The vehicle controllers, including the VSC 60 and the TCM 58 generally includes any number of microprocessors, ASICs, ICs, memory (e.g., FLASH, ROM, RAM, EPROM and/or EEPROM) and software code to co-act with one another to perform a series of operations. The controllers also include predetermined data, or “look up tables” that are based on calculations and test data and stored within the memory. The VSC 60 communicates with other vehicle systems and controllers (e.g., the BECM 54 and the TCM 58 ) over one or more wired or wireless vehicle connections using common bus protocols (e.g., CAN and LIN). The VSC 60 receives input (PRND) that represents a current position of the transmission 12 (e.g., park, reverse, neutral or drive). The VSC 60 also receives input (APP) that represents an accelerator pedal position. The VSC 60 provides output that represents a desired wheel torque, desired engine speed, and generator brake command to the TCM 58 ; and contactor control to the BECM 54 . [0024] If the vehicle 16 is a plug-in electric vehicle, the battery 52 may periodically receive AC energy from an external power supply or grid, via a charge port 66 . The vehicle 16 also includes an on-board charger 68 , which receives the AC energy from the charge port 66 . The charger 68 is an AC/DC converter which converts the received AC energy into DC energy suitable for charging the battery 52 . In turn, the charger 68 supplies the DC energy to the battery 52 during recharging. It is understood that the electric machine 18 may be implemented on other types of electric vehicles, such as a hybrid-electric vehicle or a fully electric vehicle. [0025] Now referring to FIG. 2 , a fractional-order, proportional-resonant controller 100 is shown. The controller 100 includes a stationary frame x-component current input derived from the summation 120 of i xd *, i x 110 , and i x * 136 . Input i xd * is derived from i dd * 102 having a rotating reference frame d and space vector block 104 , which incorporates the feedback phase shift angle 118 . The feedback phase shift angle 118 is derived from the phase-locked loop (PLL) 116 controller and voltage signal 114 . Input i x 110 is the stationary frame x-component of the three-phase feedback current signal i 106 from the output of the inverter (not shown). The i x * 136 is a stationary frame reference signal from a grid current or other reference current, i* 135 . Similarly, the controller 100 includes an y-component current input derived from the summation 122 of i y 112 and i y * 138 . i y 112 is the y-component of the feedback current signal from the output of the inverter (not shown). The i y * 138 is a reference signal from a grid current or other reference current, i* 135 . [0026] The summation blocks 120 , 122 are individually fed into respective FO-PR transfer functions. For example, signal i x is adjusted by a proportional gain K P 124 and a fractional-order, resonant transfer function 126 having adjustable constants K I , α, and ω. The proportional and integral components are joined at summation block 128 having an out of voltage U x * 140 . Similarly, signal i x is adjusted by a proportional gain K P 130 and a fractional-order, resonant transfer function 132 having adjustable constants K I , α, and ω. The proportional and integral components are joined at summation block 134 having an output of voltage, U y * 142 . The outputs U x * 140 and U y * 142 are fed to the space vector modulation block (SVM) 144 . The SVM 144 allows the generation of pulse width modulation signals without converting the space vector outputs from the controller, U x * 140 and U y * 142 , into three-phase values first. [0027] Referring to FIGS. 3A-B , the numerical results of the FO-PR controller are depicted. FIG. 3A discloses the gain of the FO-PR controller having wherein the natural frequency is 120π Hz, the proportional gain is four, the integral gain is 300, and alpha (fractional order) is 0.9. As shown, the reduced bandwidth PR controller 202 having a reduced bandwidth of 0.4, ω B , where ω B =(−1.196ζ+1.85)ω n . Where is the damping ratio and ω n is the natural frequency. As shown, the 1.0 bandwidth PR controller 204 has a wider bandwidth than the reduced bandwidth controller, but a smaller gain. The FO-PR controller 206 has substantially higher gain than either PR controller 202 , 204 at over 70 dB and provides a wider bandwidth. FIG. 3B depicts the phase-shift response of each controller. The reduced bandwidth PR controller 202 has a larger phase-shift near the resonant frequency of 60 Hz than the 1.0 bandwidth PR controller 204 . The FO-PR controller 206 has the best phase-shift response, as shown. [0028] The words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the disclosure. As previously described, the features of various embodiments may be combined to form further embodiments of the invention that may not be explicitly described or illustrated. While various embodiments could have been described as providing advantages or being preferred over other embodiments or prior art implementations with respect to one or more desired characteristics, those of ordinary skill in the art recognize that one or more features or characteristics may be compromised to achieve desired overall system attributes, which depend on the specific application and implementation. These attributes may include, but are not limited to cost, strength, durability, life cycle cost, marketability, appearance, packaging, size, serviceability, weight, manufacturability, ease of assembly, etc. As such, embodiments described as less desirable than other embodiments or prior art implementations with respect to one or more characteristics are not outside the scope of the disclosure and may be desirable for particular applications.
A closed-loop system may include a plant (an electric machine requiring control) and a fractional-order proportional-resonant controller. The fractional-order proportional-resonant controller may have an order greater than zero and less than or equal to one. The order for the fractional-order proportional-resonant controller may be selected to yield a target amplitude and target slope for frequency response. The frequency response may be such that a steady-state error associated with a speed of the electric machine is inversely proportional to the target amplitude and less than a predetermined threshold. The order of the controller may be 0.9.
7
FIELD OF THE INVENTION The present invention relates to a modular exercise pole and anchoring system. More particularly, the present invention relates to an exercise pole with multiple vertical and horizontal attachment points for connecting resistance training devices, the pole being attached to a base having a base post that accepts a plurality of plate-type weights for anchoring. The exercise pole and anchoring system have application to resistance training for fitness, among other uses, while the anchoring system alone has application to a number of uses where convenient, removable anchoring is desired. BACKGROUND OF THE INVENTION Current exercise poles require either permanent attachment to walls, ceilings, and floors or require bottom plate suction means that can mar a floor. In addition, floor anchored exercise poles also require the user to fill a hollow container with sand or water in order to provide adequate anchoring weight for the device. The drawbacks to the prior art methods of placing exercise poles include the unsightly and permanent destruction of walls, ceilings, and floors. Prior art devices also do not provide for simple removal of the anchoring weight, such as water or sand, when the exercise unit is to be relocated. SUMMARY OF THE INVENTION The present invention provides a novel exercise pole and anchoring system that is easily built, placed, and anchored. The anchoring device of the present invention allows a user to quickly add or remove plate-type weights commonly found in gyms to provide sufficient anchor weighting to the exercise unit. BRIEF DESCRIPTION THE DRAWINGS Various embodiments of the present invention are shown and described in reference to the numbered drawings wherein: FIG. 1 shows a top angle view of the modular exercise pole and anchoring system of the present invention; FIG. 2 shows a partially exploded top angle view of the modular exercise pole and anchoring system of the present invention, where the pole is comprised of two pole segments shown in exploded view; FIG. 3A and FIG. 3B show top perspective views of both the hexagonal and rounded configuration of the anchor base and spokes with different wheel configurations; FIG. 4 shows a side perspective view of one embodiment of the wheels attached through wheel brackets to the anchor base and configured for use with the present invention; FIG. 5 shows a side perspective view of one embodiment of foot posts configured for use with the present invention; FIG. 6 shows a top angle view of a wheel and step lifter configuration used with the present invention; FIG. 7 shows a side view of the attachment rings configured with sleeve bushings for rotational use on the modular exercise pole and anchoring system of the present invention; FIG. 8 shows a top angle view of an attachment ring with a ring hub configured for attachment to the exercise pole via a set screw; and FIG. 9 shows a side angle view of the exercise pole segments connected via a spring bar connection; and FIG. 10 shows a side angle view of one embodiment of the modular exercise pole and anchoring system of the present invention. It will be appreciated that the drawings are illustrative and not limiting of the scope of the invention which is defined by the appended claims. The embodiments shown accomplish various aspects and objects of the invention. It is appreciated that it is not possible to clearly show each element and aspect of the invention in a single FIGURE, and as such, multiple figures are presented to separately illustrate the various details of the invention in greater clarity. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel modular exercise pole and anchoring system. In one embodiment of the invention (referring to FIG. 1 ), there is a base ( 10 ) which forms an anchor to hold exercise pole ( 24 ) in place. Base ( 10 ) can be formed from any solid material that will provide rigidity and strength. Preferably, base ( 10 ) is made of square tubular steel measuring 1.5 inches square, but it can also be formed from angle iron. It is desired that base ( 10 ) have a width or diameter of at least 36 inches in order to accommodate most large plate weights found in a typical gym or exercise facility. In one embodiment of the invention, base ( 10 ) is formed in the shape of a hexagon, while another embodiment contemplates a circular shape. Base spokes ( 12 ) radiate inward and meet at spoke junction ( 14 ), located in the center of the region bounded by base ( 10 ). If base ( 10 ) is in the form of a hexagon, then three base spokes ( 12 ) are preferably used. Base post ( 16 ) is formed rising up from spoke junction ( 14 ) and is preferably made from circular tubular steel. Side arms ( 18 ) are connected to base ( 10 ) and are formed to rise vertically above base ( 10 ) and to meet at side arm junction ( 20 ), located in the center of the region above the space bounded by base ( 10 ). Together, base ( 10 ), base spokes ( 12 ), and side arms ( 18 ) form a protective cage ( 17 ) wherein plate weights ( 5 ) can be placed. A height h ( 22 ) is measured between spoke junction ( 14 ) and side arm junction ( 20 ). Base post ( 16 ) should be a length less than height h ( 22 ) such that plate weights ( 5 ) can be inserted between side arms ( 18 ) at the top of protective cage ( 17 ) and stacked over base post ( 16 ). Side arms ( 18 ) serve not only to provide a rigid frame for exercise pole ( 24 ), but also function to protect the user from inadvertently kicking or otherwise contacting plate weights ( 5 ) that anchor the exercise unit. Base ( 10 ), base spokes ( 12 ), base post ( 16 ) and side arms ( 18 ) can be connected in any number of different ways, including welding and through mechanical connections such as bolts, screws, and clamps. Side arm junction ( 20 ) is formed as a tubular sleeve connected to side arms ( 18 ). The internal diameter of side arm junction ( 20 ) should be the same as the internal diameter of base post ( 16 ) such that exercise pole 24 can be inserted downward through side arm junction ( 20 ) and into base post ( 16 ) and securely held in place through either friction or through set screws tapped into base post ( 16 ) and/or side arm junction ( 20 ). In another embodiment of the present invention, exercise pole ( 24 ) is configured such that it can be connected to base ( 10 ) without the need for base post ( 16 ). In this case, plate weights ( 5 ) are placed within protective cage ( 17 ) and are stacked over base spokes ( 12 ) in a manner that allows the exercise pole ( 24 ) to be inserted downward from side arm junction ( 20 ), through the holes in plate weights ( 5 ) and positioned for connection with spoke junction ( 14 ). In yet another embodiment, side arms ( 18 ) can be configured to support a flat surface forming the top portion of protective cage ( 17 ). In this manner, the modular exercise pole and anchor system of the present invention can be configured with a stepping platform that would allow the user to implement even more exercise routines. Spaces for storing resistance training devices ( 5 ) and other exercise equipment such as exercise gloves, gripping powders, and the like could also be configured within protective cage ( 17 ). For cosmetic purposes, side arms ( 28 ) can be covered with a plastic or cloth material. However, any such cosmetic covering should be easily detachable in order to facilitate convenient removal of plate weights ( 5 ) from the base post ( 16 ). Exercise pole ( 24 ) can be any length sufficient to offer a wide range of attachment points for accommodating exercise devices such as resistance training devices ( 2 ). One common type of resistance training device is the SLASTIX® brand sheathed elastics, which are well-known for their ease of use, versatile tensile strengths, rugged construction, and safety features. Exercise pole ( 24 ) supports attachment rings ( 28 ), which are configured at various intervals across the pole. Attachment rings ( 28 ) have ring spokes ( 30 ) that prevent the attached training devices ( 2 ) from sliding in an endless circular motion. By providing ring spokes ( 30 ), the invention allows multiple users to exercise on the same pole without compromising safety or convenience. In addition, ring spokes ( 30 ) allow a single user to perform more complicated exercises using multiple resistance devices ( 2 ). Ring spokes ( 30 ) can be welded directly to exercise pole ( 24 ). However, a preferred method is to form annular ring hub ( 62 ) within the space bounded by annular attachment ring ( 28 ) (referring to FIGS. 8 and 9 ). Ring spokes ( 30 ) are connected between the outer attachment ring ( 28 ) and the inner ring hub ( 62 ). If ring hub ( 62 ) is used, a convenient method for affixing attachment ring ( 28 ) to exercise pole ( 24 ) is to use receiving hole ( 66 ) and set screw ( 64 ). In this manner, the location of attachment rings ( 28 ) along the length of exercise pole ( 24 ) can be easily adjusted to provide a customized workout experience. In one embodiment of the invention, exercise pole ( 24 ) is formed from multiple pole segments ( 26 ) (referring to FIGS. 2 and 9 ). When pole segments ( 26 ) are used, it is important that the connection between segments is strong. Pole segments ( 26 ) can have matching male and female ends for secure end-to-end connection to each other. Those of ordinary skill in the industry will appreciate the various connection methods available for ensuring a strong, solid attachment between pole segments ( 26 ). In one embodiment, pole segments ( 26 ) are configured for mating through inset threads and screw-type action. Another connection method involves using clamps ( 68 ) across the connection joint. While yet another embodiment contemplates a spring bar ( 74 ) and spring pin ( 72 ) arrangement (shown in FIG. 9 ). Combinations of these connection techniques can also be employed. In this manner the exercise pole can be constructed of varying pole segments depending on the most cost-effective packing and shipping methods. Another novel feature of the present invention is the ability to selectively rotate certain attachment rings ( 28 ) through the use of sleeve bushings ( 70 ) (referring to FIG. 7 ). In this embodiment, clamps ( 68 ) are located along the length of exercise pole ( 24 ) and are used to prevent sleeve bushings ( 70 ) from moving beyond a determined longitudinal position along the pole. Sleeve bushings ( 70 ) are sized with an inner diameter just larger than the outer diameter of pole ( 24 ) such that the bushings can freely rotate around the pole. Attachment ring ( 28 ) is then affixed to sleeve bushing ( 70 ). In this manner, exercise pole ( 24 ) can be selectively configured with rotating attachment rings ( 28 ). The combination of rotating and non-rotating attachment rings ( 28 ) along pole ( 24 ) is a novel feature of the present invention that yields an extremely wide variety of possible exercise routines using resistance training devices ( 2 ). In yet another embodiment of the present invention, base ( 10 ) is provided with wheels ( 40 ) that can be selectively moved from a resting to a working position. Referring to FIG. 3 , wheels ( 40 ) can be located either inside or outside of base ( 10 ). If located outside base ( 10 ), wheels ( 40 ) can be configured in a square arrangement to make a more easily packaged and shipped product. Referring to FIG. 4 , wheel post bracket ( 44 ) is attached to base ( 10 ) through welding, clamps, bolts, or some other method of secure connection. Wheel post ( 42 ) can be a threaded rod adapted for adjustable vertical movement through wheel bracket ( 44 ). Wheel post ( 42 ) is connected on one end to wheel post handle ( 46 ) and the other end to wheel ( 40 ). By twisting wheel post handle ( 46 ), wheel ( 40 ) can be selectively raised or lower depending on need. To move the entire assembly, the user would simply twist each wheel post handle ( 46 ) until base ( 10 ) is raised off the floor and the unit is resting on its wheels. The unit can be easily lowered through the reverse procedure. Another wheel configuration contemplated in the present invention is shown in FIG. 5 . In this embodiment, wheel post bracket ( 44 ) is securely connected to base ( 10 ) as before. Wheel post ( 42 ) is connected on one end to wheel ( 40 ) and on the other end to wheel post bracket ( 44 ) but it is not configured for selective movement. Instead, foot post ( 48 ), which is a threaded rod, is threaded through a hole in wheel post bracket ( 44 ) and connected on one end to foot post handle ( 52 ) and on the other end to foot pad ( 50 ). By twisting foot post handle ( 52 ), the user can position the unit in a desired location by raising the unit up so that wheels ( 40 ) do not touch the floor. A reverse motion on foot post handle ( 52 ) will raise foot pad ( 50 ) up off the floor until the unit is resting on wheels ( 40 ). Yet another wheel configuration is shown in FIG. 6 . Here, hinge ( 54 ) is securely connected to base ( 10 ) and step lifter ( 56 ). Wheel post ( 42 ) connects on one end to the underside of step lifter ( 56 ) and on the other end to wheel ( 40 ). Wheel post ( 42 ) is spaced a sufficient distance away from hinge ( 42 ) such that a fulcrum point is created between hinge ( 54 ) and a distal end ( 57 ) of step lifter ( 56 ). Latch ( 58 ) is attached to base ( 10 ) such that it can selectively receive distal end ( 57 ) of step lifter ( 56 ). By stepping on distal end ( 57 ) of step lifter ( 56 ), the user can lift base ( 10 ) off the floor and cause the unit to rest on wheel ( 40 ). Distal end ( 57 ) of step lifter ( 56 ) can be latched to base ( 10 ) using latch ( 58 ) to lock wheels ( 40 ) in a useable position for moving the unit. The above-described wheel arrangements can be configured on either the inside or the outside of base ( 10 ), depending on the user's preference. In addition, ring ( 60 ) (referring to FIG. 5 ) can be attached to wheel post bracket ( 44 ) to create a low attachment point for lifting the unit with straps or for attaching resistance training devices ( 2 ) to still further expand the user's exercise possibilities. The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
A modular exercise pole and anchoring system is provided. The present invention relates to an exercise pole with multiple vertical and horizontal attachment points for connecting resistance training devices, the pole being attached to a base having a base post that accepts a plurality of plate-type weights for anchoring. The exercise pole and anchoring system have application to resistance training for fitness, among other uses, while the anchoring system alone has application to a number of uses where convenient, removable anchoring is desired.
0
BACKGROUND OF THE INVENTION The present invention relates to a suction pipe for suction dredgers with mechanical feeder and cutter means adapted to handle the material dredged. Suction dredgers of this type are adopted in large numbers to condition the beds of lakes and stream courses. It is already known in the art to associate mechanical feeder and cutter means with the suction pipes for dredging purposes. It is likewise known in the art that these feeder means as such impose a load torque on the suction pipe which the pipe would pass on to the bottom of the dredge vessel so that suction pipe and vessel bottom must be of greater size than otherwise required. On the other hand there are deadcycle times involved in the process for sucking material from below the water surface for suction dredgers and other hydraulic conveyors whenever larger size rocks are caught in front of the suction pipe, and in general wherever rock and clay material is to be handled. It is a purpose therefore of hydraulic bottom rippers or dredgers and stone crushers to excavate rocks and clay formations directly in front of the suction pipe and at the same time crush larger size rocks so that they conveniently can be conveyed through the suction pipe. Equipment of this type is also known as cutters. The dredgers on the market at present are called cutter-head dredgers because their cutter equipment is adapted to rip the bottom by rotational movement in front of or adjacent the suction pipe. Their general drawback resides in that resultant load torques are transferred either upon the suction pipe proper or, by means of a lattice construction, upon the dredge vessel. SUMMARY OF THE INVENTION One of the principal objects of the present invention is to overcome the drawbacks of these prior art arrangements and to provide a feeder and cutter system for suction dredgers which in spite of increased capacity operates substantially in the absence of load torques. According to the invention the problem, broadly speaking, is solved in that at least two functionally opposed cutter and crusher tools actuatable by hydraulic cyclinders are provided, and each is rotatable about a pivot mounted relative to the suction pipe; the cylinders move the tools in opposite directions. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other objects of the invention will be best understood from the following description of an exemplification thereof, reference being had to the accompanying drawings, wherein: FIG. 1 is a partial sectional view of a suction pipe with counteracting cylinders and cutter tools thereto attached, shown near the beginning of a cutting stroke. FIG. 1a is similar to FIG. 1 except the cutter tools are shown near the end of a cutting stroke, and FIG. 2 is a bottom plan view of the suction pipe and tools shown in FIG. 1. DESCRIPTION OF THE PREFERRED EMBODIMENT In carrying the invention into effect in one of the embodiments which has been selected for illustration in the accompanying drawings and for description in this specification, and referring now particularly to FIG. 1, an important feature of the invention is that two or more laterally arranged hydraulic cylinders are provided to rotate the cutter and crusher tools 21 about one pivot 22, 23 each in opposed sense. Said hydraulic cylinders 20 moreover have their stroke travels synchronized so that the forces produced are completely transmitted upon the cutter and crusher means and there is no torque load imposed on the suction pipe 10 or the dredge vessel and only a relatively insignifigant vertical load so that the feeder and cutter system can also be attached to existing conveyor equipment without there being need for major modifications to be effected thereto. The feeder and cutter system comprises fixing and retaining means 11 disposed on the suction pipe 10, hydraulic cylinders 20 including piston rods 25, bearing joints 26,27 with corresponding bearing blocks 28, and cutter and crusher tools 21 including cutting edges 29 and spacers 30. Cutter and crusher tools 21 are shown in a preferred embodiment, disposed symmetrically on the suction pipe 10 in FIG. 2. There are two disk-like tools 21 shown secured together with bridging means 30, on each side of the suction pipe 10, shown in FIG. 2. Saw-tooth edges 29 are shown in FIGS. 1-1a, formed on the edge of the disk-like tools 21. Operation Operation of a suction pipe thus equipped is rather simple. As the pistons of the hydraulic cylinders 20 are moved, this movement is analogously transmitted upon and imparted to the cutter and crusher tools which by their saw edges 29 rip the bottom 31 and push the material cut 32 to in front of the suction pipe mouth 33 (FIG. 1a). Larger size rocks are reduced in size between said cutter and crusher tools 21. Continuous feeding of material ensures a substantially continuous performance of the suction pipe. Another essential feature of the present invention resides in that the pivot 22, 23 can be vertically varied between a bottom pivot 22 and a top pivot 23. The position of said pivot determines the cutting depth 34. Normally the elevation of said pivot 22, 23 also is adjustable which means that additional hydraulic cylinders 24 with sliding blacks 35 are fitted on the suction pipe 10. Any hydraulic conveyor can be combined with the feeder and cutter system of the present invention to form a dredger unit adapted for continuous performance and suitable for use also to excavate in depths down to more than 100 m below the water surface. Utilization of the feeder and cutter system of the present invention not only affords the essential advantage of keeping loads away from the suction pipe and the vessel structure, but also increases the output by up more than to 100%. Depending on its design and construction the system crushes rock greater than 1 m in diameter in a matter of seconds, loosens conglomerate layers and excavates clay formations. I wish it to be understood that I do not desire to be limited to the exact details of construction shown and described, for obvious modifications will occur to a person skilled in the art.
A suction pipe device for suction dredgers having at least two functionally opposed combined cutter and crusher tools mounted near the bottom opening of the suction pipe, to cut and crush and feed material to be dredged.
4
FIELD OF THE INVENTION The invention relates to a driving and guide arrangement for a mining machine which travels along a scraper chain conveyor, in particular for a drum cutter machine, with a guide rail arranged on the trough sections of the scraper chain conveyor above the level of the trough sections, and bounding a chain channel for a chain allowing the machine to haul itself along the mining face, with the horizontal links of the chain resting on support elements arranged within the chain channel, the latter being provided with openings underneath the chain to allow fines to fall through. BACKGROUND OF THE INVENTION An arrangement of this kind is known from DE-OS 4423925. In this arrangement the support elements for the horizontal links of a pin drive chain consist of support ledges extending over the length of the conveyor trough sections, with the vertical links of the pin drive chain engaging in, and practically entirely occupying, the slot-form space between the stowing-side and face-side ledges. The discharge openings for the fines in this known arrangement are open towards the gob or stowing side of the conveyor. It has been found that the discharge of fines from the chain channel does not always function satisfactorily in the known construction. In most cases this is because the continuous support ledges and the vertical chain-links engaging in the space between them leave relatively little clearance for eg. coal dust etc. to fall through on its way to the fines discharge openings. Consequently, caking of fines on the pin drive chain in the chain channel is a frequent occurrence. As a result, a correct engagement of the chain-wheel in the pin drive chain is no longer assured, and there may even be damage to chain-wheel and guide. It is the object of the invention to provide a particularly simple and inexpensive arrangement of the above-mentioned kind in which accumulations of fines in the chain channel accommodating the pin drive chain can be more reliably avoided, and an easier discharge of fines from the openings underneath the drive chain is obtained. SUMMARY OF THE INVENTION To achieve this object the support elements are formed as rest elements spaced apart from one other and engaging the horizontal chain-links from below, the individual rest elements having a limited dimension in the direction of travel of the mining machine, and the openings for discharge of fines are provided both on the stowing side of the chain channel and on its working front-facing side. Utilizing only spaced elements that are themselves short or narrow in the travel direction of the mining machine as supports for the chain-links, fines which get into the chain channel have sufficient clearance between any two adjacent support elements on either side of the vertical chain-links to be able to fall to the bottom of the chain channel, whence they can re-emerge on the working side as well as on the gob side. This arrangement largely eliminates the risk of accumulations of fines and caking or clogging in the chain channel. In a preferred form of the invention, the chain channel is made as a welded construction bounded on its working, front-facing side by the guide rail and on its rear, gob side by a rear wall, and welded connecting plates interconnect the rear wall and the guide rail. This configuration as a welded construction yields considerable cost and weight benefits. A particularly convenient arrangement is obtained by forming the connecting plates as support elements for the horizontal chain-links and providing them with recesses for the vertical chain-links. The connecting plates then perform a dual role, as they not only provide the bridge between the guide rail and rear wall components which bound the chain channel, but simultaneously serve as support elements for the chain-links. The lower region of the rear wall may be bent towards the guide rail, so as to bound the chain channel at the bottom as well as at the rear. The guide rail preferably consists essentially of a rolled or extruded section, which can have smaller dimensions and weights in comparison with the cast section that is still often used, and to which the connecting plates can be welded without any problem. The smaller dimensions and weights and the good weldability of the components can result in quite considerable cost advantages in relation to known designs. The fines discharge openings can consist basically of cutouts in the rear wall and/or guide rail, located between the connecting plates, preferably of trapezium form with the wider parallel side at the base. A particularly advantageous configuration is obtained by locating the guide rail a certain distance above the bottom boundary of the chain channel on the front side of the chain channel, thus forming between the guide rail and the bottom boundary of the chain channel a front fines discharge opening which can then conveniently extend over the whole length of the conveyor trough sections and/or of the chain channel itself. In this case, a guide shoe may be arranged on the mining machine so as to project through the front discharge opening to the conveyor trough and underneath the guide rail. This guide shoe not only serves to guide the drum cutter machine or its equivalent correctly on the guide arrangement, but additionally may be formed as a kind of scraper which rakes out any fines which have not already emerged from the chain channel through the discharge opening. The upper part of the guide rail may have a rail profile for a slide block and/or for one or more running wheels of the mining machine. In this case it is particularly advantageous for the rail profile to be approximately semicircular, engaging in a matching groove in the periphery of a running wheel. With this configuration, the mining machine is guided in a positive manner transversely with respect to its direction of travel. It is convenient to provide the guide rail with a projection in the region of the rail profile or of the lower edge of the rail, which overhangs a derailment preventer arranged on the mining machine. This will ensure that the running wheel or slide block of the mining machine cannot be derailed. The guide rail is conveniently provided, in a manner known in itself, with ledge-like projections which protrude into the chain channel and overhang the face-side shanks of the horizontal chain-links inside the chain channel. These projections prevent the drive chain from being lifted out of the chain channel. In a similar fashion, retaining bars can also be releasably attached on the stowing side of the chain channel after the chain has been inserted, so that these bars overhang the stowing-side shanks of the horizontal chain-links. After the retaining bars have been removed, the drive chain can be laid in the chain channel from above, or removed from above when replacement is necessary. The bottom boundary of the chain channel may be given a ridged, somewhat roof-like form, in which the ridge may be located approximately in the longitudinal centre plane of the chain channel and chute surfaces for the fines falling away on either side of the ridge to the fines discharge openings. The provision of such sloping chute surfaces assists the unhindered discharge of the fines which have entered the chain channel. Further features and advantages of the invention will be apparent from the description which follows and from the drawings, in which preferred embodiments of the invention are described in detail with reference to some examples. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an end view, partly in section, showing an individual trough section of a scraper chain conveyor with a pin drive and guide arrangement according to the invention mounted on the gob side of the conveyor trough; FIG. 2 is an enlarged sectional view of the pin drive and guide arrangement mounted on the conveyor trough shown in FIG. 1; FIG. 3 is a view of the region shown in FIG. 2, as seen in the direction of the arrow III; FIG. 4 shows a second embodiment of a pin drive and guide arrangement according to the invention, in a similar view to FIG. 2; FIG. 5 is a view of the region in FIG. 4, as seen in the direction of the arrow V; and FIG. 6 shows, in cross-section, a third embodiment of an arrangement according to the invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS The scraper chain conveyor used as a longwall face conveyor in underground mining normally consists of individual trough sections which are joined to one another with no longitudinal play, but with limited angular play; a single such trough section 10 together with its mountings is shown in the drawing in FIG. 1 . The drum cutter machine 11 , which straddles the scraper chain conveyor and travels along it for coal getting, is merely indicated in the drawing by chain-dotted lines. The trough sections 10 which together form the conveyor trough of the scraper chain conveyor consist, in a manner known in itself, of side-profiles 12 and 13 which are disposed symmetrically with respect to each other and are connected to each other by the conveyor deck 14 . An endless scraper chain loop, which in the illustrated example consists of a double centre endless chain loop 16 , with scraper flights 15 attached, runs in the troughs of the trough sections 10 bounded by the side-profiles and the conveyor deck. A running track 17 upon which the cutter machine is supported and guided by working-side track rollers 18 is mounted at the foot of the working-side profile 12 of the trough sections 10 . The drum cutter machine, which straddles the scraper chain conveyor, is guided on the gob side on guide rails 19 which are secured above the trough sections 10 and the gob-side side profiles 13 and which form part of a pin drive and guide arrangement 20 , the subject of the present invention. The pin drive and guide arrangement 20 essentially comprises for each conveyor trough section 10 an angle section 21 or profile member extending over the entire length of the trough section and the guide rail 19 likewise extending over the length of the trough section. The angle section 21 and the guide rail 19 are joined to one other by a plurality of connecting plates 22 which are welded to them at intervals, thus forming a chain channel 23 to receive a pin drive chain 24 . This chain channel 23 is bounded on the gob side by a rear wall 25 formed by the angle section 21 , on the working side by the guide rail 19 , and on the underside by a bottom chain channel boundary enclosure 26 formed by the second leg of the angle section 21 . The pin drive chain 24 lies with its horizontal chain-links 27 resting firstly on narrow rest bars 28 protruding a short way into the chain channel from the rear wall and from the guide rail, and partly on the narrow connecting plates 22 located between every two rest bars, the connecting plates 22 being provided for this purpose with recesses 29 which the vertical chain-links 30 can enter. The chain channel 23 has fines discharge openings 31 , 32 both on the gob side and on the working side, between the chain channel bottom boundary 26 on the one hand and rear wall 25 or guide rail 19 on the other hand. The rearward discharge openings 31 in the rear wall 25 are each located between two adjacent connecting plates 22 , and each has the shape of a trapezium with the wider parallel side at the chain channel bottom boundary 26 . In the embodiments shown in FIGS. 1, 2 , 3 and 6 , the working side fines discharge openings 32 are formed as a continuous discharge channel 33 which extends over the entire length of the individual trough sections 10 . In order to form this discharge channel 33 , the feet 34 of the guide rails 19 are not placed on the chain channel bottom boundary 26 , but are welded to the connecting plates 22 to lie some distance above the bottom boundary. In the embodiments shown in FIGS. 1, 2 , 3 and 6 , the guide rails 19 are also provided with additional discharge openings 35 , approximately oval in shape, immediately below the rest bars 28 . In the embodiment of the invention shown in FIGS. 1 to 3 , the guide rails have at the top a profile 36 with an approximately semicircular cross-section 36 which engages in a matching groove 27 in a running wheel 38 of the cutter machine 11 . The running wheel 38 is provided on its gob-side outer face 39 with the pin drive sprocket 40 , the teeth 41 of which engage between adjacent vertical links 30 of the pin drive chain 24 lying in the chain channel and thus with rotation of the running wheel 38 haul the cutter machine 11 along the conveyor. To prevent the running wheel 38 from lifting off the guide rail 19 , the drum cutter machine is provided with a derailment preventer 42 which projects under the foot 34 of the guide rail 19 into the discharge channel 33 . This arrangement ensures that the cutter machine is not only guided transversely with respect to the running direction of the machine because of the interlocking forms of the running wheel and rail profile cross-sections, but also that it cannot be accidentally derailed. The same applies to the embodiment according to FIGS. 4 and 5, in which the guide rail is provided with an additional projection 43 which overhangs the derailment preventer 42 arranged on the getting machine 11 . In the pin drive and guide arrangements which have been described and illustrated, fines, such as coal dust or the like, entering the chain channel 23 from above descend between—and largely unhindered by—the connecting plates 22 and rest bars 28 , since these have a limited extent in the travel direction, and can be discharged through the fines discharge openings 31 , 32 , 33 and 35 both towards the gob side and towards the working side. Because the cross-sections of the discharge openings are relatively large and because there are sufficiently large gaps between the connecting plates 22 and the rest bars 28 , there is no tendency for the fines to cake and clog the chain channel. With the embodiment shown in FIG. 2, an additional chain channel cleaning action can be obtained by constructing the derailment preventer 42 engaging in the discharge channel as a scraper which scrapes the chain channel as it moves along the foot 34 of the guide rail, at least as far as the connecting plates, and rakes out the fines through the discharge channel 33 and/or towards the rear fines discharge openings 31 . In the embodiment shown in FIG. 6, the discharge of fines is additionally assisted by giving the bottom boundary 26 of the chain channel 23 a convex or roof-shaped form, with a ridge 44 extending approximately along the chain channel 23 in the longitudinal centre plane of the channel, and with chute surfaces 45 for the fines falling away on either side of the ridge 44 to the fines discharge openings 31 , 32 . In this embodiment, fines dropping through the chain channel from above fall on the sloping chute surfaces and are at once led down the slopes and out through the discharge openings. The rail profile 36 illustrated in this embodiment has a flat upper surface 46 for a running wheel (not shown in the drawing) which has no special profile on its periphery. To prevent the chain from being unintentionally lifted out of the chain channel while the machine is in operation, projections 47 which overhang the working side shanks 48 of the horizontal chain-links 27 in the chain channel, are formed by the guide rail in all the illustrated embodiments, in the region of its rail profile 36 . The gob-side shanks 49 are similarly retained in the chain channel by releasably attaching a retaining bar 50 or the like to the working side of the rear wall 25 , as indicated in FIG. 1 . This retaining bar together with the shoulders 47 on the rail profile keeps the pin drive chain on the rest bars 28 and connecting plates 22 , and prevents it from creeping out of the chain channel, which is open at the top. With the retaining bar 50 removed, the pin drive chain 24 can, with a slight twist, be laid in the chain channel of the conveyor trough sections from above, or lifted out of the chain channel again when chain replacement is necessary.
In the driving and guide arrangement according to the invention, the drive chain in a chain channel bounded by a guide rail and a rear wall is supported only on series of spaced, narrow support elements at least some of which may form connecting plates welded between the rear wall and the guide rail. As the narrow support elements are spaced apart from one another, fines getting into the chain channel from above readily drop between them, and emerge freely through face side and gob-side discharge openings in the chain channel. Caking of fines in the chain channel is largely prevented in the arrangements, which are fabricated as welded constructions and are therefore particularly economical to produce.
4
CROSS-REFERENCE TO RELATED APPLICATION [0001] This application is a national stage application and claims the benefit of the priority filing date in PCT/RU2011/000552 referenced in WIPO Publication WO2013/015704 filed on Jul. 26, 2011. The earliest priority date claimed is Jul. 26, 2011. FEDERALLY SPONSORED RESEARCH [0002] Not Applicable SEQUENCE LISTING OR PROGRAM [0003] Not Applicable BACKGROUND [0004] The invention is directed to the fields of pharmaceutics, pharmaceutical nanotechnology and pharmacology and relates to a system for the delivery of biologically active compounds, including medicinal products, into an organism and to a method for the preparation of said system, wherein said invention can be used in medicine. [0005] Systems for the delivery of biologically active compounds, including medicinal products, into an organism in the form of phospholipid nanoparticles with particle size of 10-30 nm, comprising phosphatidylcholine from plants and maltose (1), are known in the art. [0006] Systems for the delivery of biologically active compounds, including medicinal products, into an organism as a combination thereof with a polymer excipient are known in the art. Nanoparticle-containing medications may be prepared by introducing a biologically active substance, or a medicinal product, during or after obtaining a polymeric dispersion. The active ingredients are dissolved, captured, or adsorbed on the surface of nanoparticles. A combination of said mechanisms is also possible [2]. However, polymer nanoparticles may have substantial disadvantages. With the exception of alkyl cyanoacrylate, most monomers form slowly biodegradable or non-biodegradable polymers. In addition, the molecular weight of the polymeric material cannot be fully controlled. The residues in the polymerization medium may be toxic, which would require a follow-up purification of the colloid system. Often, during polymerization, monomer molecules can react with medicinal product molecules, which results in the deactivation or destruction thereof [3]. [0007] A nanodiamond-based system for the delivery of medicinal products, with particle size of 5 nm, comprising an adsorbed antibiotic Doxorubicin and hydrated water molecules is known in the art [4]. [0008] A nanodiamond-based system for the delivery of medicinal products, comprising carboxylated nanodiamond particles with particle size of 3-5 nm, wherein CH 2 0(CH2)6NH2-groups with the antitumor diterpenoid paclitaxel covalently bonded thereto attach to the surface of said nanodiamond in the course of several chemical transformations is known in the art [5]. [0009] Fluorine-modified nanodiamond particles with particle size of 2-10 nm containing up to 5% of fluorine at are known in the art [6]. The obtained nanodiamond that is modified with fluorine is used to prepare conjugants with such substances as alkyl lithium compounds, diamines, and amino acids. Said conjugants can be used as bonding agents in polymer compositions, abrasives and coatings, adsorbents, biosensors, and nanoelectromechanical systems. [0010] A method for improving the efficacy of medicinal products by chemically (covalently) bonding the molecules of medicinal products to nanodiamond particles, 10 nm in size, via fluorine atoms and/or hydroxyl groups on the surface thereof is known in the art [7]. [0011] Fluorine atoms in an organic substance increase its toxicity; in particular, such substance can damage the nervous system, lungs, and liver. Despite being chemically inert, even the perfluorinated organic compounds alter the microsomal system of the xenobiotic biotransformation indicators (foreign bodies) in the liver [8]. Thus, the fluorine atoms covalently bound to the C 60 fullerene molecule, which is the closest nanostructured carbon analog of the nanodiamond, have been shown to increase its overall toxicity 2.4-5 times [9]. [0012] Thus, preparation of nanodiamond particles with no fluorine atom content, which could be used as a system for the delivery of biologically active substances into an organism, present an important and practically relevant task for medical and pharmaceutical industries. [0013] A method to increase the efficacy of medicinal products by chemical (covalent) bonding of the medicinal product molecules with nanodiamond particles 10 nm in size via amino or acyl chloride groups on the surface thereof is known in the art [10]. [0014] Nanodiamond particles modified with chlorine, wherein the chlorine content is up to 12%, wherein the particle size in the suspension one month post synthesis is 70 nm, and 9 months post synthesis is 180 nm, respectively, are known in the art [11]. These particles are larger in size than the optimally sized particles required for medical use. In addition, this work was not able to produce the highest chlorine content on the nanodiamond's surface, which, in turn, would, subsequently, not yield a maximum content of the medicinal product on the nanodiamond's surface, which invariably reduces the efficacy of the delivery system. Although the inventors [11] point out that testing of nanodiamond samples, modified with chlorine, by the X-ray photoelectron spectroscopy (XPE) method confirm the bonding of chlorine atoms with the surface carbon atoms, the supporting data are not listed. In addition, the analysis of the IR-spectra presented in the article, which the inventors themselves conducted, does not confirm the presence of such chemical bonds. Purportedly, this is because the chlorine atoms are bound to the nanodiamond's surface by way of adsorption and not by covalent bonds. Consequently, medicinal products do not create sufficiently strong chemical bonds with said surface of the nanodiamond, and the system becomes inefficient. [0015] The following method for the preparation of said nanodiamond's particles, modified with chlorine, and the embodiment thereof are also known in the art [11]. Chlorination of the nanodiamond's particles is conducted by liquid-phase chlorination of the reduced nanodiamond in a CC1 4 solution saturated with chlorine at room temperature with constant stirring for 72 hours and exposure to visible light. Upon chlorination, the nanodiamond particles are washed with dry CC1 4 , centrifuged, and the residue is dried for 5-6 hours under 13-26 Pa pressure at 70-80° C. [0016] In the embodiment of said method, the particles of nanodiamond modified with chlorine are prepared in the CC1 4 plasma for 4 hrs. [11]. [0017] The inventors [11] concluded that the bond they created between the chlorine atoms and the nanodiamond is less stable in air (due to the purported adsorption nature of the bond) than the bond between the nanodiamond and the fluorine atoms. In addition, the highest possible number of fluorine atoms bound to the surface of the nanodiamond is higher than that of chlorine atoms, which makes the chlorinated nanodiamond particles less favorable for the participation in the future covalent bonding reactions of chemical compounds as compared to the fluorinated nanodiamond particles. [0018] Thus, the task of creating nanodiamond particles that do not contain fluorine and can effectively form covalent bonds with various biologically active compounds, comprising medicinal products, has been only partially solved. Moreover, a complete substitution of the chlorine atoms (covalently bound to the nanodiamond's surface with molecules of biologically active compounds) creates perspective systems for the delivery of biologically active compounds containing no halogen atoms on their surface, which inhibits uncontrollably increased toxic effects. This requirement is of utmost importance for any medicinal and medical products used in the medical and pharmaceutical industry. SUMMARY [0019] A system for the delivery of biologically active compounds into an organism according to the present invention is described as a grey ultradispersed nanodiamond powder ( FIG. 1 ) with particle sizes of 2-10 nm ( FIG. 2 ), wherein the surface of said particles is modified with chlorine, wherein the chlorine content is up to 14% ( FIG. 3 ). In the claimed delivery system, distribution of the aggregate sizes in an aqueous suspension is 40-70 nm ( FIG. 4 .). DRAWINGS [0020] FIG. 1 . Photomicrographs of the ultradispersed structure of the system for the delivery of biologically active compounds obtained by scanning with an electron microscope; a—23.83 thousand times magnification, b—8.57 thousand times magnification. [0021] FIG. 2 . Photomicrographs of the system for the delivery of biologically active compounds obtained by transmission electron microscopy. [0022] FIG. 3 . C 1s, O 1s, N 1s, Cl 2p XPE-spectra of the particle surfaces of the system for the delivery of biologically active compounds. [0023] FIG. 4 . Size distribution of the particles of the system for the delivery of biologically active compounds in an aqueous suspension prepared by the laser dynamic light scattering method. [0024] FIG. 5 . IR-spectrum of the system for the delivery of biologically active compounds. [0025] FIG. 6 . Preparation scheme for the system for the delivery of biologically active compounds. [0026] FIG. 7 . Preparation scheme for the nanodiamond and ethylenediamine conjugate. [0027] FIG. 8 . Preparation scheme for the nanodiamond and glycine conjugate. [0028] FIG. 9 . Raman-scattering spectrum of the nanodiamond and ethylenediamine conjugate. [0029] FIG. 10 . Biodistribution of the nanodiamond and ethylenediamine conjugate in rats. [0030] FIG. 11 . IR-spectrum of the nanodiamond and glycine conjugate. [0031] FIG. 12 . Photomicrograph of the nanodiamond and glycine conjugate obtained by the X-ray photoelectron spectroscopy method. [0032] FIG. 13 . Photomicrograph of the nanodiamond and glycine conjugate's penetration into the lymphoblast MOLT-4 cell; a and b—are the areas of particle penetration into cells. DESCRIPTION [0033] FIG. 1 clearly shows that the claimed delivery system possesses an ultradispersed structure created by particles with a diameter smaller than the resolution ability of the used instrument (from 20 nm). Photomicrographs were obtained on a super high resolution auto emission scanning electron microscope Zeiss Ultra Plus (Carl Zeiss, Germany). The conditions of the film taking are cited on the photomicrograph. [0034] FIG. 2 shows that the claimed system for the delivery of biologically active compounds has the particle size distribution of 2-10 nm. Photomicrographs were obtained on a transmission electron microscope Jeol 1011 (JEOL, Japan). [0035] FIG. 3 shows XPE-spectra of the claimed system for the delivery of biologically active compounds. Said spectra define the nature, energy condition, and number of surface atoms of nanodiamond particles. [0036] The surface of the claimed system for the delivery of biologically active compounds is examined on a LAS-3000 instrument (Riber, France) equipped with a hemispherical analyzer OPX-150. The non-monochromatized X-ray radiation from an aluminum anode (A1a=1486.6 eV) (12 kV voltage on the tube and 20 mA emission current) is used for photoelectron excitation. Calibration of the photoelectron peaks is conducted along the C 1s carbon line with 285 eV binding energy (E b ). Vacuum in the work chamber is 6.7×10 −8 Pa. High vacuum is achieved with an ion pump. [0037] The elemental composition on the surface of the claimed system for the delivery of biologically active compounds according to the XPE data is shown in Table 1. [0000] TABLE 1 Elemental composition and surface atom-binding energy of the claimed system for the delivery of biologically active compounds. Name of the Chemical Elements Characteristics C O N Cl At % 76.7-91.2 5.0-7.1 1.8-2.2 2-4 Binding 285.3 ± 0.5 530.7 ± 0.5 399.5 ± 0.5 200.3 ± 0.5 energy, eV 408.7 ± 0.5 [0038] FIG. 4 shows the distribution curve of particle sizes in an aqueous suspension of the claimed system for the delivery of biologically active compounds, wherein the aggregate sizes are 40-70 nm. [0039] Distribution of particle sizes in the aqueous suspension of the claimed delivery system is determined by laser dynamic light scattering on a ZetaSizer instrument (Malvem Instruments, USA). [0040] FIG. 5 a shows an IR-spectrum of the claimed system for the delivery of biologically active compounds, wherein the content of chlorine on the surface is 14%. The spectrum shows a broad intense band with a maximum at 3,430 cm −1 ; a broad band with a maximum at 1,262 cm −1 ; five bands of medium intensity at 2,929, 2,892, 1,131, 846, and 680 cm −1 ; and a weak signal at 743 cm −1 . Said spectrum confirms the presence of covalently bound chlorine atoms on the surface of the claimed delivery system, the characteristic valence frequencies of said chlorine atoms are in the 650-850 cm −1 range [12]. FIG. 5 b shows an IR-spectrum of the claimed system for the delivery of biologically active compounds with a minimal chlorine content on the surface (0.1%). The spectrum shows a broad intense band with a maximum at 3,430 cm −1 ; two broad bands with maximums at 1,136 and 621 cm −1 ; two bands of medium intensity at 2,929 and 2,892 cm −1 ; and a weak signal at 1,331 cm −1 . Such low chlorine concentration on the surface of the claimed system for the delivery of biologically active compounds does not show on the IR-spectrum in the 650-850 cm −1 range. [0041] IR-spectra were registered on a FTIRS IR200 Thermonicolet instrument (Thermo Scientific, USA). Resolution—2 cm −1, number of scans—64. For testing, carefully weighed samples were mixed with the KBr powder and pressed into a tablet. [0042] Because the obtained system is not hazardous to humans and does not contain animals fluorine and fluorine compounds, which are left after biologically active compounds are bound to the nanodiamond's surface, the system can be effectively used for the delivery of biologically active compounds, including medicinal products, to humans. [0043] The invention also claims a method for preparing the system for delivery of biologically active compounds; the scheme thereof is shown on FIG. 6 . [0044] The claimed method for preparing the system for delivery of biologically active compounds into an organism comprises annealing of nanodiamond particles at 500-1,200° C. in a hydrogen gas stream and subsequent chlorination of the obtained annealed particles of the nanodiamond with molecular chlorine dissolved in CCl 4 under visible light at temperatures ranging from 50 to 70° C. Annealing is conducted at a speed of the hydrogen gas of 2-3 L/hour. Chlorination is conducted largely between 36 to 60 hours with a molecular chlorine concentration in CCl 4 of 3 to 5 wt %, followed by centrifugation, washing with CCl 4 , and drying. [0045] More precisely, the method comprises annealing of the nanodiamond in a hydrogen gas stream at 2-3 L/hour at 500-1,200° C. for 1-8 hours. The annealed particles of the nanodiamond are then chlorinated in a liquid phase with molecular chlorine. For that, chlorine obtained in the reaction between K 2 Cr 2 0 7 (or KMn0 4 ) and hydrochloric acid is dissolved in CCl 4 to 3-5 wt %. Chlorination is conducted by photochemical exposure to visible light for 36-60 hours at 50-70° C. The suspension is then centrifuged at over 6,000 rpm, washed with CCl 4 , the process is repeated 3-5 times, and the residue is dried in a vacuum to constant weight. [0046] The resulting delivery system is used to prepare conjugates with biologically active compounds, including medicinal products, from various pharmacological groups comprising: alkylating agents, in particular those containing ethylene diamines, excipients, reagents and intermediate products, and also amino acids. [0047] For diamines, the obtained particles of the claimed delivery system are suspended in dimethyl sulfoxide (CH 3 ) 2 SO; ethylenediamine is then added to the resulting suspension, followed by the addition of several drops of pyridine, and said suspension is kept at 120° C. for 24 hours. [ FIG. 7 ]. The resulting conjugate of the nanodiamond and ethylenediamine is then centrifuged at over 6,000 rpm, washed with water and acetone multiple times, and dried in a vacuum to constant weight. [0048] Said conjugate is used to deliver ethylenediamine to an organism. To prove that the set objective has been met, in preparation of said system for the delivery of biologically active compounds into an organism, after annealing, the nanodiamond is labeled with tritium by the thermal activation method [13]. The system for the delivery of biologically active compounds with a radioactive label on its surface is then prepared according to the present invention. A conjugate of said delivery system with ethylenediamine is then prepared following the aforementioned method. Said conjugate with the radioactive label is then intraperitoneally administered to a rat. The rat is euthanized, its organs are extracted, homogenized, and the radioactivity of the obtained homogenate is measured on a liquid scintillation spectrometer. [0049] For amino acids, with glycine as an example, the conjugate thereof with the delivery system is prepared according to the following procedure ( FIG. 8 ): The obtained particles of the delivery system are dissolved in a polar water-organic solvent or in water. Glycine, as amino acetic acid NH 2 CH 2 COOH, and tertiary amine are then added to the obtained suspension. Organic solvents that dissolve glycine, such as pyridine or lower aliphatic alcohols, are preferred. The obtained mixture is treated with ultrasound (50 W) for 5-60 minutes, and then kept at 50-80° C. with constant stirring for 12-48 hours. The resulting product is centrifuged at 6,000 rpm, washed with ethanol, and the residue is dried in a vacuum overnight at 70° C. [0050] The obtained conjugate is used to deliver glycine to an organism. For that, the reaction between the obtained conjugate and cellular cultures is studied under the electron microscope by cellular biology methods. [0051] The invention is illustrated by the following examples. EXAMPLE 1 [0052] A 200 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.5 L/hr. and 800° C. for 5 hours. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (4.7 wt %) in 40 ml of CCl 4 under exposure to visible light for 48 hours at 60° C. The suspension is then centrifuged at 8,000 rpm and washed with dry CCl 4 . The process is repeated 4 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 181 mg (90.5%). [0053] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing up to 14% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 50 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—78.1, O—6.0, N—1.9, Cl—14%, respectively. EXAMPLE 2 [0054] A 250 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.4 L/hr. and 800° C. for 5 hours. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (4.8 wt %) in 50 ml of CCl 4 under exposure to visible light for 36 hours at 60° C. The suspension is then centrifuged at 8,000 rpm and washed with dry CCl 4 . The process is repeated 3 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 198 mg (79.1%). [0055] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing 4.2% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 67 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—87.9, O—5.9, N—2.0, Cl—4.2%, respectively. EXAMPLE 3 [0056] A 400 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.7 L/hour and 800° C. for 5 hours. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (3.5 wt %) in 80 ml of CCl 4 under exposure to visible light for 60 hours at 60° C. The suspension is then centrifuged at 7,000 rpm and washed with dry CCl 4 . The process is repeated 3 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 339.6 mg (84.9%). [0057] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing 7.8% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 56 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—84.1, O—6.3, N—1.8, Cl—7.8%, respectively. EXAMPLE 4 [0058] A 200 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.0 L/hr. and 800° C. for 5 hours. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (5.0 wt %) in 40 ml of CCl 4 under exposure to visible light for 48 hrs. at 50° C. The suspension is then centrifuged at 6,000 rpm and washed with dry CCl 4 . The process is repeated 5 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 149.2 mg (74.6%). [0059] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing 3.0% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 70 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—87.8, O—7.1, N—2.1, Cl—3.0%, respectively. EXAMPLE 5 [0060] A 200 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.9 L/hour and 800° C. for 5 hours. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (5.0 wt %) in 40 ml of CCl 4 under exposure to visible light for 48 hrs. at 70° C. The suspension is then centrifuged at 9,000 rpm and washed with dry CCl 4 . The process is repeated 3 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 144.6 mg (72.3%). [0061] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing 9.4% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 61 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—83.3, O—5.5, N—1.8, Cl—9.4%, respectively. EXAMPLE 6 [0062] A 500 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.5 L/hour and 500° C. for 5 hours. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (5.0 wt %) in 100 ml of CCl 4 under exposure to visible light for 48 hours at 60° C. The suspension is then centrifuged at 6,000 rpm and washed with dry CCl 4 . The process is repeated 5 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 433.5 mg (86.7%). [0063] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing 5.2% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 63 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—86.5, O—6.1, N—2.2, Cl—5.2%, respectively. EXAMPLE 7 [0064] A 500 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.5 L/hour and 1,200° C. for 5 hours. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (3.3 wt %) in 100 ml of CCl 4 under exposure to visible light for 48 hours at 60° C. The suspension is then centrifuged at 7,000 rpm and washed with dry CCl 4 . The process is repeated 4 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 370.5 mg (74.1%). [0065] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing 8.8% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 58 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—83.9, O—5.5, N—1.8, Cl—8.8%, respectively. EXAMPLE 8 [0066] A 200 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.0 L/hour and 800° C. for 1 hour. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (4.6 wt %) in 40 ml of CCl 4 under exposure to visible light for 48 hours at 60° C. The suspension is then centrifuged at 9,000 rpm and washed with dry CCl 4 . The process is repeated 3 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 180 mg (90.0%). [0067] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing 3.5% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 70 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—87.5, O—6.9, N—2.1, Cl—3.5%, respectively. EXAMPLE 9 [0068] A 300 mg sample of nanodiamond is annealed in a hydrogen gas stream at 2.0 L/hour and 800° C. for 8 hours. The annealed nanodiamond particles are subjected to liquid-phase chlorination with molecular chlorine (4.6 wt %) in 60 ml of CCl 4 under exposure to visible light for 48 hours at 60° C. The suspension is then centrifuged at 6,000 rpm and washed with dry CCl 4 . The process is repeated 5 times, and the resulting residue is dried in a vacuum to constant weight. The yield of the final product is 256.2 mg (85.4%). [0069] The obtained product is a grey ultradispersed powder with particle sizes of 2-10 nm, containing 13.2% chlorine on its surface, wherein the size of the aggregates thereof in an aqueous suspension is 55 nm, said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,430 cm −1 , a broad band with a maximum at 1,262 cm −1 , five moderately intense bands at 2,929, 2,892, 1,331, 846, 680 cm −1 , and a weak signal at 743 cm −1 . The elemental composition of the surface is as follows: C—79.8, O—5.2, N—1.8, Cl—13.2%, respectively. [0070] Characteristics of the system for the delivery of biologically active compounds and parameters of the procedure by which it is prepared are listed in Table 2 for each of the examples. [0000] TABLE 2 Table summarizing characteristics of the claimed system for the delivery of biologically active compounds and conditions of its preparation. Process Example #/Process Conditions Parameters 1 2 3 4 5 6 7 8 9 Annealing 5 5 5 5 5 5 5 1 8 Time (1-8), hr. Annealing 800 800 800 800 800 500 1200 800 800 Temperature (500- 1200), ° C. Chlorination 48 36 60 48 48 48 48 48 48 Time (36-60), hr. Chlorination 60 60 60 50 70 60 60 60 60 Temperature (50-70), hr. Product 90.5 79.1 84.9 74.6 72.3 86.7 74.1 90.0 85.4 Yield, % Delivery System Characteristics Chlorine 14 4.2 7.8 3.0 9.4 5.2 8.8 3.5 13.2 Content, at % Particle Size 50 67 56 70 61 63 58 70 55 in Suspension, nm EXAMPLE 10 [0071] A 500 mg sample of the claimed delivery system prepared according to the procedure described in Example 1 is suspended in 50 ml of the solvent dimethyl sulfoxide; 2.5 ml of ethylenediamine are added to the resulting suspension followed by the addition of 2 drops of pyridine, and the suspension is then kept at 120° C. for 24 hours. The resulting conjugate of the nanodiamond and ethylenediamine is then centrifuged at 6,000 rpm, washed with water and acetone 5 times, and dried in a vacuum to constant weight. [0072] The obtained conjugate is a grey ultradispersed powder with particle sizes of 2-10 nm, characterized by Raman Scattering with strong luminescence exceeding the intensity of the nanodiamond's R-spectrum more than 50 times ( FIG. 9 ). The elemental composition of the surface is as follows: C—86.4, C—8.9, N—4.7%, respectively. [0073] The obtained conjugate is used to deliver ethylenediamine into an organism. [0074] To achieve said objective when preparing the system for the delivery of biologically active compounds, the annealed nanodiamond is labeled with tritium by the thermal activation method [13]. After the annealed nanodiamond has been labeled with tritium, it is kept in water for 48 hours, centrifuged, and the supernatant is separated and combined with a new portion of the solvent. The resulting product is a preparation of the annealed nanodiamond with the specific radioactivity of 90 Gbq/g. The system for the delivery of biologically active compounds with a radioactive label on its surface is then prepared according to the claimed method. A conjugate of the delivery system with ethylenediamine is subsequently prepared according to the method described above. The prepared radioactively labeled conjugate is then intraperitoneally administered to a rat (white outbred male, 400 g weight) as an aqueous suspension. Four hours later, the animal is euthanized, its internal organs and tissues are extracted and weighed, homogenized in aqueous NaOH and H 2 O 2 solutions, and the radioactivity of the obtained homogenate is measured on a RackBeta 1215 (Finland) liquid scintillation spectrometer (Table 3, FIG. 10 ). [0000] TABLE 3 List of the organs extracted from the rat to study distribution of the nanodiamond and ethylenediamine conjugate Type of Organ NaOH H 2 O 2 Sample # or Tissue Weight, g amount, ml amount, ml 1 Liver 0.42 2 0.05 2 Lungs 0.13 1.5 — 3 Spleen 0.26 2 0.15 4 Kidneys 0.22 1.5 0.05 5 Large 0.17 2 — Intestine 6 Small 0.12 1 — Intestine 7 Heart 0.27 2.05 0.05 8 Stomach 0.08 1.5 — 9 Muscles 0.1 1.5 — 10 Blood 0.27 3 0.25 12 Frontal Cortex 0.18 1.5 — 13 Brain Stem 0.31 2 0.05 15 Cerebellum 0.32 2.5 0.05 16 Adrenal 0.08 1 — Glands [0075] It is evident from FIG. 10 that the nanodiamond and ethylenediamine conjugate is distributed practically throughout all vital organs, while passing through the hematoencephalic barrier in different quantitative ratios. EXAMPLE 11 [0076] 200 mg of the claimed delivery system prepared according to the method described in Example 1 are suspended in 40 ml of water-alcohol mixture (water:methanol=1:1), 300 mg of glycerin as free amino acid NH 2 CH 2 COOH and 1 ml triethylamine are then added to the resulting suspension. The resulting mixture is treated with ultrasound (50 W) for 40 minutes and kept at 65° C. with constant stirring for 30 hours. The resulting product is centrifuged at 6,000 rpm, washed with ethanol, and dried in a vacuum at 70° C. overnight. The residual moisture content of the product is 2.2%. The yield of the final product is 186 mg (93%). [0077] The obtained product is an ultradispersed powder, dark grey with a bluish tint, with 2-10 nm primary particle sizes and a surface layer membrane measuring up to 1 nm ( FIG. 1 ), said product is characterized by IR-spectroscopy: a broad intense band with a maximum at 3,400 cm −1 , a strong signal at 1,621 cm −1 , six moderately intense bands at 2,924, 2,881, 1,383, 1,306, 1,212, and 1,154 cm −1 , and a weak signal at 504 cm −1 ( FIG. 12 ). The elemental composition of the surface is as follows: C—91.5, O—6.0, N—2.5%, respectively. [0078] The obtained conjugate is used for the delivery of glycine into an organism. The presence of the nanodiamond and glycine conjugate in an organism is confirmed by electron microscopy in the reaction thereof with the lymphoblast MOLT-4 cell culture. FIG. 13 demonstrates that the conjugate causes invagination of the lymphoblast's cellular membrane and subsequent penetration thereof into the cytosol. REFERENCES [0000] 1. RFPat RU 2391966, C1 06.20.2010 2. Nanotherapeutics. Drug delivery concepts in nanoscience. Translated from the English. Edited by Alf Lamprecht, M.: Nauchny Mir, 2010, pp. 10-20. 3. J. L. Grangier, M. Puygrenier, J. C. Gautier, P. Couvreur. Nanoparticles as carriers for growth hormone releasing factors//J. Control. Rel. 1991. V.15, pp. 3-13. 4. A. Adnant, R. Lam, H. Chen et al. Atomistic Simulation and Measurement of pH Dependent Cancer Therapeutic Interactions with Nanodiamond Carrier//Mol. Pharmaceutics. 2001. V. 8., pp. 368-374. 5. K.-K. Liy, W.-W. Zheng, C.-C. Wang et al. Covalent linkage of nanodiamond-paclitaxel for drug delivery and cancer therapy//Nanotechnology. 2010. V. 21. #315106. 14 pp. 6. USPat 2005/0158549 A1, Jul. 21, 2005. 7. USPat 2010/0129457 A1, May 27, 2010. 8. Russian encyclopedia of job safety. 3 volumes. 2 nd edition. Revised and enlarged edition, Volume 3. M: pub. NTs ENAS. 2007, p. 181. 9. N. N. Karkischenko, Nanoengineered drugs: Novel biomedical initiatives in pharmacology//Biomeditsina, 2009, N2, pp. 5-26. 10.USPat 2009/0226495 A1, Sep. 10, 2009. 11.G. V. Lisichkin, I. I. Kulakova, Y. A. Gerasimov et al. Halogenation of detonation-synthesized nanodiamond surfaces. Mendeleev Commun. 2009. V. 19, pp. 309-310. 12.A. Smith. Applied IR-spectroscopy. Translated from the English. M.: Mir, 1982, p. 307. 13.G. A. Badun. Compounds labeled with tritium./Methodological guidelines. M., MSU, 2008, pp. 36-37.
The invention relates to the field of pharmaceutics, pharmaceutical nano-technology and pharmacology and concerns a system for delivering biologically active agents into an organism, the system comprising a nano-diamond with a particle size of 2-10 nm, the surface of said particles being modified by chlorine with a chlorine content of up to 14%, and to a method for producing said system.
2
CLAIMS OF PRIORITY [0001] This application claims priority to an application entitled “MOBILE TERMINAL HAVING FOLDABLE DISPLAY AND OPERATION METHOD FOR THE SAME” filed in the Korean Intellectual Property Office on Jan. 9, 2009 and assigned Serial No. 10-2009-0001771, the contents of which are incorporated herein by reference. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates generally to a mobile terminal having a foldable display and, more particularly, to a mobile terminal having a foldable display that can provide a variety of functions in a user friendly and convenient manner, and an operation method for the same. [0004] 2. Description of the Related Art [0005] Recently, mobile terminals have been widely used and provide various functions related to, for example, audio file playback through an MP3 player, image capture through a digital camera module, and mobile gaming or arcade gaming. [0006] A mobile terminal is equipped with a display unit, which has a limited size owing to portability of the mobile terminal. To overcome the size and space limitations while supporting portability, mobile terminals having a foldable display unit have been developed. [0007] A mobile terminal having a foldable display unit has a mechanical structure of a folder type. Such a mobile terminal may have to perform a special operation for removing image discontinuity and blurring near the foldable zone at the middle of the display unit to produce continuous images even when the display unit is folded at a particular angle. However, it is very difficult to install a separate keypad in an existing mobile terminal having such a foldable display unit. That is, allocating separate installation space to the keypad may hinder portability and miniaturization of the mobile terminal. SUMMARY OF THE INVENTION [0008] The present invention has been made in view of the above problems, and the present invention provides a mobile terminal having a foldable display unit and an operation method for the same that can perform a variety of functions in a user friendly and convenient manner in response to input signals generated according to the folding angle. [0009] In accordance with an exemplary embodiment of the present invention, a mobile terminal having a foldable display, includes: a display unit having multiple linked display zones; an angle sensor sensing the folding angle between adjacent display zones and generating a folding event according to the folding angle; and a control unit activating an application program or controlling execution of an activated application program according to a folding event from the angle sensor. [0010] In accordance with another exemplary embodiment of the present invention, an operation method for a mobile terminal having a foldable display unit having multiple linked display zones, includes: generating a folding event by sensing the folding angle between adjacent display zones; and performing application control by activating an application program or controlling execution of an activated application program according to a generated folding event. [0011] The inventive operation method enables the user of a mobile terminal having a foldable display unit to execute a desired function by folding the mobile terminal at a specific angle. In addition, when the display unit includes a touch screen, the user can manipulate the mobile terminal in much easier and intuitive manner. BRIEF DESCRIPTION OF THE DRAWINGS [0012] The features and advantages of the present invention will be more apparent from the following detailed description in conjunction with the accompanying drawings, in which: [0013] FIG. 1 shows a mobile terminal having a foldable display unit according to an exemplary embodiment of the present invention; [0014] FIG. 2 is a block diagram of the mobile terminal in FIG. 1 ; [0015] FIG. 3 is a detailed diagram of a control unit in the mobile terminal; [0016] FIG. 4 illustrates operation of the mobile terminal according to folding angles; [0017] FIG. 5 shows an example of executing an application program on the mobile terminal; [0018] FIG. 6 shows another example of executing an application program on the mobile terminal; [0019] FIG. 7 shows yet another example of executing an application program on the mobile terminal; and [0020] FIG. 8 is a flow chart of an operation method for the mobile terminal according to another exemplary embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0021] Hereinafter, exemplary embodiments of the present invention are described in detail with reference to the accompanying drawings. The same reference symbols are used throughout the drawings to refer to the same or like parts. For the purposes of clarity and simplicity, detailed descriptions of well-known functions and structures incorporated herein may be omitted to avoid obscuring the subject matter of the present invention. Particular terms may be defined to describe the invention in the best manner. Accordingly, the meaning of specific terms or words used in the specification and the claims should not be limited to the literal or commonly employed sense, but should be construed in accordance with the spirit of the invention. The description of the various embodiments is to be construed as exemplary and illustrative purposes only and does not describe every possible instance of the invention. Therefore, it should be understood that various changes may be made and equivalents may be substituted for elements of the invention. [0022] FIG. 1 shows a mobile terminal 100 having a foldable display unit according to an exemplary embodiment of the present invention. In the description, it is assumed that the display unit includes multiple display zones, adjacent display zones can be folded at a specific angle or unfolded, and each display zone is made of a touch screen. However, the input means generating input signals or events for the multiple display zones is not limited only to the touch screen. That is, to generate input signals, a separate keypad may be provided to the mobile terminal or a removable keyboard or keypad may be utilized. [0023] Referring to FIG. 1 , the mobile terminal 100 may include a foldable display unit 101 , a frame 190 enclosing the display unit 101 , a hinge unit 170 enabling the display unit 101 to be folded and unfolded, and a touch sensor (not shown) attached on the display unit 101 . [0024] As explained hereinafter, the mobile terminal 100 having the above configuration may perform a preset function according to the folding angle of the display unit 101 , and may provide a convenient user interface that enables systematic interworking of application programs running on two display zones. [0025] The display unit 101 is foldable, and outputs a screen related to a function of the mobile terminal 100 . For example, the display unit 101 may output a boot screen, an idle screen, a menu screen, or a program activation screen. The display unit 101 may be realized using flexible liquid crystal display (FLCD) technology, and may include an LCD controller, a memory storing data, and LCD elements. In particular, the display unit 101 may be partially or completely folded relative to the hinge unit 170 . That is, two adjacent display zones of the display unit 101 may form an angle of zero to 360 degrees with each other. The display unit 101 may include a first touch screen 110 and a second touch screen 120 . The first touch screen 110 and the second touch screen 120 are joined together at one side, and they appear as a single wide screen when completely unfolded at a folding angle of 180 degrees. Each of the first touch screen 110 and the second touch screen 120 may be composed of a display panel and a touch sensor arranged on the display panel. [0026] The frame 190 encloses the foldable display unit 101 , and supports folding of the display unit 101 utilizing the hinge unit 170 . In addition to the display unit 101 and the hinge unit 170 , the frame 190 provides a space in which a printed circuit board containing a control unit, storage unit, audio processing unit and interface unit can be mounted. The frame 190 may be made of a sash or plastic material. The frame 190 may include a coupling mechanism such as a hook that fixes the display unit 101 when the display unit 101 is completely folded at a folding angle of 0 or 360 degrees. When the first touch screen 110 and the second touch screen 120 each include an LC display panel, the frame 190 may further provide a space to accommodate a backlight unit for lighting the LC display panel and optical sheets for diffusing and concentrating light. [0027] The hinge unit 170 placed on the frame 190 enables folding of the frame 190 and the foldable display unit 101 . In fact, as the frame 190 accommodates the display unit 101 , folding of the frame 190 results in folding of the display unit 101 . That is, when the user folds the frame 190 with respect to the hinge unit 170 , the display unit 101 is folded accordingly. The hinge unit 170 may support a rotation corresponding to the maximum folding angle of the display unit 101 . Next, a detailed description is given of the mobile terminal 100 . [0028] FIG. 2 is a block diagram of the mobile terminal 10 . In the description, it is assumed that the mobile terminal 100 has two display zones, each of which is composed of a touch screen. However, it should be noted that the teachings of the present invention may apply to a terminal having additional number of display zones. [0029] Referring to FIG. 2 , the mobile terminal 100 includes a first touch screen 110 , a second touch screen 120 , an audio processing unit 130 , an interface unit 140 , a storage unit 150 , a hinge unit 170 accommodating an angle sensor 180 , and a control unit 160 . [0030] The mobile terminal 100 having the above configuration may sense the folding angle of the display panel through the angle sensor 180 in the hinge unit 170 , and selectively control the activation of application programs and the operation of an activated application program on the basis of the sensed folding angle. [0031] The first touch screen 110 may include a display panel to produce images under the control of the control unit 160 , and a touch sensor to generate input signals corresponding to touch events of the user. The first touch screen 110 is accommodated in the frame so as to be rotatable at a preset angle relative to the hinge unit. The first touch screen 110 may display various screens, such as an application related screen for activating one of application programs stored in the storage unit 150 , a photograph related screen for browsing photographs, a message screen for composing a message or memo, and an icon screen for icons associated with various menu items. The first touch screen 110 detects a touch event occurring at a point in a displayed screen and sends the detected touch event to the control unit 160 . The first touch screen 110 is adjacent to the second touch screen 120 and is joined thereto. [0032] The second touch screen 120 may have the same structure as that of the first touch screen 110 . Under the control of the user or the control unit 160 , the second touch screen 120 may output the same screen as that of the first touch screen 110 or may output a screen different from that of the first touch screen 110 . For example, while the first touch screen 110 displays a screen related to an activation of a first application program, the second touch screen 120 displays another screen related to an activation of a second application program. Alternatively, the first touch screen 110 and the second touch screen 120 may display different screens related to the same application program. For example, when the first touch screen 110 outputs video images related to playback of a video file, the second touch screen 120 may display a screen containing buttons for controlling playback of the video file. The second touch screen 120 is adjacent to the first touch screen 110 and is joined thereto. Utilization of the first touch screen 110 and the second touch screen 120 is further detailed later. [0033] The audio processing unit 130 includes a speaker SPK to reproduce audio data received during a call, and a microphone MIC to collect an audio signal such as a voice signal of the user. In particular, the audio processing unit 130 may reproduce an audio signal of an application program executed according to the folding angle of the display unit 101 . For example, when an audio file is mapped to a specific folding angle of the display unit 101 , folding the display unit 101 at the folding angle may cause the audio file to be played back through the audio processing unit 130 under the control of the control unit 160 . [0034] The interface unit 140 provides a communication path leading to another mobile terminal or an external memory chip. The interface unit 140 may act as a radio frequency unit for wireless communication, and may act as an USB (universal serial bus) interface or UART (universal asynchronous receiver/transmitter) interface for serial communication. The interface unit 140 may establish a communication channel to one of an external mobile terminal, a memory chip, a mobile communication system and an Internet network, and may receive a content such as an image file or an audio file through the communication channel. The interface unit 140 may act as a broadcast receiving module, and send a broadcast signal received from a broadcast network to the control unit 160 . [0035] The storage unit 150 stores application programs related to functions of the present invention, an application program for operating the angle sensor, application programs for playing back various stored files, and key maps or menu maps for operating the first touch screen 110 and second touch screen 120 . The key maps may include a keyboard map, a 3*4 key map, a qwerty key map, a control key map, and other form of map know to artisians for controlling a currently active application program. The menu maps may include a menu map for controlling a currently active application program, and a menu map containing various menu items of the mobile terminal. The key maps and menu maps may be output according to settings given by the designer or may be changed according to user settings. The storage unit 150 may provide a buffer temporarily storing sensing data collected by the angle sensor and touch screens. The storage unit 150 may include a program area and a data area. [0036] The program area may store an operating system (OS) for booting and operating the mobile terminal 100 , and various application programs, such as an application program for playing back various files, an application program for handling calls, a web browser for connecting to an Internet server, an application program for playing back MP3 audio materials, an application program for outputting photographs and images, and an application program for playing back moving images. In particular, the program area may store an application program for operating the angle sensor 180 , and an application program for operating the touch sensor on the touch screen. [0037] The data area may store data generated by the user of the mobile terminal 100 , contents received through the interface unit 140 , and user data input through the first touch screen 110 or the second touch screen 120 . In particular, the data area may store a function table. The function table defines mappings between touch events from the touch sensor or folding angles from the angle sensor 180 and control commands. For example, the function table may include a mapping between a folding angle of 90 degrees and a control command “output the menu icon to at least one of the first touch screen and the second touch screen”. In this case, when the angle sensor 180 generates a sensing signal indicating a folding angle of 90 degrees, the menu icon is output to at least one of the first touch screen 110 and the second touch screen 120 . The function table may include a mapping between a folding angle of 180 degrees and a control command “play back a video file pre-selected or selected through a touch event on at least one of the first touch screen and the second touch screen”. In this case, when the angle sensor 180 generates a sensing signal indicating a folding angle of 180 degrees, the selected video file is played back on at least one of the first touch screen 110 and the second touch screen 120 . The function table may include a control command “output the key map or menu map according to a specific folding angle of the display unit 101 ”. As described above, the function table contains control commands for activating application programs or controlling operation of an activated application program according to detected touch events and folding angles sensed by the angle sensor 180 . Application activations and controls based on the function table are further described later. [0038] The angle sensor 180 is installed in the hinge unit 170 , and measures the folding angle of the display unit 101 and sends the measured angle value to the control unit 160 . The angle sensor 180 may be realized using a geomagnetic sensor, a gyro sensor, an acceleration sensor, or other sensors know by artisians that can measure an angle relative to the ground. The angle sensor 180 may also be realized using a mechanical structure. For example, a hinge-shaped member with regular grooves or prominences and depressions, or a gear-shaped member may be used to measure the folding angle of the display unit 101 . When the angle sensor 180 is realized using a geomagnetic sensor or a gyro sensor, it can sense not only the folding angle of the display unit 101 but also the placement angle of the mobile terminal 100 . For example, when the display unit 101 is folded at an angle of 90 degrees, the angle sensor 180 may generate a folding event indicating a 90-degree angle and send the folding event to the control unit 160 . Thereafter, when the mobile terminal 100 is placed vertically upright so that a side of the first touch screen 110 and a side of the second touch screen 120 are placed on the same surface, the angle sensor 180 may generate an event indicating the placement angle and send the generated event to the control unit 160 . To achieve this, the angle sensor 180 may include a first sensing element for sensing the folding angle of the display unit 101 and generating a corresponding event, and a second sensing element for sensing the placement angle of the mobile terminal 100 and generating a corresponding event. The angle sensor 180 may include a single sensing element capable of sensing both the folding angle of the display unit 101 and the placement angle of the mobile terminal 100 , and generating corresponding events. [0039] The control unit 160 controls supply of power to the individual components of the mobile terminal 100 , and controls signal exchange between the components thereof to carry out necessary functions. In particular, the control unit 160 controls the operation of the mobile terminal 100 in various ways on the basis of the function table stored in the storage unit 150 . To achieve this, as shown in FIG. 3 , the control unit 160 includes a sensing detector 161 and a function controller 163 . [0040] The sensing detector 161 detects a touch event generated by a first touch sensor of the first touch screen 110 , a touch event generated by a second touch sensor of the second touch screen 120 , a folding event generated by the angle sensor 180 measuring the folding angle of the display unit 101 , and a placement event generated by the angle sensor 180 measuring the placement angle of the mobile terminal 100 , and sends the detected event to the function controller 163 . The sensing detector 161 may control the time points at which the first touch sensor, the second touch sensor and the angle sensor 180 are activated. For example, the sensing detector 161 may activate the angle sensor 180 after turning on of the mobile terminal 100 . The sensing detector 161 may activate the first touch sensor and the second touch sensor when the folding angle of the display unit 101 measured by the angle sensor 180 is greater than or equal to a preset angle. The sensing detector 161 may deactivate the angle sensor 180 in response to a particular touch event generated by the first touch sensor and the second touch sensor (i.e. by the user). The sensing detector 161 may output a key map or menu map to the display unit 101 under the control of the control unit 160 after an activation of the first touch sensor and the second touch sensor. Hence, the sensing detector 161 may identify a selected key or menu item by matching a touch event generated by one of the first touch sensor and the second touch sensor with the key map or menu map, and notify the function controller 163 of the selected key or menu item. [0041] The function controller 163 may receive various events including a folding event, a placement event, a touch event generated by the first touch sensor and a touch event generated the second touch sensor from the sensing detector 161 , and may control a currently active application program or activate a new application program according to the received events. Thereto, the function controller 163 may refer to the function table stored in the storage unit 150 , and control the operation of a currently active application program or activation of a new application program on the basis of the current event and the function table. Application control of the function controller 163 is further described below with reference to the drawings. [0042] As described above, the mobile terminal having a foldable display unit employs an angle sensor to measure the folding angle of the display unit, and controls the operation of an active application program or activates a new application program according to folding angles measured by the angle sensor. In addition, the mobile terminal may execute application programs in an independent or unified way on two display zones that are manipulated respectively by two touch sensors. [0043] FIG. 4 illustrates the operation of a mobile terminal according to folding angles. As the following description, representative folding angles including 0, 90, 120 and 180 degrees are selected and utilized. However, the present invention is not limited to such angles, and other angles, not limited to, such as 30, 60, 150, 210, 240, 270, 300 and 330 degrees may also be utilized as folding angles. In the mobile terminal, the folding angle may be sensed at an increment of 5 or 10 degrees from zero degrees for application control. [0044] Referring to FIG. 4 , folding state A (folding angle of 120 degrees), folding state B (180 degrees), folding state C (0 degrees) and folding state D (90 degrees) are depicted. The mobile terminal is initially in folding state C where the first touch screen and the second touch screen face each other. In folding state C, the folding angle is zero degrees, and, if an application program is in execution, the mobile terminal may stop execution of the application program. For example, it is assumed that the mobile terminal is playing back a video file in folding state A or D. Thereafter, when the mobile terminal is transitioned to folding state C, it may pause the playback of the video file. To be more specific, when the mobile terminal is transitioned from folding state A or folding state D, the angle sensor may detect a change in the folding angle and send a zero-degree folding event to the control unit. The control unit may refer to the function table and perform the application control corresponding to a folding angle of zero degrees, i.e. folding state C. For a zero-degree folding event, the control unit may apply different control operations to application programs of different types. For example, in response to occurrence of a zero-degree folding event during playback of a video file, the mobile terminal may pause a playback of the video file. In response to occurrence of a zero-degree folding event during web browsing, the mobile terminal may terminate an execution of the web browser or pause execution thereof with browser window minimization according to the user's settings, and may control the audio processing unit to stop audio output. Thereafter, when the mobile terminal is transitioned from folding state C back to folding state A or D, it may resume a playback of the video file or restore the original browser window. In the case when no active application program was present at the previous folding state (for example, idle state), the mobile terminal may automatically play back a video or audio file pre-selected by the user. In response to occurrence of a 90 or 120-degree folding event when the display unit is turned off, the mobile terminal may turn on the display unit and activate a preset application program, for example, a web browser for accessing the Internet. Note that application control described above may be specified in the function table, and the contents of the function table may be changed by the user. For user convenience, the mobile terminal may display a textual description regarding mappings between folding events and control operations according to the folding angle. [0045] Upon being transitioned from folding state A or D to folding state B, the mobile terminal may display video images in a wide screen mode. For example, it is assumed that the mobile terminal displays video images on the first touch screen and displays keys for controlling video playback on the second touch screen in folding state A or D. When transitioned to folding state B, the mobile terminal may display video images on both the first touch screen and the second touch screen as a single screen. At this time, the mobile terminal may adjust the video format from a 4:3 ratio for the first touch screen to a 16:9 ratio for the first and second touch screens. Thereafter, upon being transitioned from folding state B back to folding state A or D, the mobile terminal displays video images on the first touch screen and displays keys for controlling video playback on the second touch screen. [0046] As another example, it is assumed that the mobile terminal in folding state A or D displays photographs on the first touch screen for browsing and displays a window for playing back a music file on the second touch screen. Upon being transitioned from folding state A or D to folding state B, the mobile terminal 100 may display photographs on both the first touch screen and second touch screen, and may continue playing back the music file through background processing. As described above, for a transition from folding state A or D to folding state B, the mobile terminal may give a priority to the first touch screen over the second touch screen, or the priority can be given to the second touch screen. That is, when being transitioned from folding state A or D to folding state B, the mobile terminal may display a window that was activated on the first touch screen in a full screen mode on both the first touch screen and second touch screen, may hide a window that was activated on the second touch screen, and may pause or end execution of an application activated on the second touch screen or process the same in the background. Alternatively, the mobile terminal may assign priority values to application programs. That is, when being transitioned from folding state A or D to folding state B, the mobile terminal may display a window related to a high-priority active application program in a full screen mode on both the first touch screen and second touch screen, and may pause or end execution of a low-priority active application program or process the same in the background. [0047] For a transition from folding state B to folding state A or D, it is assumed that the mobile terminal displays a window related to an active application program such as a video player or web browser in a full screen mode on both the first touch screen and second touch screen in folding state B. When being transitioned to folding state A or D, the mobile terminal may display a resized window related to the active application program on the first touch screen, and may display a window containing a key map or menu map for video playback or web browsing on the second touch screen. [0048] When being transitioned from folding state B directly to folding state C, the mobile terminal may pause or end execution of an active application program, or minimize the window related to the same. When being transitioned rapidly from folding state B via folding state C back to folding state B, the mobile terminal may perform a special operation such as decalcomania. For example, it is assumed that a particular image is displayed on the first touch screen in folding state B. Upon being transitioned from folding state B via folding state C back to folding state B, the mobile terminal may display the same image on both the first touch screen and the second touch screen (a decalcomania). For another example, it is assumed that the mobile terminal displays icons or contents on the first touch screen and the second touch screen in folding state B. Upon being transitioned from folding state B via folding state C back to folding state B, the mobile terminal may display randomly mixed icons or contents on the first touch screen and the second touch screen. Here, the mobile terminal may apply the decalcomania operation only to an image selected by a tap or to a section selected by a drag on the first touch screen. [0049] When being transitioned from folding state C to folding state A or D, the mobile terminal may display the current time as a text string or as a round clock with hour, minute and second hands on the first touch screen, and may display a single photograph in a fixed form or many photographs in a slide form on the second touch screen. At this time, the mobile terminal may deactivate the touch sensors of the first touch screen and second touch screen. [0050] When being transitioned from folding state A, B or D via folding state C back to the original folding state, the mobile terminal may perform a special function (such as content mixing) of an active application program. To be more specific, it is assumed that the mobile terminal activates a search function for photographs or moving images using icons or images on the first touch screen, and activates a search function for music files on the second touch screen in folding state A, B or D. Upon being transitioned from folding state A, B or D via folding state C back to the original folding state, the mobile terminal may create a new content by mixing a photograph or moving image on the first touch screen with a music file on the second touch screen. For example, it is assumed that ten photographs are listed in a multi-view format on the first touch screen, and three music files are listed as icons on the second touch screen in folding state A, B or D. Upon being transitioned from folding state A, B or D via folding state C back to the original folding state, the mobile terminal may combine the ten photographs into a slide format and edit the three music files into a background music file for the combined photographs. Thereafter, the mobile terminal may save the content composed of the photographs and music files. [0051] When the mobile terminal is transitioned from folding state C via folding state D and folding state A to folding state B, it may activate an application program for each folding state transition. That is, upon being transitioned from folding state C to folding state D, the mobile terminal activates a first application program and outputs a to corresponding window on the first touch screen. Upon being transitioned from folding state D to folding state A, the mobile terminal activates a second application program and outputs a corresponding window on the second touch screen. Upon being transitioned from folding state A to folding state B, the mobile terminal activates a third application program and outputs a corresponding window on one of the first touch screen and the second touch screen. Here, the mobile terminal may continue the execution of a selected one of the first application program and the second application program without activating a third application program. [0052] In particular, to suppress the generation of inadvertent folding events caused by transitions between folding states, only when a specific folding angle is sustained by the mobile terminal for longer than or equal to a preset time, the angle sensor may generate a corresponding folding event and send the folding event to the control unit. [0053] The mobile terminal may perform further application control according to occurrence of a placement event. For example, when being transitioned to folding state A or D, the mobile terminal may refers to the function table, activate a preset application program, and display a corresponding window on one of the first touch screen and the second touch screen. When the user places the mobile terminal in folding state A or D vertically upright so that a side of the first touch screen and a side of the second touch screen are placed on the same surface, the angle sensor may generate a corresponding placement event and send the placement event to the control unit. Upon reception of the placement event, the control unit may refer to the function table and control execution of the activated application program on the touch screen. Here, the function table may contain triples of application program, placement event, and control command as entries. [0054] When the mobile terminal is in folding state A or D, the control unit may control the first touch screen to display a window related to the activation of a scheduler and control the second touch screen to display a photograph, image or moving image. Thereafter, when the user changes the placement of the mobile terminal, the control unit may control the touch screens to fix screen images or to rotate screen images with reference to the function table. For example, when the scheduler window and the image window are in a landscape orientation, the control unit may control the touch screens to rotate the scheduler window and the image window in portrait orientation according to the occurrence of a placement event. After occurrence of the placement event, the control unit may deactivate the touch sensors of the touch screens. Thereby, the mobile terminal may act as an electronic frame for a calendar or photograph. In folding state A or D, the folding angle of the mobile terminal is less than 180 degrees. The above description is also applicable to a folding angle greater than 180 degrees. For example, when the folding angle of the mobile terminal is fixed at 270 or 300 degrees, the mobile terminal may act an electronic frame in a direction opposite to the case of folding state A or D. In particular, to suppress an excessive sensitivity to minor movement or shaking, it is preferable to generate a placement event for operation control only when a specific placement condition is sustained for longer than or equal to a threshold time. The mobile terminal may provide a menu enabling the user to set the threshold time for sensitivity adjustment. If the sensitivity level is high (i.e. the threshold time is short), the mobile terminal may regard shaking as a placement condition. [0055] As described above, the mobile terminal of the present invention may receive a folding event as an input signal from the angle sensor, and perform application control in various ways conformable to the touch screens on the basis of the function table and received folding events. [0056] FIG. 5 shows one example of executing an application program on the mobile terminal having a foldable display unit. [0057] In FIG. 5 , the mobile terminal displays a menu map on the first touch screen 110 . The menu map on the first touch screen 110 includes a message menu 111 , a video menu 113 , and a file menu 115 . The present invention is not limited to theses menus, and may further provide other menus or menu items. The mobile terminal lists various image files as icons on the second touch screen 120 . The image files listed on the second touch screen 120 may be associated with the file menu 115 activated on the first touch screen 110 . The control unit of the mobile terminal may control the execution of application programs separately on the first touch screen 110 and the second touch screen 120 . [0058] In operation, the user selects the video menu 113 on the first touch screen 110 by tapping (denoted by ‘A’) with a left hand finger, and selects an image icon 121 on the second touch screen 120 by tapping (denoted by ‘B’) and dragging (flick) toward the first touch screen 110 with a right hand finger. [0059] Then, the mobile terminal may move the selected image icon 121 on the second touch screen 120 toward the selected video menu 113 on the first touch screen 110 . As shown in FIG. 5 , the image icon 121 is continuously displayed during the movement, and is removed from the second touch screen 120 after the movement. [0060] To be more specific, when the folding angle of the mobile terminal is sustained at 180 degrees, the control unit may control the first touch screen 110 and the second touch screen 120 to display a menu map in full screen mode. Later, when the user selects and activates a file menu 115 of the menu map, the control unit may control only the first touch screen 110 to display a window for an application program related to the menu map and to resize the menu map on the first touch screen 110 , and may control the second touch screen 120 to display image icons contained in the file menu 115 . Here, the control unit may distinguish a sensing signal from the touch sensor of the first touch screen 110 from a sensing signal from the touch sensor of the second touch screen 120 . [0061] When a touch event occurs on the touch screen 110 or 120 , the control unit may output an indication of event application. For example, when the video menu 113 is selected through tap ‘A’ on the first touch screen 110 , the control unit may indicate the selection by changing the video menu 113 in color or shading so that the video menu 113 is easily distinguished from other items. When the image icon 121 is selected through tap ‘B’ on the second touch screen 120 , the control unit may indicate the selection by changing the image icon 121 in color or shading. [0062] When tap ‘B’ is extended to a flick, the control unit may move the selected image icon 121 according to the flick event (file moving). Hence, the control unit may apply touch events generated by the first touch screen 110 and the second touch screen 120 respectively to a menu handling program and a file search program. [0063] As described above, the mobile terminal, having a foldable display unit with two adjacent touch screens, may cause two application programs separately running on the two touch screens to cooperate with each other according to generated touch events. [0064] FIG. 6 shows another example of executing an application program on the mobile terminal having a foldable display unit. [0065] In FIG. 6 , the mobile terminal displays an idle window on the first touch screen 110 and displays a book 123 with multiple bookmarked pages on the second touch screen 120 . When the user touches a bookmarked page A and a bookmarked page B, the control unit of the mobile terminal may recognize the touched bookmarked page A and bookmarked page B as being selected by matching touch points on the second touch screen 120 with the bookmarked pages. [0066] Then, the control unit may control the first touch screen 110 to display the selected bookmarked pages, and control the second touch screen 120 to continue the display of the book 123 . Here, the control unit may control the first touch screen 110 to separately display the bookmarked page A (denoted by 112 ) and the bookmarked page B (denoted by 114 ). In other words, upon selection of a bookmarked page A on the second touch screen 120 , the control unit may display the bookmarked page A on the first touch screen 110 . Upon selection of a bookmarked page B on the second touch screen 120 , the control unit may display the bookmarked page B on the first touch screen 110 . Here, the control unit may control the first touch screen 110 to display the bookmarked page A and bookmarked page B so that the bookmarked page A and bookmarked page B do not overlap with each other. Alternatively, the control unit may control the first touch screen 110 to display the bookmarked page A and bookmarked page B so that the bookmarked page A and bookmarked page B partially overlap with each other to make them further selectable. [0067] In the above description, the second touch screen 120 displays a book 123 with multiple pages. This description may also be applied to a phone directory with multiple bookmarked phonebooks, where the phonebooks are associated with groups of members. That is, upon selection of a bookmarked phonebook of a phone directory displayed on the second touch screen 120 , the control unit may control the first touch screen 110 to display the selected bookmarked phonebook. The displayed phonebook may contain a list of contacts such as a telephone number, photograph, address, birth date, anniversary, and so forth. [0068] As described above, the mobile terminal having a foldable display unit may display a window for a particular application program on one of the touch screens, and display an auxiliary window for the application program on the other touch screen. [0069] FIG. 7 shows yet another example of executing an application program on the mobile terminal having a foldable display unit. [0070] In FIG. 7 , the mobile terminal displays a plurality of images or icons associated with images on the first touch screen 110 . This may be caused when the user selects a menu associated with an image browsing function. Alternatively, in the case where the image browsing function is set as a default function for a 180-degree folding event, the mobile terminal may display images or icons as shown in FIG. 7 when unfolded at 180 degrees. The image browsing function may also be set as a default function for a 120-degree folding event or a 90-degree folding event, and but this setting may be changed or adjusted by the user. [0071] The mobile terminal displays an edit area 126 and an edit tool area 128 on the second touch screen 120 for editing one of the images listed on the first touch screen 110 . An image editing function may be activated on the second touch screen 120 by selection of a menu. The image editing function may also be activated on the second touch screen 120 by a folding event generated according to the folding angle of the mobile terminal. For example, in response to occurrence of a 120-degree folding event or a 90-degree folding event, the image browsing function may be activated on the first touch screen 110 . Later, in response to occurrence of a 180-degree folding event, the mobile terminal may activates the image editing function on the second touch screen 120 and display windows related to the image editing function. Here, the function table may contain an entry linking the image editing function to the image browsing function. That is, the function table may contain a control command that causes an activation of the image editing function in response to occurrence of a particular folding event after the image browsing function is activated. Hence, the mobile terminal may control execution of the image browsing function and image editing function in a coordinated manner. [0072] Thereafter, the user may select an image or icon to be edited on the first touch screen 110 , and move the selected image or icon to the edit area 126 of the second touch screen 120 through dragging. For easy editing, the control unit may fit the image or icon into the edit area 126 by resizing. In this case, the control unit may enlarge the image or icon for better view. In addition to dragging as described above, image movement may be performed through various schemes. For example, the control unit may move a particular image, which is indicated by a touch event such as a double tap, long tap and flick on the first touch screen 110 , to a preset area of the second touch screen 120 . After moving the image, the control unit may remove the image or icon from the first touch screen 110 . [0073] The user may edit the image in the edit area 126 of the second touch screen 120 using individual editing tools in the edit tool area 128 provided therein. In response to occurrence of a touch event such as a flick or double tap after the completion of editing the image, the mobile terminal may move the edited image to the first touch screen 110 . The edited image may be resized for the first touch screen 110 . [0074] When the folding angle is 120 degrees or 90 degrees, the mobile terminal may activate the image editing function on the second touch screen 120 with reference to the function table. When the folding angle becomes 180 degrees, the control unit may deactivate the image editing function on the second touch screen 120 and display a window in full screen mode for the image browsing function on both the first touch screen 110 and the second touch screen 120 . The control unit may resize the images or icons for smooth image browsing by the use of both the first touch screen 110 and the second touch screen 120 or only the first touch screen 110 . [0075] As described above, the mobile terminal may activate related application programs on the first touch screen and the second touch screen 120 , and control execution of the application programs in a coordinated manner according to folding events and user requests with reference to the function table. [0076] FIG. 8 is a flow chart of an operation method for the mobile terminal having a foldable display unit according to another exemplary embodiment of the present invention. [0077] Referring to FIG. 8 , upon power on, the components of the mobile terminal are initialized ( 201 ). After initialization, the mobile terminal activates preset application programs related to, for example, the idle screen, a menu window, and a sleep feature ( 203 ). The mobile terminal supplies power to the angle sensor and activates an application program for operating the angle sensor. [0078] The control unit senses the folding angle of the mobile terminal ( 205 ). That is, the angle sensor measures the folding angle between the first touch screen 110 and the second touch screen 120 , and sends the measured folding angle to the control unit. [0079] When the measured folding angle is received from the angle sensor, the control unit reads the function table from the storage unit ( 207 ). The function table may contain control commands that specify application programs to be activated according to sensed folding angles and output screens (first touch screen or second touch screen) for activated application programs. [0080] The control unit controls the activation of an application program according to the sensed folding angle on the basis of the function table ( 209 ). For example, as described before, the control unit may activate various application programs related to clock display, viewing of photographs, web browsing, display of a key map or menu map, playback of a video file, playback of an audio file, file classification, image browsing, image editing, phonebook browsing, and book reading. [0081] The control unit checks whether an end-of-use signal is input ( 211 ). If an end-of-use signal is not input, the control unit returns to step 203 for continued processing. [0082] As is apparent from the foregoing, the present invention has an advantage in that various angle of folding manner enable activation of various modes in the mobile terminal. In the description, it is depicted that the mobile terminal of the present invention includes two touch screens. However, the present invention is not limited thereto. That is, the present invention is also applicable to a mobile terminal having a foldable display unit composed of three, four or more touch screens. In this case, the function table may contain control commands that specify application programs to be activated according to sensed folding angles and output screens for activated application programs, and the mobile terminal may activate application programs and control execution of activated application programs by use of the angle sensor and the function table. Further the shape of mobile display is represented in a rectangular form, but it should be noted that other shapes of display can be applied according to the teachings of the present invention. [0083] Although exemplary embodiments of the present invention have been described in detail hereinabove, it should be understood that many variations and modifications of the basic inventive concept herein described, which may appear to those skilled in the art, will still fall within the spirit and scope of the exemplary embodiments of the present invention as defined in the appended claims.
A mobile terminal having a foldable display and an operation method for the same are disclosed. The foldable display unit includes a plurality of display zones, wherein the application of program depends on the degree of folding angle of the display unit, and the display unit displays on its screen according to the folding angle. Further, variations of closing and opening motion of the foldable display unit triggers different modes of operation and displays
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TECHNICAL FIELD This invention relates to a method of making a catalyst in which small catalyst particles are dispersed on the surface of larger catalyst carrier particles. More specifically, it relates to using a dry-coating process to coat nanometer-sized catalyst particles on the surface of larger catalyst carrier particles. The dry-coated catalyst particle/carrier particle composite mixture is then adapted for a catalyst application, such as automotive exhaust gas treatment or for a fuel cell reformer. BACKGROUND OF THE INVENTION Catalysts are used in many different applications. Their compositions and structures vary, as do the processes by which they are prepared. In applications where the catalyst used is present as a separate phase from the reacting chemical species that it contacts, i.e., heterogeneous catalysis, a method must be employed to support the catalytic entity in the presence of the reacting phase. Automotive exhaust treatment catalysts are an example of heterogeneous catalysts, and the background for this invention will be illustrated in that context. Automotive vehicles have used catalytic converters to treat unburned hydrocarbons, carbon monoxide and various nitrogen oxides produced from the combustion of hydrocarbon fuels in the engine. The engine exhaust gases flow through a catalytic converter that contains a very small amount, e.g., an ounce, of noble metals, such as palladium, platinum and rhodium. The catalytic converter comprises a stainless steel can that houses an extruded ceramic body, such as cordierite composition, in the shape of an oval honeycomb, generally referred to as a monolith. The extruded body contains several hundred small longitudinal passages per square inch of its cross-section. The engine exhaust passes through these channels, contacts the catalyst coated thereon, and the hazardous constituents are oxidized and/or reduced. The catalyst combination coated on the walls of the monolith passages, or channels, comprises particles of activated alumina, or the like, which carry much smaller and dispersed particles of the noble metals. A challenge in preparing such exhaust treatment catalysts lies in making maximum use of the relatively expensive noble metal. The noble metal must be distributed so that all of it, or nearly all of it, is exposed to contact the exhaust gas. Thus, catalyst particles are distributed on carrier particles and this combination supported on the walls of the monolith for contacting the exhaust gas. In accordance with present practice, an aqueous slurry of activated alumina is first applied as a thin film on the walls of the monolith passages. Activated alumina is a material that is processed to have a very large surface area per unit mass/volume. To enhance its catalyst carrier properties, the alumina may contain small amounts of other metal oxides, such as cerium oxide and lanthanum oxide. The aqueous slurry of finely divided carrier particles is drawn through the channels of the monolith and the excess drained off. The coated monolith is dried, and the coating calcined. A thin layer of alumina catalyst carrier particles is thus fixed to the walls of the channel. The noble metal(s) to be coated on the alumina is prepared as a water-based solution of suitable salts. This solution is used to soak and impregnate the alumina coating, thus permitting the noble metal compounds to infiltrate the irregular surface of the alumina particles that provides its remarkably large area. Residual solution, containing the noble metal, if any is removed. This impregnation of the alumina with a noble metal solution is referred to as a wet process. The noble metal/alumina coating on the walls of the monolith passages is known as a wash coat of the catalyst. Exhaust catalysts prepared in this way have worked well for many years. However, losses and inefficiencies remain from using this wet processing. Moreover, if possible, there is a great need to disperse the expensive metal even further so that smaller quantities can be used and/or even more complete elimination of undesirable exhaust products can be obtained. SUMMARY OF THE INVENTION This invention uses nanometer-sized particles of catalytic noble metals, such as platinum, and certain metal oxides, such as copper oxide and zinc oxide. These metals and metal oxides are commercially available in batch quantities in size ranges of, for example, 5-50 nanometers. Since such particles are usually somewhat irregular in shape, “size” means the “diameter” of a particle or like or equivalent characteristic linear dimension. In general, catalyst particle lots where the particle size distribution is within the size range of about 1 to 500 nanometers are suitable for use in the practice of this invention. A special feature of this invention is a process of dispersing, or coating, such small catalytic particles on the surfaces of larger catalyst carrier particles. The preferred carrier particles include, but are not limited to; high surface area alumina particles and alumina that incorporates metal oxides, such as cerium and lanthanum. The coating process of this invention yields high effective surface area of catalyst particles on the catalyst carrier particles. In the process, the catalyst particles and catalyst carrier particles are mechanically mixed under conditions under which they impact each other and most of the catalyst particles surprisingly end up adhering to the surface of the larger carrier particles. The process works most favorably when the carrier particles are substantially larger than the catalyst particles. Preferably, the median diameter, or other characteristic dimension, of the carrier particles is at least ten times the median diameter of the catalyst particles to obtain the catalyst particle-on-carrier particle composite material. The median particle diameter is suitably determined by the dynamic light scattering particle size measurement method. While given batches of both catalyst and carrier particles will have ranges of dimensions, it is preferred that there be suitably large carrier particles in the mix for each catalyst particle. However, as illustrated in Example 2 below, smaller (less than 10× catalyst particle size) carrier particles can be used to make the composite material when they are first coated on a larger support material such as micrometer sized ceramic fibers. The coating process is a dry process. It does not require the use of water or any other constituent to accomplish the coating of the catalyst particles on their carrier particles. Often the nanometer sized catalyst particles are initially present in clusters or agglomerates. The suitable dry mixing processes break up these agglomerates and disperse the catalyst particles on the carrier particles. The resulting catalyst particle/catalyst carrier combination evidences uniform and well-dispersed catalyst particles on the carrier particles. The catalyst particle/carrier particle composite, thus produced, is in the form of a powder. In many applications, application of this powder to a suitable support structure will be necessary. For example, the composite powder could be slip coated on the walls of the channels of a corderite monolith for the treatment of automotive exhaust gas. In other applications, the composite powder could be coated on ceramic fibers, carbon fibers, or other kinds of catalyst support structures. For these applications, the carrier particles could be coated on the support bodies and the catalyst particles later coated on the carrier particles. Regardless of the support means for the composite catalyst/carrier particles, this invention provides a simple and dry coating process by which nanometer-sized catalyst particles are dispersed on the surfaces of larger catalyst carrier particles in a form in which the catalyst surfaces can be effectively utilized. In essence, suitable quantities of catalyst particles and carrier particles are incorporated in the mixer and the mixed product is useful as is without recycling or purification. Other objects and advantages of this invention will become apparent from a detailed description of specific embodiments that follow. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a scanning electron microscope photomicrograph of ceramic fibers dry coated with alumina particles and then platinum particles in accordance with example 2A of this specification. FIG. 1 includes a 10 micrometers scale line. FIG. 2 is a transmission electron microscope photomicrograph of the blocked region indicated on FIG. 1 . FIG. 2 includes a 100 nanometers scale line and shows alumina particles on the surface of the ceramic fiber with platinum particles coated on the alumina particles. DESCRIPTION OF PREFERRED EMBODIMENTS The desired catalyst structure comprises nanometer-sized catalyst particles uniformly dispersed, or coated, on the surface of larger catalyst carrier particles. Suitably, the size of the catalyst particles is less than approximately five hundred nanometers in the largest dimension. For example, limited quantities of commercially available particles of platinum and other noble metals, as well as copper oxide and zinc oxide particles, can be obtained in the 5-50 nanometer size range. These materials comprise a relatively low number of atoms or oxide molecules per particle and offer an efficient use of these catalytic substances provided they can be dispersed on larger carrier particles. The catalyst carrier particles will generally be of micrometer scale size although alumina particles in the fifty to one hundred nanometers size range have been used in the practice of this invention after being dry coated on micron sized ceramic fibers. Catalyst particles for use in the present invention include the various noble metals, specifically those selected from the group consisting of platinum, palladium, rhodium, or mixtures thereof. These metals are well known as oxidation catalysts and catalysts for other purposes. Metallic oxides, e.g. copper oxide or zinc oxide, have demonstrated utility as catalysts and can also be used in the practice of this invention. In fact virtually any solid material available as small particles and displaying desirable catalytic activity can be employed. In order to achieve proper, uniform coating the ratio of the median diameters, as determined by dynamic light scattering, of the carrier particles to catalyst particles is ten or greater. In the present invention, nanometer sized catalyst particles were used. The catalyst particles were initially physically present in the form of agglomerates and were dispersed as nanometer scale particles on the surface of the carrier particles during processing. Suitable catalyst carrier particles for use in this invention have a large surface area for dispersion of the catalyst particles. They must be chemically compatible with the catalyst in the intended reactive environment and they must display strength and stability for the application. Gamma alumina, or other suitable forms of aluminum oxide, Al 2 O 3 , is often used as the catalyst carrier because it can be readily produced as a strong small particle with very high specific surface area. Sometimes small amounts of cerium oxide (i.e. ceria) and/or lanthanum oxide (i.e. lanthana) are mixed with alumina to enhance its oxygen storage capacity or other desirable carrier properties. A dry mixing and coating process is used to coat the nanometer-sized catalyst particles onto the larger carrier particles. In general, the coating process blends pre-measured portions of catalyst particles and carrier particles and then subjects them to high impact forces for a time suitable to coat and disperse the smaller catalyst particles on the surface of the carrier particles. Two different commercially available machines have been found to accomplish this coating operation. One machine is the Hybridizer produced in various sizes by the Nara Machinery Company of Tokyo, Japan. A second suitable mixing machine is the Theta Composer produced by Tokuju Corporation, also of Tokyo, Japan. The Hybridizer mixing machine used in the examples described below in this specification appears to be described in U.S. Pat. No. 4,915,987. FIGS. 2-4 illustrate the operation of this mixing device and, accordingly, the disclosure of that patent is hereby incorporated by reference into this specification for a more complete description of mixing processes it performs. In summary and as seen, for example, in FIG. 2 the mixer comprises a vertically oriented, rotatable circular plate supported in a mixing chamber. The plate has several radially aligned impact pins attached to its perimeter and can be driven at a range of speeds up to 15,000 rpm. The plate rotates within a collision ring having an irregular or uneven surface facing the impact pins. A powder comprising premixed catalyst particles and catalyst carriers are fed into a hopper leading to the powder inlet at the rotational axis of the machine. Air or other suitable atmosphere is used during the mixing. The incoming powder mixture is carried in the air stream by centrifugal force to the edge of the rotor plate. The powder particles receive a momentary strike by many pins or blades on the rotor and are thrown against the collision ring. The airflow generated by the fan effect of the rotating plate and pins causes repeated impacts between the catalyst particles and carrier particles and the collision ring. The design of the Hybridizer machine permits selective withdrawal of the mixed powder along with recycling of some powder and continuation of the mixing. In accordance with this invention, the product produced by this dry coating process is a mixture in which the nanometer-sized catalyst particles are coated on the surfaces of the carrier particles. Dry coating in accordance with this invention has also been accomplished using a Theta Composer. The operation of this machine appears to be illustrated in U.S. Pat. No. 5,373,999 and the disclosure of that patent is hereby incorporated into this specification by reference. As seen in FIGS. 1, 2, 3( a ) and 3( b ) of the '999 patent, the Theta Composer comprises a horizontally disposed, rotary cylindrical tank with an oval cross section mixing chamber. Supported within the oval mixing chamber is a smaller oval mixing blade that is rotatable separately from the tank in the same or opposite direction. The long axis of the mixing blade is slightly smaller than the short axis of the oval chamber to effect a gathering and compression of particles caught between them in the operation of the machine. The outer vessel rotates relatively slowly to blend the particles while the inner rotor rotates at relatively high speed. The catalyst and carrier particles drop freely by gravitation in the moving large volume swept by the mixing blade and fluidize along the inner wall of the mixing chamber. Particles that are wedged in the moving narrow clearance between the inner wall of the oval cross-section and the mixing blade are suddenly subjected to strong shearing forces. This action is found to coat and embed the catalyst particles on the surface of the larger particles to form a catalyst/carrier composite. The practice of the invention will now be illustrated by some specific examples. EXAMPLE 1 Dry Coating Method Platinum nanoparticles (Nanophase Technologies) were added to aluminum oxide (alumina) particles (Condea Corporation) to achieve a platinum composition equal to 0.4% of the total sample weight. The particles were blended in a conventional laboratory mixer at 1000 rpm for two minutes. The alumina particles had a median particle size of three microns and a specific surface area of 150 m 2 /g. The platinum particles were obtained in a particle diameter size range of 10-40 nanometers and specific surface area of 12 m 2 /g. At this stage, the blended mixture consisted simply of a relatively low number of platinum particle agglomerates interspersed with alumina particles having diameters on average about 100× the size of the platinum particles. This large particle/small particle mixture was then transferred into the chamber of a laboratory Hybridizer mixing machine and processed for 12 minutes at a blade rotation speed of 8000 rpm. The resulting mixture is identified as Sample 1A. The Sample 1A powder was compressed into pellets that, while porous, had sufficient mechanical strength for handling. The compaction was accomplished using a 0.52 inch diameter stainless steel die in a hydraulic press. A force of three tons was applied to the powder. The apparent void volume of the porous pellet was about 65% of the densities of its constituents. The pellets were then placed in a Micromeritics AutoChem 2910 instrument for determination of the catalyst metal surface area per unit loading. The pellets were initially treated with 10% hydrogen in argon at 120° C. for 30 minutes to remove the residual water followed by chemical reduction to platinum metal at 350° C. for 4 hours. The pulsed chemisorption with 10% carbon monoxide in helium was conducted on sample 1A material following the sample reduction. Comparison Sample A comparison sample, Sample 1B, was prepared using a conventional wet coating method. Platinum particles (Nanophase Technologies) were added to alumina particles (Condea Corporation) to achieve a platinum composition equal to 0.9% of the total (dry) sample weight. More than twice as much platinum was used in this comparison experiment. This dry mixture was then slurried in de-ionized water to form a suspension. The solid content of the wet mixture was approximately 45% by weight. The suspension was stirred for several minutes to distribute the small platinum particles on the much larger alumina particles. The mixture was slowly dried so as not to disturb any coated particles. The dried mixture was then calcined in a crucible in air at 400° C. for 1 hour. The above dried and calcined mixture was then compressed into pellets by the same pressing device as was done with the sample 1A material. The same apparent density was achieved and the porous pellets were strong enough for handling. The pellets were initially treated with 10% hydrogen in argon at 120° C. for 30 minutes to remove the residual water followed by chemical reduction to platinum metal at 350° C. for 4 hours. The pulsed chemisorption with 10% carbon monoxide in helium was conducted on the sample 1B comparison material following the sample reduction. Example 1 Results Following sample reduction and cooling, the active surface area of the platinum particles on Sample 1A was determined by pulse chemisorption using 10% carbon monoxide in helium. It is, of course, known that platinum chemically adsorbs carbon monoxide, and this practice is recognized as a suitable method of measuring the active surface area of platinum dispersed on alumina. The active platinum surface area as measured was about 17.8 square meters per gram of platinum in the sample, and about 0.07 square meters per gram of sample. The sample 1A powder and the pellets were further examined by scanning electron microscope (SEM) surface analysis, energy dispersion spectrometer surface analysis and X-ray diffraction. All analyses showed, or were consistent with, the conclusion that the dry mixing in the Hybridizer machine had resulted in the platinum particles being substantially completely coated on the much larger alumina particles. For the catalyst prepared using the conventional, wet process (i.e. Sample 1B), the active platinum surface area as measured was only about 3.7 square meters per gram of platinum in the sample, and only about 0.03 square meters per gram of sample (despite the higher platinum content). Thus, catalyst preparation using the dry mixing process provides a better surface coating and higher surface area of noble metal on the surface of the catalyst carrier as compared to that obtained using the conventional, wet process. EXAMPLE 2 Dry Coating Method Sample 2A was prepared by first combining alumina nanoparticles (Nanophase Technologies) with ceramic fibers to achieve a nanoparticle composition equal to 3% of the total weight. The alumina particles were generally spherical in shape with diameters in the range of 50-150 nanometers. The particles had a BET specific surface area of 37 m 2 /g. The ceramic fibers had average diameters of 2-3 microns with an average length of about 150 microns. The ceramic fibers are viewed as support materials, not catalyst carriers. But in this example the combination of the nanometer sized alumina particle with the micron sized ceramic fibers enable the smaller platinum particles to be dispersed on the alumina particles. The alumina particles were coated on the ceramic fibers using a laboratory scale Theta Composer. The outer oval cross-section vessel was rotated at 75 rpm and the oval blade was rotated at 2500 rpm. This mixing and coating operation was continued for 30 minutes. The mixture was examined after this mixing and coating step and it was observed that the alumina particles were adhered to and dispersed on the surfaces of the ceramic fibers. Platinum particles (Nanophase Technologies) were then added to the coated fiber sample to achieve a platinum composition equal to 0.8% of the total sample weight. The platinum particle size range was 10-40 nanometers with a specific surface area of 12 m 2 /g. In this example, the alumina particles did not have a median diameter that was ten times the median diameter of the platinum particles. However, alumina particles were coated on the much larger ceramic fibers and this facilitated dry coating of the platinum particles on the alumina particles. The mixing and coating process was repeated using the operating speeds and mixing time stated above. A portion of the above mixture was then compressed into porous pellets using the tool described in Example 1. Again, the pellets were strong enough for handling and had a void volume of 54%. The pellets were then placed in the Micromeritics AutoChem 2910 instrument for determination of the catalyst metal surface area per unit loading. The pellets were initially dried to remove residual moisture and then calcined at 400° C. for one hour. Following calcination, the pellets were treated with 10% hydrogen in argon at 120° C. for thirty minutes and then heated at 350° C. for four hours in the same atmosphere to chemically reduce the platinum metal particles. The pulsed chemisorption with 10% carbon monoxide in helium was conducted on the sample following sample reduction. Comparison Sample A comparison sample 2B was prepared by mixing platinum nanoparticles, alumina nanoparticles and ceramic fibers. The platinum and alumina nanoparticles comprised 1% and 5% of the total sample weight respectively. The respective materials were the same as those used in Example 2A. The dry mixture was slurried in deionized water and agitated sonically to enhance the mixing of the different sized particles and fibers, resulting in a more homogeneous suspension. The solid content of the mixture was about 45% by weight. The mixture was then slowly dried and calcined in air in a crucible at 400° C. for 1 hour. The above dried and calcined mixture was compressed into porous pellets by the method described above. These Sample 2B pellets also had a void volume of 54%. The Sample 2B pellets were dried with 10% hydrogen in argon at 120° C. for 30 minutes followed by reduction at 350° C. for 4 hours. The pulsed chemisorption with 10% carbon monoxide in helium was conducted following the sample reduction. Example 2 Results FIG. 1 is a scanning electron microscope photograph of the several alumina and platinum coated ceramic fibers. The fibers were not fully coated with alumina particles but the alumina is seen distributed on the two to three micron diameter fibers. The platinum particles can not be distinguished from the alumina particles at the magnification of this photograph. However, FIG. 2 is a transmission electron microscope photograph of the region □indicated in FIG. 1 . In FIG. 2, the platinum nanoparticles (dark) are seen distributed on the alumina carrier particles. Following sample reduction and cooling, the surface area of the platinum particles for both Sample 2A and the comparative sample 2B was determined by pulse chemisorption of 10% carbon monoxide in helium. Again, the observation that platinum adsorbs carbon monoxide validates this practice as a suitable method of measuring the active surface area of platinum dispersed on alumina particles and fibers. The active platinum surface area as measured on Sample 2A was about 9.3 square meters per gram of platinum in the sample, and about 0.07 square meters per gram of sample. The sample 2A powder and the pellets were further examined by scanning electron microscope surface analysis, energy dispersion spectrometer surface analysis and X-ray diffraction. All analyses showed, or were consistent with, the conclusion that the dry mixing in the Theta Composer machine had resulted in the platinum particles being substantially completely coated on the much larger alumina particles that in turn were coated on the larger alumina fibers. The catalyst prepared using the conventional, wet process (i.e. Sample 2B), the active platinum surface area as measured was only about 7.2 square meters per gram of platinum in the sample, and only about 0.07 square meters per gram of sample. Thus, catalyst preparation using the dry coating process provides a better surface coating and higher surface area of noble metal on the surface of the catalyst carrier as compared to that obtained using the conventional, wet process. EXAMPLE 3 Dry Coating Method Sample 3A was prepared by initially blending alumina nanoparticles (Nanophase Technologies) with ceramic fibers (Zircar Ceramics) using a laboratory mixer at 1000 rpm for 2 minutes. The alumina particles comprised 6.5% of the total weight. The alumina nanoparticles had a nominal particle size range of 50-150 nanometers and a specific surface area of 37 m 2 /g. The ceramic fibers had an average diameter of 2-3 microns and an average length of about 150 microns. The alumina particle/ceramic fiber mixture was then transferred into the chamber of the Hybridizer and processed for 3 minutes using a blade rotation speed of 8000 rpm, thus coating the alumina particles onto the ceramic fibers creating a first layer. In the second coating step, copper oxide nanoparticles (Nanophase Technologies) were then added to the above mixture to achieve a copper oxide composition equal to 5.5% of the total sample weight. The copper oxide nanoparticles had a median diameter of 23 nanometers and a specific surface area of 38 m 2 /g. The components were processed under the same operating conditions, thus coating the copper oxide nanoparticles onto the surface of the above mixture creating a second layer. Again, the relatively small alumina particles were first coated on micrometer sized ceramic fibers. This enabled the copper oxide particles to be coated on the alumina particles. The above mixture was then compressed into a pellet structure, with a pellet void volume of 48%, using a 0.52-inch diameter stainless steel die and a hydraulic press to apply 3-tons of force. The pellets formed were placed in the Micromeritics AutoChem 2910 to determine the active metal surface area per unit loading. The pellets were initially dried with argon, first at 110° C. for 30 minutes and then at 400° C. for another 30 minutes. Reduction of the sample was conducted at 220° C. for 4 hours with 10% hydrogen in argon. The pulse chemisorption with 10% N 2 O in helium was conducted following the sample reduction. Comparison Sample A comparison sample, Sample 3B, was prepared by copper oxide nanoparticles, alumina nanoparticles and ceramic fibers with deionized water to form a suspension. The copper oxide and alumina particles comprised 5.5% and 5.5% of the total sample weight respectively. The respective materials were the same as those used in Example 3. The mixture was agitated sonically to enhance the mixing of the different sized particles and fibers, resulting in a more homogeneous suspension. The solid content of the mixture was maintained within a range of 40% to 55% by weight. The mixture was slowly dried and calcined in air in a crucible at 400° C. for 1 hour. The above dried and calcined mixture was compressed into porous pellets by the method described above. These Sample 3B pellets had a void volume of 48% as well. The Sample 3B pellets were initially dried with argon, first at 110° C. for 30 minutes and then at 400° C. followed by chemical reduction of the copper oxide at 350° C. for 4 hours. The pulse chemisorption with 10% N 2 O in helium was conducted following the sample reduction. Sample 3 Results Following sample reduction and cooling, the surface area of the copper oxide particles for Sample 3A was determined by pulse chemisorption of 10% N 2 O in helium. Again, the observation that the N 2 O reacts with the copper particles, formed from the reduction of copper oxide, validates this practice as a suitable method of measuring the surface area of copper dispersed on alumina particles and fibers. The active copper surface area as measured on Sample 3A was about 7.1 square meters per gram of copper in the sample, and about 0.31 square meters per gram of sample. The sample 3A powder and the pellets were further examined by scanning electron microscope surface analysis, energy dispersion spectrometer surface analysis and X-ray diffraction. All analyses showed, or were consistent with, the conclusion that the dry mixing in the Theta Composer machine had resulted in the copper oxide particles being substantially completely coated on the somewhat larger alumina particles that in turn were coated on the larger alumina fibers. The catalyst prepared using the conventional, wet process (i.e. Sample 3B), the active copper surface area as measured was only about 1.3 square meters per gram of platinum in the sample, and only about 0.07 square meters per gram of sample. Thus, catalyst preparation using the dry coating process provides a better surface coating of the base metal oxide on the surface of the catalyst carrier as compared to that obtained using the conventional, wet process. The previous examples demonstrate how the catalyst particle/catalyst carrier composite can be applied onto support materials such as ceramic fibers. Other suitable support materials that can be employed that are similar to that of ceramic fibers are carbon based nanotubes, carbon fibers, ceramic powders, alumina fibers, or the like. These support materials are advantageous in that dry mixing can be used to coat the composite (catalyst and carrier particles) on the surface of the support material and thus, better surface area coating of the composite on the support material can be achieved. In automotive applications, the catalyst structure will typically be housed in a stainless steel can, known as a catalytic converter. The catalyst support material used is usually an extruded ceramic body, such as a corderite body, in the shape of an oval honeycomb, and is generally referred to as a monolith. The catalyst composite layer is typically applied to the surfaces of the monolith and the catalyst structure comprising the monolith support and its composite catalyst layer is placed inside the stainless steel can. The corderite monolith support structure generally has a very complex geometry. The support resembles a honeycomb structure that comprises several small channels, or pores. The catalyst composite material is coated on the walls of these channels and thus, the most desirable coating method used is one in which the composite particles will have access to the channel wall surface. Therefore, the conventional slip coating is the most advantageous way of properly coating the channels of a monolith support structure with the dry coated catalyst composite. While this invention has been described through application and through the examples described above, it is not intended to be limited to the above description, but rather only to the extent set forth in the following claims.
A method of dispersing nanosized catalyst particles on the surface of larger catalyst carrier particles is disclosed. The coating process is done dry and yields high effective surface area of nanosized catalyst particles coated on the surface of catalyst carrier particles. In this process, nanosized catalyst particles and catalyst carriers are mechanically mixed in a high velocity and impact force environment to which catalyst particles are embedded, or filmed, on the surface of catalyst carrier particles without using water or any other additional chemicals. The catalyst composite structure produced comprises better coating uniformity of the catalyst particle on its catalyst carrier. The catalyst particle/catalyst carrier composite produced can be applied to a support structure, such as a monolith as readily used in automotive or other applications.
1
CROSS-REFERENCE TO RELATED APPLICATIONS The present application is a continuation-in-part of U.S. patent application Ser. No. 08/633,696, filed Apr. 18, 1996 now U.S. Pat. No. 5,681,385. TECHNICAL FIELD The present invention relates to a method for improving building materials such as portland cement-based building products, masonry, brick, concrete, mortar, and the like, and more particularly, relates to coating or incorporating polyvinyl alcohol onto or into building materials to thereby influence or control the effective moisture content and moisture migration in building materials. BACKGROUND OF THE INVENTION Many building materials, and particularly those that are comprised largely of inorganic compounds, such as masonry, cement, brick, concrete, and the like, are naturally porous. Thus, these building materials possess capillary networks that allow water to penetrate and evaporate from the building material, as well as migrate through the building material. It is common practice to build structures wherein units of building material are placed adjacent to one another, with the expectation that the two units will form a strong bond. Placing bricks into a Portland cement-based bonding agent, such as mortar, is one example. While the strength of such a bond will depend on several factors, one important factor is the relative suction of the two building materials. In essence, "suction" refers to the tendency of a building material to draw moisture from, or release moisture to, a neighboring structure. Suction may also be referred to as the degree of water absorption exhibited by a material. The use of bricks and mortar to form a wall provides one illustration of the importance of suction. Brick is typically formed in a kiln, and is quite dry upon leaving the kiln. However, upon sitting under ambient conditions, bricks may absorb some moisture from the air, in an amount depending on ambient temperature and humidity. On the other hand, mortar is quite wet in the uncured state which is used to join bricks together. When brick and uncured mortar come into contact, moisture from the mortar will migrate into the adjacent brick. If the brick exhibits high suction, moisture will migrate rapidly and to a large extent from the mortar into the brick. However, mortar has an optimum curing rate and water content in order for the mortar to fully hydrate and form a strong, non-crumbling structure. Rapid and/or large loss of moisture from the mortar can lower the internal strength of the mortar, as well as the strength of the bond that forms between the brick and the mortar. In theory, compensation for undesirable suction may be achieved by adjusting the water content of building materials. For example, extra water may be added to grouts, mortars, and other cementitious materials to compensate for the amount that will be absorbed by the brick. Another approach that is sometimes taken is to "pre-wet" the brick, that is, dip the brick in water or spray water on the brick, so that it will display reduced suction. However, in practice, it is very difficult to determine how much extra water should be added to grout or brick, and it is typically the case that the desired bond strength is not obtained by these approaches. The moisture content of building materials, and the degree and rate at which moisture moves through and/or evaporates from building materials, has implications beyond an effect on bond strengths. For example, excess moisture within porous building materials is a serious problem to the industry. Freeze--thaw cycles create alternate expansion and contraction of the porous building materials that can lead to spalling and disintegration. Biological growth of microbes, mosses, lichens and the like also cause damage and are an aesthetic detriment. Porous building materials that are damp have a decreased R - value and thereby cause heat loss in winter and overheating in summer. Movement of moisture through building materials can cause concomitant salt migration to the surface of building material, thus giving rise to efflorescence. Accordingly, there is a need in the art for a method to treat building materials in order to affect the moisture content of the building material, and to affect the rate and extent to which moisture migrates into, through and out of building material. The present invention solves these long-standing needs, and provides other related advantages, as discussed below. SUMMARY OF THE INVENTION The present invention is directed to a method for affecting the movement of moisture through a porous building material. The method comprises the step of applying a coating composition onto a surface of the building material. The coating composition contains polyvinyl alcohol (PVOH) in addition to optional ingredients. The building material may be, for example, brick, cement, concrete, mortar, plaster or stucco. The coating may be applied to either a cured or uncured surface. Preferably, the PVOH has a hydrolysis percent of at least about 70%, and more preferably has a hydrolysis percent of about 87% to about 99.9%. The coating composition is preferably aqueous, and has a PVOH concentration of about 0.01% to about 30% by weight, based on the total weight of the PVOH and water in the composition. The coating composition may be applied to the surface in an amount of about 1 to about 1000 square feet of surface/gallon of composition. Another aspect of the invention is a method for affecting the movement of moisture through a porous building material, wherein the components of the building material are mixed with a composition containing polyvinyl alcohol (PVOH). Preferably, the PVOH is admixed with the building material at a PVOH concentration of about 0.001% to about 50% by weight based on the total weight of PVOH and building material. Another aspect of the invention is an article of manufacture which comprises porous building material that has a surface coated with a coating composition comprising polyvinyl alcohol (PVOH). A further aspect of the invention is an article of manufacture which comprises an admixture of porous building material and polyvinyl alcohol (PVOH). These and other aspects of the invention will become evident upon reference to the following detailed description. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method of enhancing suction and bonding by using polyvinyl alcohol to attract and temporarily hold moisture onto and into the surfaces of porous building materials. Bonding agents such as Portland cement-based bonding agents are strengthened by a temporary retention of water and thereby achieve a stronger bond. A porous masonry unit treated by the method disclosed in the present invention has an increased attraction for the moisture in Portland cement-based mortar and consequently the porous masonry unit experiences increased suction of the moisture in the mortar. Temporary retention of moisture helps to delay the initial set of Portland cement. This initial moisture that normally flashes off is delayed with a stabilization of moisture loss imparted by the PVOH. Thus, the invention provides a method for affecting the movement of moisture through a porous building material. The term "affecting the movement of water" as used herein means that one or more of the following effects are achieved: the suction of the porous building material is influenced, typically reduced, so that stronger bonding occurs between the porous building material and an adjacent building material; moisture content within porous building material is reduced so that freeze-thaw cycles cause less spalling and disintegration; moisture content within porous building material is reduced so that the environment within the porous material is less amenable to supporting microbial life; moisture content within a porous building material remains low so that the insulative capacity of the building material remains relatively high; movement of moisture and salts within the moisture is reduced so that effloresence is retarded. An effective amount of a PVOH-containing composition is sufficient to achieve one or more of the above effects when placed in contact with building material. The present invention provides articles of manufacture useful in building or constructing structures that experience improved suction and bonding, and optimum moisture content, and provides a method of improving a building material that would otherwise be susceptible to uncontrolled degrees of suction, bonding, and moisture loss. The building material which is suitably employed in the invention is any material that can exhibit, or is subject to uncontrolled degrees of suction, bonding, and moisture loss. Brick, cement, concrete, mortar, plaster and stucco are non-limiting examples of such building materials. Building materials which are mainly inorganic are a suitable class of building materials for use in the invention. Preferred mainly inorganic building materials are formed in whole or in part from portland cement, including normal portland cement, modified portland cement, high-early-strength portland cement, low-heat portland cement, sulfate-resisting portland cement, air-entrained portland cements, portland blast-furnace slag cements, white portland cement, portland-pozzolana cement, redi-mix concrete, precast concrete, architectural concrete, concrete paving, prestressed concrete and masonry based on portland cement. Another preferred group of building materials subject to uncontrolled degrees of suction, bonding, and moisture loss are common masonry materials such as brick (including adobe, clay, reinforced clay, clay tile and clay pavers), stone (including granite, limestone and river rock), concrete block (including architectural building block, prefaced or glazed block, common building block and concrete products) and mortar (such as lime mortar and lime-and-portland cement mortar). Cementitious materials such as inorganic hydraulic cement, portland cement, masonry cement, waterproofed cement, pozzolana cement, alumina cement, synthetic calcium aluminate cement, expanded concrete, concrete, concrete block, slump block, concrete pavers, concrete roofing tiles, precast concrete, poured-in-place concrete, tilt-up concrete, ready-mixed concrete, architectural concrete, structural concrete, glass fiber reinforced concrete, exposed aggregate, grout, plaster, stucco, joint cement and natural cement are another category of building material that may be used in the invention. Plaster and stucco are exemplary building materials of the invention, where Keene's cement, gypsum plaster, cement plaster are representative examples. The building material includes brick and other fired clay-based products such as ceramic, tile and terra-cotta. The building material of the invention will typically be formed in whole or part of inorganic material, because many inorganic building materials are subject to uncontrolled degrees of suction, bonding, and moisture loss. The building material may be formed from a composite or blend of organic material and inorganic material, or entirely from organic material, as long as the building material is subject to uncontrolled degrees of suction, bonding, and moisture loss. For example, some clays as obtained or mined from the earth contain organic components such as coal, and are suited for treatment according to the invention. In order to beneficially affect moisture content and movement in porous building material, it has been discovered that the building material should be contacted with polyvinyl alcohol (PVOH). PVOH is available commercially from a number of suppliers, where Air Products (Allentown, Pa.) is a representative supplier of PVOH. PVOH is a white to cream granular powder, having a bulk density of about 40 lbs./cu. Ft. and a Tg (° C.) of about 75-85. PVOH is typically prepared by hydrolyzing polyvinyl acetate, where polyvinyl acetate is typically prepared by homopolymerization of vinyl acetate. PVOH is typically characterized in terms of its hydrolysis percent, where hydrolysis percent reflects the percentage of the acetate groups of the polyvinyl acetate which were hydrolyzed in order to form the PVOH. The PVOH useful in the invention typically has at least 70% hydrolysis, preferably has at least about 87% hydrolysis, and more preferably has about 87%-99.5% hydrolysis, according to values provided by the manufacturer. The PVOH useful in the invention may also be characterized in terms of its molecular weight. The number average molecular weight of the PVOH useful in the invention is typically at least about 5,000, preferably about 7,000 to about 500,000. The weight average molecular weight of the PVOH is at least about 5,000, and is more preferably about 7,000 to about 190,000. The PVOH is preferably dissolved in water before being combined with the building material, although it could be dissolved in non-aqueous solvents as well. Techniques to dissolve PVOH in water are known in the art, and are described in the Examples herein. As a general procedure, the PVOH is gradually added to cold or room temperature water, using sufficient agitation to wet out all particles with water and form a dispersion. The surface of the water should be moving vigorously during the PVOH addition. According to a preferred embodiment of the invention, the PVOH will not dissolve in this cold or room temperature water, and the dispersion must be heated to obtain a solution. In one embodiment, the PVOH will dissolve in water at about 1° C. to about 100° C. The heating temperature is generally at least about 50° C., and is preferably in the range of about 80° C.-100° C. (ca. 180° F.-212° F.), and upon being maintained within this temperature range for about 30 minutes, the dispersion of PVOH in water will form an aqueous solution of PVOH. The aqueous solution of PVOH may be cooled back to room temperature, and will remain as a solution. Alternatively, an aqueous solution of PVOH may be prepared by jet cooking. Aqueous solutions of certain grades of PVOH are cold water soluble and accordingly, aqueous solutions may formulated by introduction of said PVOH into cold water followed by sufficient agitation to dissolve the PVOH. These same cold water soluble grades of PVOH may also be mixed into building materials that will eventually be treated with water such as in the event of masonry mortar. In this event the cold water soluble PVOH may be blended with the dry cement or other dry ingredients of the mortar. When water is introduced for the purpose of hydrating the cement, the cold water PVOH will dissolve upon agitation of the mortar. The PVOH solution typically contains about 0.001%-50% by weight PVOH, preferably about 0.01%-30% by weight PVOH in an aqueous solution. In general, the upper limit to the PVOH concentration in water is determined only by the viscosity of the resulting aqueous solution. As the content of PVOH increases, the solution becomes more viscous and less easy to handle, and at above about 50% by weight, PVOH solutions are very viscous and difficult to handle. The precise PVOH content of a PVOH solution useful according to the invention will depend on the exact identity of the PVOH. A lower molecular weight PVOH can generally be formed into a higher solids solution. However, a low solids solution may be readily used in the present invention, although repeated coatings of such a low solids solution onto a surface of a building material may be necessary to achieve the desired effect on moisture. The desired concentration of PVOH in a solution may be influenced by the surface of the building material that is being coated. For example, where the surface is formed from lightweight concrete block, which is highly absorbent and will require a relatively large amount of PVOH coating to achieve the desired control of suction, bonding, and moisture loss, an approximately 12% PVOH solution is conveniently used. However, where the surface is very dense, the coating may contain only about 2% PVOH. Higher or lower concentrations may be used, depending on the preference of the user. The PVOH solution may contain ingredients other than PVOH and solvent. For example, where the PVOH solution will be stored for more than a day or two, it is preferred to include a biocide in the solution. One or more of a surface active agent, defoamer and crosslinker may also be added to the solution. Some examples of additives are as follows: Biocides such as KATHON™ LX biocide (Rohm & Haas, Philadelphia, Pa.) at <50 ppm and DOWICIL™ 75 biocide from Dow Chemical (Midland, Mich.) at 100-200 ppm; surface active agents such as SURFYNOL™ 465 surfactant (Air Products, Allentown, Pa.) at about 0.2% d/d and SURFYNOL™ 440 surfactant (Air Products) at about 0.2% d/d; defoamers such as FOAMASTER™ defoamer (Henkel) at <1% d/d, FOAMASTER™ KB defoamer (Henkel) at <1% d/d, DREWPLUS™ L474 defoamer (Drew Industrial, Division of Ashland Chemical Co.) <1% d/d, SURFYNOL™ 61 defoamer (Air Products) at about 0.9% by weight of aqueous, and SURFYNOL™ DF-75 defoamer (Air Products) at about 0.2% by weight of aqueous; and crosslinkers such as SUNREZ™ 700 crosslinker (Sequa) at 1-4% d/d, BACOTE™-20 crosslinker (Magnesium Elektron, Ltd.) at 2-10% d/d and GLYOXAL™ crosslinker (American Hoechst) at 5-15% d/d. The PVOH coating may be applied to a surface of a building material, or it may be incorporated into the building material during the manufacture thereof. The building material to which the PVOH is applied may be uncured (has not yet hardened, e.g., a concrete surface which has not totally hardened) or it may be cured. Alternatively, the PVOH may be used as a component to form the building material, which is subsequently cast and cured. The PVOH coating may be applied to the building material over a wide range of temperatures, including sub-freezing temperatures (less than 32° F.) and high temperatures (greater than 100° F.). The coating of PVOH may be cast or applied to a dry or wet surface by rolling, brushing, spraying, rolling, pouring, dipping and backrolling, etc. The coating may be applied by transfer pump at about two to three gallons/minute from a container to the surface of the building material, followed by rolling or brushing as with standard waterproofing paints. A densely filled, soft-fibered brush is preferably used to make sure that the PVOH solution evenly but liberally penetrates all surfaces of the building material. The amount of PVOH desirably applied to the surface of a building material should be sufficient to achieve the desired control of suction, bonding, and moisture loss, i.e., an effective amount of PVOH should be applied to the building material surface. The precise amount will vary depending on the ambient temperature, and on the concentration and viscosity of the PVOH solution, as well as the nature, particularly the porosity, of the surface. A surface with high porosity, such as concrete block, will require more PVOH per surface square foot than will a less porous, less absorbent surface such as dense fired clay. As a rough rule of thumb, where the PVOH is applied as an aqueous solution having a concentration of about 0.001% to about 50% (percentages are by weight based on total weight of PVOH and water in the composition), the coverage rate will be about 1 to about 1,000 square feet of the surface per gallon of the coating, preferably about 10 to about 500 square feet/gallon, and more preferably about 40 to about 200 square feet/gallon. When using a solution having about 7% PVOH, about 40-200 square feet per gallon, preferably about 100-150 square feet/gallon of coating is applied to the surface, depending on the surface porosity. After being coated with the PVOH solution, the surface of the building material should be allowed to dry, preferably for at least about 4 hours, in the absence of precipitation. When applied in extreme cold temperatures or under high humidity conditions, it will take longer for the PVOH coating to dry than is the case under high temperature, low humidity conditions. Drying time will also increase with increased coating thickness. The surface of the building material is preferably clean before being coated with the PVOH solution of the invention. Methods to clean the surfaces of a building material are well known in the art. The surface may be slightly moistened prior to being coated with the PVOH solution, however is preferably dry to the touch when being coated with the PVOH solution. It is preferred to maximize the extent to which the PVOH solution penetrates the building material. Penetration may be assisted by lowering the viscosity of the solution. Viscosity may be lowered by reducing the molecular weight of the PVOH. Penetration may also be enhanced by the addition of a surface active agent to the PVOH solution. External variables can also enhance penetration. This includes temporarily (15 minutes or less) heating the building material to a temperature of up to about 300° F., or heating the building material for an extended period of time at a temperature not exceeding about 212° F. Alternatively, or in addition, the PVOH solution may be heated while it is being applied to the building material. Heating the PVOH solution reduces its viscosity, and this can increase penetration. Furthermore, the present invention relates to a method for improving a building material, wherein a composition comprising polyvinyl alcohol (PVOH) is mixed with components needed to form the building material. The PVOH typically has a hydrolysis percent of at least about 70% and is mixed into the building material components at a concentration effective to achieve the desired control of suction, bonding, and moisture loss. According to this method, the PVOH is an integral component of the building material. According to this embodiment of the invention, PVOH is preferably dissolved in solvent, and more preferably dissolved in water as described above, and the PVOH solution is added to the components that form the building material. For example, where the building material is cement, the PVOH solution can be added along with the water that is used to form the pre-cast concrete slurry. Another example would be the addition of cold water soluble grade PVOH to the dry ingredients of portland cement products followed by the addition of water in the cement hydration of these portland cement products that would result in building materials that would achieve the desired level of suction, bonding, and moisture loss. The PVOH should be present in the building material in an amount effective to achieve the desired level of suction, bonding, and moisture loss of the building material, and should have a hydrolysis percent of at least about 70%. An effective amount of PVOH to achieve the desired control of suction, bonding, and moisture loss in a building material is generally about 0.001% to about 50% by weight based on the total weight of PVOH and building material. Preferably, about 0.01% to about 10%, and more preferably about 0.05% to about 5% of PVOH is incorporated into the building material. Because PVOH rapidly decomposes above about 200° C., it should not be contacted with the building material at any point before which the building material will be exposed to 200° C. For example, the PVOH is preferably not incorporated into brick before the brick is fired. When PVOH is contacted with brick according to the invention, the PVOH is preferably applied to the brick after the brick has been cured and cooled. The PVOH solution can be added to the wet phase of cementitious materials, preferably as a replacement for some of the water that is used to form the wet phase cementitious material. Dry cold water soluble grade PVOH may be added to the wet phase of cementitious materials as well. According to the afore-described methods, an article of manufacture is provided which contains building material subject to uncontrolled degrees of suction, bonding, and moisture loss and polyvinyl alcohol (PVOH). The article of manufacture may be a block or other form useful in building and constructing various structures, e.g., walls, roofs, fireplaces, etc. The article of manufacture may be building material coated with PVOH, or it may be building material wherein the PVOH is an integral component of the building material. The following theory is offered to explain the efficacy of PVOH in achieving the desired control of suction, bonding, and moisture loss in building material. PVOH is comprised of long, straight chains of carbon, having hydroxyl groups appended thereto. The structure of PVOH may be abbreviated as (--CH2--CHOH--)n and thus it can be seen that hydroxyl groups are present on alternating carbon atoms of the straight carbon chain of PVOH. PVOH thus has a high density of hydroxyl groups. These hydroxyl groups have the ability to hydrogen bond to water, but they do not hydrogen bond to water as well as water hydrogen bonds to itself. For this reason, PVOH initially hydrogen bonds to water and causes at least a temporary retardation of moisture loss (phase one). Since water that has hydrogen bonded to PVOH is not as strongly bonded as if it were bonded to water, it evaporates more quickly than water that is hydrogen bonded to water (phase two). The presence of PVOH within building materials continually causes moisture within said building materials to be temporarily hydrogen bonded to the PVOH and then released which causes a reduced moisture content in that building material (phase three). Phase one results in a period of time where water is temporarily held which serves to optimize suction and bonding. Phase two results in accelerated water loss. Phase three results in an overall reduced moisture content. The present invention helps to optimize suction such that moisture from water-based bonding agents (e.g., mortar) is not overly sucked into adjacent porous building material (e.g. brick). In this way, the present invention not only attracts moisture in the bonding agents to the surface of the porous building material, but also it prevents moisture from being overly attracted into the porous building material beyond the useful reach of the bonding agent. In this way optimal suction is achieved. Porous building materials that are not treated with the present invention will have bond strengths that are subject to varying circumstances. Porous building materials that have a dense surface have diminished suction and bonding. Unusually porous building materials will have too much suction and diminished bonding. Weather and other conditions that accelerate evaporation cause less than optimal suction, and diminish bonding. Porous building materials that are treated with the present invention experience an initial retardation of moisture loss, then an accelerated evaporation rate that corresponds favorably to the curing of Portland cement, and finally result in an overall water reduction. The initial retardation of moisture loss optimizes suction and increases bond strength. The second phase exemplified by accelerated evaporation and the final stage exemplified by lowered water content offset the deleterious effects of excess moisture and thereby improve the porous building materials. Current art is severely restricted in the control of suction, bonding, and moisture content. Materials are not designed to control these aspects, but rather are subject to such factors as available materials, design choice, and weather conditions. One method of offsetting overly porous building materials and or high water loss conditions such as warm weather is to add excessive amounts of water to Portland cement based bonding materials. While this may somewhat offset overt suction, the resultant grout/bonding agent and consequent structure is weakened. During production of some porous building materials, evaporation is accelerated by means of kilns and other such dryers. Once these materials are removed from these apparati, they are subject to moisture gain and retention the same as if they had never been dried. The following specific examples serve to further illustrate the invention. These examples are merely illustrative of the invention are not to be construed as a limitation thereof. EXAMPLE 1 TREATMENT OF RED INCA BRICK (DENSE BRICK) A 2% aqueous solution of PVOH was prepared for use on red inca brick. The PVOH was a 50%/50% blend by weight of AIRVOL™ 107 polyvinylalcohol and AIRVOL™ 321 polyvinylalcohol. The solution also contained 0.9% SURFYNOL™ 61 Surfactant from Air Products and Chemicals, Inc., Allentown, Pa. The bricks were immersed in the solution for about ten seconds and allowed to dry for a period of about a few days. These same bricks and another set of untreated bricks were formed into eight brick high prisms that were stack bonded with a conventional mortar mix. Four prisms were tested in all. One treated and one untreated prism were covered with a plastic bag, while one treated and one untreated prism were left uncovered and all were left outside during varying weather conditions that included rain. After approximately 28 days the prisms were tested under ASTM C1072 Masonry Flexural Bond Strength by an independent testing laboratory. The average tensile strength for the uncovered/untreated prism was 127.17 psi while the uncovered/treated prism was 163.0 psi. The average tensile strength for the covered/untreated prism was 158.0 psi, while the covered/treated prism was 219.8 psi. The results indicated considerably increased bond strength resulting from the treatment of the preferred embodiment. EXAMPLE 2 TREATMENT OF CASCADE SPICE BRICK (POROUS BRICK) An aqueous PVOH solution was prepared according to the procedure of Example 1, but applied to a porous brick type. The PVOH was a 50%/50% blend by weight of AIRVOL™ 107 polyvinylalcohol and AIRVOL™ 321 polyvinylalcohol. The solution also contained 0.9% SURFYNOL™ 61 Surfactant from Air Products and Chemicals, Inc., Allentown, Pa. The aqueous PVOH solution was applied to the porous brick by an approximate ten second immersion. After curing for about a few days the brick were formed into eight high prisms and stack bonded with a conventional mortar mix. Two such prisms were formed, one treated, one untreated, both were covered with a plastic bag. After about 28 days the prisms were tested by an independent lab in accordance with ASTM C1072 Masonry Flexural Bond Strength test. The result was that the average bond strength of the untreated prism was 32 psi, while the treated prism's bond strength was 143. In this test the treated prism exhibited bond strength more than 4.4 times that of the untreated prism. EXAMPLE 3 TREATMENT OF DENSE CONCRETE PAVERS The dry weights of two separate dense concrete pavers was determined. A 7% aqueous solution of PVOH was prepared. The PVOH was a 50%/50% blend by weight of AIRVOL™ 107 polyvinylalcohol and AIRVOL™ 321 polyvinylalcohol. The solution also contained 0.9% SURFYNOL™ 61 Surfactant from Air Products and Chemicals, Inc., Allentown, Pa. A dense concrete pavers was treated on all but the bottom and about 1 inch of the sides with the 50/50 formula. After curing for about a few days the two pavers were weighed and then immersed in water for about 48 hours in order to become saturated with water. The rate of water (weight) loss was then observed and recorded. After 128 days, water loss of the pavers was considered to be stabilized. At that point the treated paver had lost over 41% more moisture than the untreated paver. In this example the treated paver exhibited accelerated moisture loss and an overall reduced moisture content over the untreated paver. From the foregoing it will be appreciated that, although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the invention. Accordingly, the invention is not limited except as by the appended claims.
The moisture content within, and moisture flow in and out of, porous building materials such as masonry, brick, concrete, and mortar, can be affected by coating the building material with polyvinyl alcohol, or by incorporating polyvinyl alcohol into the building material. The resultant control of moisture movement can influence the suction of the building material, leading to improved bonding with adjacent building material, and can also retard efflorescence.
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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for recording and retrieving transducer positioning information in a magnetic disc storage system and, more particularly, to such a method and apparatus which incorporates features which improve system reliability in the presence of noise, media defects and spindle speed variations. 2. Description of the Prior Art Magnetic disc storage systems are widely used to provide large volumes of relatively low-cost computer accessible memory or storage. A typical disc storage system includes a number of discs coated with a suitable magnetic material mounted for rotation on a common spindle and a set of transducer heads carried in pairs on elongated supports for insertion between adjacent discs, the heads of each pair facing in opposite directions to engage opposite faces of adjacent discs. The support structure is coupled to a positioner motor, the positioner motor typically including a coil mounted within a magnetic field for linear movement and oriented relative to the discs to move the heads radially over the disc surfaces to thereby enable the heads to be positioned over any annular track on the surfaces. In normal operation, the positioner motor, in response to control signals from the computer, positions the transducer heads radially for recording data signals on or retrieving data signals from a preselected one of a set of concentric recording tracks on the discs. In such a system, it is necessary to record data on a disc to enable the transducer heads to locate the desired recording track. Accordingly, a number of track following systems for magnetic disc drives have been developed. Most commonly, a disc surface and a head have been dedicated to the recording of position information for use by the track following servo system. In these systems, position information is recorded continuously around the disk. Typical techniques for recording position information are disclosed in U.S. Pat. No. 3,534,344 to Santana and U.S. Pat. No. 3,691,543 to Mueller. In both of these patents, position information is derived from single pulse amplitudes which are time-gated from recorded clock pulses. In the continuous systems for which they were designed, these pulses are repeated continuously around the disc and position information is continuously derived at the output of a comparator. In such a continuous system, each track crossing can be detected by the track following circuitry no matter how fast the head carriage might be moving. For this reason, track identification information can be derived by simply decrementing a track difference counter until the difference is equal to zero, meaning that the transducer head has arrived at the desired track. For a variety of practical reasons, it is desirable to place track position information on the same surface as the data information and to eliminate the use of a dedicated surface and head for track position information. One reason is that misregistration of the disc center due to disc interchange or temperature variations can be accommodated since the head is moved directly to the track of interest. Another reason is that the physical alignment of the heads in a disc drive is not as critical as it is where there are multiple heads which must be aligned on multiple surfaces. As a result, no field adjustments are generally required. Another obvious reason is that an entire disc surface need not be dedicated to track position information. As a result, most recently developed systems have employed embedded servo information (i.e., prerecorded identification information, on the same surface used for recording data, for use by the head tracking servo system). In the most practical form of embedded servo system, each track is divided into a plurality of sectors and the track identification and fine position information is recorded at the beginning of each data sector. This information is then read by the same head that reads and writes data on the disc. Previous embedded servo systems are exemplified by U.S. Pat. No. 4,208,679 to Hertrich, U.S. Pat. No. 4,163,265 to Van Herk et al, U.S. Pat. No. 4,149,201 to Card, U.S. Pat. No. 3,812,533 to Kimura, U.S. Pat. No. 3,185,972 to Sipple and British Patent Application No. 2017364 to Droux. Several problems arise from the use of embedded servo information. The data/servo head is capable of writing over and therefore destroying the servo information and this must be prevented. During a high speed search for a given track and sector, the head may cross several tracks between sectors of embedded servo information. Since servo information is recorded only once per sector in a short burst, the effect of a defect in the disc or a noise burst is much more severe. SUMMARY OF THE INVENTION According to the present invention, there is provided a method and apparatus for recording and retrieving embedded servo information which incorporates a variety of features which improve system reliability in the presence of noise, media defects and spindle speed variations. The present method and apparatus is capable of an extremely high degree of accuracy, even in the presence of high head carriage speeds. The present system has a significantly reduced susceptibility to noise bursts and to defects in a disc surface. The present system virtually eliminates the possibility of the data/servo head writing over and therefore destroying the servo information. Briefly, the present invention achieves the above by recording a unique pattern of servo data at the beginning of each data sector. Specifically, the embedded servo data includes a gap which is fully DC erased and which is used as an initial time sync for the servo information recovery system. A multiple-bit burst of "zeros" is recorded following the erase gap in order to provide a clock synchronization signal for a data separator. This burst of zeros is followed by a special sector mark code consisting of a multiple-bit burst of "ones" which is used as an additional verification of embedded servo timing information from which the next multiple bits are expected to be track identification data and a check code. A track identification code in Gray code format is repeated three times in succession. This code changes between adjacent sectors of adjacent tracks and provides tolerance for media defects. Following the three track identification codes, a special clock shift check code which is the same for all sectors and all tracks is recorded as a means of verifying that a noise pulse or media defect has not caused a time shift error in the previous bits of track identification data. Two bursts of high density transitions are recorded on the disc following the check code for the purpose of providing fine position information. These bursts are written so as to equally overlap adjacent tracks and to be offset in time so that they may be readily separated by the servo information recovery system. These bursts are recorded so that when a head is on track, the amplitude of the signal from one burst is equal to the amplitude of the signal from the other burst. OBJECTS, FEATURES AND ADVANTAGES It is therefore an object of the present invention to solve the problems associated with the unreliability of detected servo information as a result of noise, media defects and spindle speed variations. It is a feature of the present invention to solve these problems by recording servo data in a format such that a unit distance track identification code is recorded a plurality of times in succession followed by an unvarying clock shift checkcode. An advantage to be derived is a system capable of an extremely high degree of accuracy. Another advantage is a system having a significantly reduced susceptibility to media defects. A still further advantage is the virtual elimination of the possibility of a data/servo head writing over and therefore destroying servo information. Another advantage is a system which detects spindle speed variations. Still another advantage is a system which detects time shift errors. Still another advantage is the elimination of precise timing accuracy for the obtaining of position data. Still another advantage is an improvement in signal-to-noise ratio. Still other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment constructed in accordance therewith, taken in conjunction with the accompanying drawings wherein like numerals designate like parts in the several figures and wherein: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows diagrammatically the information recorded on a disc surface together with a timing diagram showing the normal timing of the various signals; and FIG. 2 is a block diagram of a preferred implementation of a servo information recovery system. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to FIG. 1, there is diagrammatically shown the information recorded on the surface of a disc (not shown) adapted for use in a magnetic disc recording system (not shown). FIG. 1 shows adjacent portions of adjacent tracks 10, specifically the portions of tracks 10 at the beginning of a sector where the head positioning data is recorded for use by a servo system for deriving position information. From an inspection of FIG. 1, it is seen that the embedded servo data for each data sector includes an erase gap 11, i.e. a band at the beginning of each servo sector which is fully DC erased. In the recording codes generally used in magnetic disc recording systems, "ones" and "zeros" are both identified by the existence of recorded transitions so that a fully erased area is distinctly identifiable. Erase gap 11 is used for initial time synchronization for the servo information recovery system, to be described more fully hereinafter. Following erase gap 11 are two bands 12 and 13 of prerecorded sector identification data. Band 12 is referred to herein as a preamble and preferably consists of a thirteen-bit burst of "zeros" recorded immediately following erase gap 11 in order to provide a clock synchronizing signal for a data separator, to be described more fully hereinafter. Immediately following the preamble in band 12 is a sector mark code in band 13, preferably a three-bit burst of "ones" used as an additional verification of embedded servo timing information to indicate that the next bits should be track identification data and a check code. In magnetic disc drives using embedded servo techniques, the requirement exists for knowledge of which track the head is currently positioned over. To accommodate this requirement, track boundary crossings are typically counted. In continuously recorded servo implementations, counting boundaries during high speed head moves is no problem since information is available continuously. However, in an embedded servo system where track boundary information is available only on an intermittent basis, as here, it is possible to skip track boundaries. Hence, there arises a need for track identification. This identification could go to the extreme of recording an absolute track address for every track on the disc. A more practical implementation is to record repeated bands wherein the tracks are identified within the band, i.e. groups of sixteen tracks per band where the tracks within the band are numbered 0-15. This requires only four bits of data for track identification. In recording this type of data, it is preferable to use a unit distance code, commonly referred to as a Gray code. These codes were developed so that only one bit of the code changes as a boundary between tracks is crossed. Use of a Gray code limits ambiguity to a head position uncertainty of ±1/2 track. According to the present invention, sector mark band 13 is followed by a band 14 containing a four-bit track identification code in Gray code format which is repeated three times in succession (a total of twelve bits). Recording the Gray code track identification information three times provides for more than mere redundancy. More specifically, one of the purposes and objects of the present invention is to record data in a way that the servo information recovery system is insensitive to media defects. Such media defects typically occur in the form of pinholes on the surface of the disc where magnetic signals are not recorded. If a track identification code is recorded only once and a pinhole obliterates one or more of the bits of data, it would be impossible to read a correct code. If a track identification code is recorded twice and a pinhole obliterates one or more of the bits of data in one of the codes, again it would be impossible to determine which code is the correct one. On the other hand, by recording the track identification code three times, a two-out-of-three vote can be implemented in a microprocessor such that if two out of the three track identification codes agree, it may be assumed that valid track identification information has been detected. Even if the microprocessor determines that two out of the three or all three track identification codes agree, it still cannot be stated with assurance that valid track identification information has been detected. The reason for this is that the loss of one or more data bits could cause a time shift in the data so that all data bits are shifted by one or more bits. If this should occur, each of the three track identification codes could be the same, but each could be wrong. In order to eliminate time shift errors, band 14 is followed by a band 15 having recorded therein a special clock shift check code as a means of verifying that a noise pulse or media defect has not caused a time shift error in the previous twelve bits of track identification data. As shown in FIG. 1, the check code selected consists of four bits, specifically "0010". This exact same check code appears at the end of the track identification data in every sector of every track 10. The servo information recovery system looks to see whether this bit pattern follows the track identification data and, if it exists, it is now assumed that the data just read is correct. From an inspection of the check code, it will be apparent that any time shift error will cause a change in the location of the "1" so as to invalidate the track identification data. The fact that the exact same check code appears in every sector of every track 10 is significant. Conventional check codes would be ineffective in a magnetic disc recording system. Conventional check codes are generated by performing a mathematical algorithm on recorded data and forming data bits which relate to the recorded data. In data retrieval, the mathematical algorithm is performed on the recovered data and the derived check code is compared with the recorded check code. However, in a magnetic disc storage system where a head is positioned between adjacent tracks, recording data in a Gray code format will limit head position ambiguity, but there is no way to insure that the retrieved check code will relate to the retrieved track identification data if the check code is different for each track. This leads to the present use of the exact same check code in every sector of every track. According to the preferred embodiment of the present invention, band 15 is followed by bands 16 and 17 in which there is recorded high density transitions, generally designated "A" and "B", respectively, for the purpose of providing fine position information. Bands 16 and 17 are offset in time and are offset laterally relative to each other and relative to tracks 10 so that each band equally overlaps adjacent tracks 10. It will be apparent that when a transducer head, to be described more fully hereinafter, is in position 18 (FIG. 1), where it is exactly aligned with a track 10, the amplitude of the signal received by such head from band 16 will be equal to the amplitude of the signal received from band 17. This information can be used by the servo information recovery system to indicate that the head is "on track". On the other hand, when the head is in position 19 between adjacent tracks 10, the head will receive a signal only from band 17. In intermediate positions, the inequality of the A and B signals from bands 16 and 17 may be used to indicate the location of the head relative to any one of tracks 10. Following bands 16 and 17 appear bands 20 having no data recorded therein for receipt of data from the user of the system. Each band 20 will be followed by a band 11 and the pattern will repeat. Referring now to FIG. 2, there is shown a preferred implementation of a servo information recovery system, generally designated 30. System 30 is adapted for use in a magnetic disc storage system of the type described hereinbefore. Such a system incorporates one or more transducer heads 31 carried at the end of an elongated support to thereby enable such head to be positioned over any annular track on the surface of a disc. For a fuller discussion of a magnetic disc storage system, reference should be had to copending U.S. patent application Ser. No. 321,884 filed Nov. 16, 1981, now U.S. Pat. No. 4,376,294, entitled "Head Loading and Retraction Apparatus for Magnetic Disc Storage Systems" and assigned to DMA Systems Corporation, the assignee of the present application. Head 31 is flying over the surface of the rotating magnetic disc producing read-back signals in response to the prerecorded servo data shown in FIG. 1. The signal from head 31 is amplified by an amplifier 32, the output of which is conducted to additional amplifiers 33 and 34 and a differentiator and crossover detector 35. Amplifiers 32-34 simply increase the amplitude of the signal from head 31 in order to provide an adequate signal level for the various recovery electronic functions. The analog signal from amplifier 32 is differentiated and crossover detected by circuit 35 to provide a digital version of the recorded analog information. Accordingly, the output of circuit 35 is a logic level signal with pulses occurring at each plus or minus peak of the original waveform from magnetic head 31. Such a differentiator and crossover detector is well known to those skilled in the art. The output of circuit 35 is then applied to a data separator 36 which is capable of decoding the train of pulses from circuit 35 into "ones" and "zeros" according to the recording code used when the servo data format was recorded. The exact construction and function of data separator 36 will, therefore, depend upon the particular recording data format used. Data separator 36 requires a preamble of all "zeros" in order to distinguish the clock transitions of the recorded data code and to synchronize its circuit function for reliable data decoding. Thus, data separator 36 utilizes the burst of zeros recorded in preamble 12. In any event, circuits capable of decoding a train of pulses into "ones" and "zeros" in accordance with a particular recording code are well known to those skilled in the art. The output of data separator 36 on a line 37 consists of a serial string of data which is fed to the input of a sixteen-bit shift register 38. In addition, data separator 36 generates a clock signal that is applied to the clock input of shift register 38, to be used as a shift clock, and to a sixteen-clock counter 40. Shift register 38 is a conventional shift register and counter 40 is a conventional digital counter. An erase gap detector 41 responsive to the output of amplifier 34 is the circuit that starts the entire process of servo data recovery. That is, at the end of erase gap 11, which is detected by an interval wherein no signal is received from head 31, the onset of preamble data in band 12 causes erase gap detector 41 to generate a logic level "one" on a line 42 indicating that there is "signal present". This signal on line 42 is applied together with a "timer enable" signal on a line 43 from a timer 44 to the input of an AND gate 45. When both inputs to AND gate 45 are true, an "erase gap enable" signal is generated on a line 46 which is used to activate a sector mark decoder 47. Sector mark decoder 47 is connected to the output of shift register 38 so as to monitor the first three bits of data. Accordingly, sector mark decoder 47 outputs a "start" pulse on a line 48 on the occurrence of the sector mark code "111" provided "erase gap enable" line 46 is true. The start pulse on line 48 is applied to counter 40. Erase gap detector 41 may be implemented by combining a conventional peak detector with a threshold circuit in order to detect the presence of a signal from head 31. Sector mark decoder 47 may be a simple three-input AND gate to detect the presence of three "ones" in shift register 38. System 30 has now been conditioned to receive and analyze the next sixteen bits of data from magnetic head 31. It should be noted that in order for this to occur, erase gap detector 41 must sense the erase gap, timer 44 must enable gate 45, and sector mark decoder 47 must detect the sector mark code recorded in band 13. The start pulse on line 48 initiates a counting of the next sixteen clock pulses from data separator 36 by counter 40, at the end of which an "end 16 clock count" line 49 goes true. The signal on line 49 is applied as one input to a three input AND gate 50. AND gate 50 also receives an input on line 43 from timer 44 and a signal from a clock detecter 51. Clock check decoder 51 may be a circuit similar to sector mark decoder 47 and is coupled to the output of shift register 38 so as to monitor the most recently recorded four bits of data. Since the track identification data on band 14 is received first, the most recently recorded four bits should be the data in check code band 15. When these four bits are "0010", the output of decoder 51 will be true. Thus, if the three inputs to AND gate 50 are simultaneously true, gate 50 will generate a true "load Gray code" signal on a line 52 connected to a microprocessor 53. Microprocessor 53 is also coupled to the output of shift register 38. It should be noted here that at the end of sixteen clock pulses, the three successively recorded track identification bits in Gray code format and the clock check code should be present in register 38. As mentioned previously, the clock check code is used to insure that no noise or media defects have caused a clock pulse failure which may mean that every bit of the sixteen bits could be mispositioned in register 38 by one or more bits. In such a case, even a majority vote of three Gray codes could be in error. The bit pattern selected for the clock check code in band 15 is absolutely reliable for protection against a ±2 bit shift error so that the presence of a "load Gray code" signal on line 52 is a highly reliable indication of the validity of the Gray code data. Accordingly, a command on line 52 is used to instruct microprocessor 53 to read the twelve bits of track identification data and to determine a majority decision on the track just read by magnetic head 31. If two out of the three Gray code signals are consistent, microprocessor 53 outputs track information on a line 54 which is used by the servo control circuitry (not shown). The "load Gray code" signal on line 52 is also used to start timer 44, which has several functions. Timer 44 is a very accurate device, preferably including a precise crystal oscillator, so that time decodes can be accurate to within 0.01%. The first function of timer 44 is to bring true the "timer enable" signal on line 43 at a time just before the next expected "signal present" occurrence on line 42 and to set it false again just after the next expected clock check decode signal from decoder 51. This time accurate "timer enable" gate provides protection against the possibility that the speed of the spindle driving the disc is out of speed tolerance, an occurrence which could endanger the embedded servo data. Writing of data on the disc is allowed by the write control circuitry (not shown) only after a proper occurrence of a "load Gray code" signal on line 52 in the embedded servo field preceding the data field to be written. This assures that the track following servo information is acceptable and that the spindle speed control system is functioning properly so as to prevent the head 31 from writing over and therefore destroying the embedded servo information. FIG. 1 also shows the normal timing of the various signals. That is, the "timer enable" pulse on line 43 from timer 44 is shown at 55. It is seen that this signal goes true just prior to band 12 and goes false again just after band 15. The distance between the time when the "timer enable" pulse goes true and the "signal present" signal on line 42 goes true, as shown at 56, is the degree of speed tolerance permitted by system 30. The output of sector mark decoder 47 on line 48 is shown in FIG. 1 at 57, the "end 16 clock count" signal on line 49 from counter 40 is shown at 58, the output of clock check decoder 51 is shown at 59, and the "load Gray code" signal on line 52 from gate 50 is shown at 60. Timer 44 also provides time gate pulses for sampling the high density data bursts from bands 16 and 17. Thus, timer 44 provides accurately timed gate signals on lines 61 and 62 (shown at 63 and 64, respectively, in FIG. 1) which are applied to A and B sample and hold circuits 65 and 66, respectively. Circuits 65 and 66 receive the output of amplifier 33. The outputs of circuits 65 and 66 are applied to a third A-B sample and hold circuit 67 which receives a timing signal from timer 44 over a line 68. Circuits 65 and 66 are conventional analog sample and hold circuits which, when activated, sample the analog level of an input signal and hold it for further use. As can be seen from an inspection of the timing diagrams of FIG. 1, timer 44 activates circuit 65 at a time when the A position data is expected from band 16 and activates circuit 66 at a time when the B position data is expected from band 17. The A and B data from bands 16 and 17 as sampled by circuits 65 and 66 is applied to circuit 67 which forms the difference (A-B) therebetween. This difference signal is a "position error signal" which is applied via a line 69 to the servo control circuitry to correct the location of magnetic head 31 and to hold it "on track". In the event of noise at the output of magnetic head 31 during the servo data time, the absence of a "load Gray code" signal on line 52 will inhibit the issuance of new "track information" on line 54 and an updated "position error signal" on line 69 so that bad data is not sent to the servo control circuitry, thus preserving the last good (noise-free) sample of information. If two consecutive "load Gray code" signals on line 52 are missed by timer 44, a "fault" signal is sent over a line 70 to microprocessor 53 and appropriate system action is taken. A "clear" signal is issued by microprocessor 53 and applied to timer 44 over a line 71 to enable timer 44 to accomplish a restart of servo information recovery system 30. In summary, in embedded servo applications where position information is available only intermittently at the beginning of each data sector, it is extremely important to acquire position information in a timely manner. It is also imperative that this position information be free from noise effects from all sources. It is particularly important that minor defects in the recording media itself not affect the integrity of the position information. It can therefore be seen that according to the present invention there is provided a method and apparatus for recording embedded servo information which incorporates a variety of features which improve system reliability in the presence of noise, media defects, and spindle speed variations. The present method and apparatus is capable of an extremely high degree of accuracy, even in the presence of high head carriage speeds. The present system has a significantly reduced susceptibility to noise bursts and to defects in the disc surface. Furthermore, the present system virtually eliminates the possibility of the data/servo head writing over and therefore destroying the servo information. While the invention has been described with respect to the preferred physical embodiment constructed in accordance therewith, it will be apparent to those skilled in the art that various modifications and improvements may be made without departing from the scope and spirit of the invention. Accordingly, it is to be understood that the invention is not to be limited by the specific illustrative embodiment, but only by the scope of the appended claims.
In a magnetic disc storage system and a magnetic disc therefor, the disc having opposed surfaces, at least one of the surfaces being coated with a magnetic material, the disc being adapted to be mounted on a spindle for rotation relative to a magnetic transducer positioned for recording data on and retrieving data from the disc, a plurality of concentric annular tracks being defined on the surface of the disc, each of the tracks being divided into a plurality of sectors, each sector having associated therewith prerecorded servo data for identification thereof, the improvement wherein the servo data for each sector comprises a unit distance track identification code recorded three times in succession, the code changing between adjacent sectors of adjacent tracks, and a clock shift check code recorded immediately following the last recorded one of the track identification codes, the same clock shift check code being recorded for each sector of every track.
6
BACKGROUND OF THE INVENTION The present invention relates generally to the field of catheters. More specifically, the present invention relates to catheters which are adapted to be inserted into the urethral lumen to alleviate obstructive prostatism, a condition quite common in males over the age of 50. The prostate is a somewhat pear-shaped gland that extends around the urethral lumen from the neck of the bladder to the pelvic floor. Because of the close relationship of the prostate to the urethra, enlargement of the prostate, usually referred to as hypertrophy or hyperplasia, may fairly quickly obstruct the urethra, particularly if the hyperplasia occurs close to the lumen. Such an obstruction inhibits normal micturition, which causes an accumulation of urine in the bladder. The surgical treatment of hyperplasia of the prostate gland has been a routine procedure in the operating room for many years. One method of surgical treatment is open prostatectomy whereby an incision is made to expose the enlarged prostate gland and remove the hypertrophied tissue under direct vision. Another method of treating obstructive prostatism is a technique known as transurethral resection. In this procedure, an instrument called a resectoscope is placed into the external opening of the urethra and an electrosurgical loop is used to carve away sections of the prostate gland from within the prostatic urethra under endoscopic vision. The technique of transurethral resection offers many benefits to the patient as compared to open prostatectomy. Using this technique, the trained urologist can remove the hypertrophied prostate with less patient discomfort, a shorter hospital stay and lower rates of mortality and morbidity. Over 333,000 patients underwent this procedure in the United States in 1985, with an average hospital stay of six days. Notwithstanding the significant improvement in patient care resulting from the widespread application of transurethral resection, there remains a need for a less invasive method of treating the symptoms of prostate disease. One of the earliest methods of relieving acute urinary retention, a symptom associated with prostate disease, was the placement of a catheter through the external urethral opening into the bladder, thereby allowing the outflow of urine from the bladder by way of the catheter lumen. These urinary catheters typically employ a balloon at the tip which, when inflated, prevents the expulsion of the catheter from the body. However, due to problems of infection, interference with sexual activity, and maintenance involved with such catheters, they are generally unacceptable for long term treatment of micturition problems. U.S. Pat. No. 4,432,757 to Davis, Jr. teaches the use of an indwelling urethral catheter assembly, having a Foley-type balloon disposed near the distal end thereof and a substantially non-compliant balloon lead shaft proximate to the Foley-type balloon. The device is adapted to be inserted through the urethra up into the bladder. The Foley-type balloon and the balloon lead shaft are then inflated, although the balloon lead shaft remains relatively non-compliant and therefore does not expand appreciably. Gentle traction is then applied to a catheter sleeve head to sever the sleeve from the remainder of the catheter, leaving the balloon lead shaft in position within the urethra. Another method of treating hypertrophy of the prostate gland without the need for surgery has been to inject medications into the prostate gland by means of a catheter. Such a device is disclosed in U.S. Pat. No. 550,238 to Allen, wherein two balloons are disposed along two sections of a catheter, and inflated to isolate an area within the urethra prior to the injection of the medication. However, these injections are frequently ineffective as the prostate gland exhibits only a limited ability to absorb the injected antibiotics, and proper positioning and retaining of the catheter with respect to the affected area is extremely difficult. A substantial improvement in an apparatus and corresponding method of treatment for obstructive prostatic hypertrophy is disclosed in Klein, U.S. Pat. No. 4,660,560. In Klein's method, a calibrating catheter is used to measure the distance between the neck of the bladder and the bottom of the prostate gland. A dilatation catheter, having an annular balloon with a length equivalent to the measured length, and a Foley-type balloon at the distal end thereof is then inserted into the urethra until the Foley-type balloon is within the bladder. The Foley balloon is then inflated in the bladder and is used to position the dilatation balloon in the prostrate. The latter balloon is then inflated, to force the prostate away from the urethral lumen. Use of the Klein catheter can effectively eliminate uncertainty regarding positioning of the upper (distal) end of the dilatation balloon, thereby significantly facilitating the treatment of prostatic hypertrophy. In practicing the Klein method, after the calibration catheter is used to measure the length of the affected prostate, it is withdrawn from the urethra, and the dilatation catheter is then inserted. Proper insertion of the dilatation catheter is crucial, as stretching of the external urethral sphincter muscle, which lies just below the prostate, could cause incontinence. Although some means of visualizing placement of the proximal end of the dilatation balloon is therefore desirable, the catheter is too large to fit through a conventional cystoscope sheath. Moreover, bleeding, which is common during such a procedure, not infrequently obscures the field of view of a cystoscope lens, making it useless. Accordingly, in practicing the method of the Klein patent, there is a need for a method and apparatus to permit effective and sure positioning of the proximal end of the dilatation balloon with respect to the external urethral sphincter. There is a particular need to permit visualization of the balloon placement in vivo during the course of the surgical procedure. SUMMARY OF THE INVENTION Briefly, the present invention provides a dilatation catheter and sheath of novel design for use as a non-surgical alternative to the treatment of the symptoms of obstructive prostatism. Advantageously, the sheath for the catheter of the present invention is uniquely sized and shaped so as to provide a path through which the catheter may travel, and leaves sufficient room for a standard cystoscopic lens. Preferably, the sheath is elliptically shaped so as to minimize the circumference thereof. The proximal end of the dilatation balloon is marked with a heavy line which may be viewed by the urologist through the lens. To facilitate the urologist's view within the urethra, or other bodily organ, an irrigation conduit is provided in the catheter. Saline or other irrigating solution is allowed to flow through the irrigation conduit, to an area proximate the line at the proximal end of the dilatation balloon. The saline solution flushes the blood associated with the procedure away from the lens, so that the urologist's view is no longer obstructed. A significant feature of the dilatation catheter of the present invention is the unique, squared-off configuration of either or both end of the dilatation balloon. This feature enables dilatation of the affected prostatic urethra, in close proximity to the bladder and/or external urethral sphincter muscle without inadvertent dilatation of these structures. Due to the fact that common angioplasty balloons are, in general, not strong enough withstand the pressures necessary to properly dilate the prostate, the dilatation balloon of the present invention is made from a material which has a high tensile strength, rated at between 20,000 to 50,000 psi., and although somewhat stiff, is of a sufficiently small thickness so as to provide a catheter which is of substantially the same size and shape of that of the unstretched lumen. Another significant advantage of the present invention is that the sheath is provided with a flexible tip which readily deforms to accommodate the sharp edges which may form when the dilatation balloon is deflated. The sheath also performs the function of evacuating the irrigation fluid from the urethral lumen during the irrigation process. Yet another key feature of the present invention is the ability to yield optimal dilatation of the prostate, even at the proximal and distal edges of the affected prostatic urethra. This is accomplished by subjecting the balloon material to elevated temperatures, controlled internal pressures and axial tension during the molding process, which stretch the balloon both axially and radially to form a balloon having a somewhat squared configuration at one or both ends. In accordance with one aspect of the present invention, there is provided an intraurethral dilatation device for relieving the symptoms of obstructive prostatism which is adapted for easy insertion into the urethra for pressure dilatation of the prostate, so as to force the prostate away from the urethral lumen and thereby eliminate the obstruction. The dilatation device includes an introduction sheath, suitable for housing a catheter and a cystoscope lens; a catheter shaft having a plurality of lumen therethrough; an expansible locating balloon, disposed near the distal tip of the catheter which, when inflated within the bladder, will provide an anchor with the bladder neck; and a dilatation balloon, proximate the locating balloon which, when inflated, conforms to a preselected configuration, so as to radially outwardly dilate the obstruction away from the urethral lumen. In an alternative embodiment, the means for inflating the dilatation catheter is provided with a clipping mechanism which is adapted to receive a portion of the sheath, and enable the urologist to perform the procedure without assistance. Advantageously, the clip is situated on the inflation device such that the urologist may view the location of the dilatation balloon through the endoscopic lens with one eye and at the same time monitor the pressure gauge with the other eye. Further objects, features and other advantages of the present invention will become apparent from the ensuing detailed description, considered together with the appended drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a dilatation catheter and sheath assembly in accordance with one embodiment of the present invention; FIG. 2 is a partial assembly view of the clipping mechanism; FIG. 3 is a perspective view of a septum, showing an inwardly extending boot sleeve in cut away; FIG. 3a is a perspective view of a second type of septum, having both boot sleeves projecting outwardly; FIG. 4 is an end view of the sheath, showing the unique ellipsoid shape of the inner walls thereof; FIG. 5 is a perspective view of the tip of the sheath, as being deformed by a once-inflated dilatation balloon, so as to guide the balloon into the sheath before removal from the urethral lumen; FIG. 6 is a side view of the tip of an obturator; FIG. 7 is a side view of the sheath, having an obturator disposed therein, as ready for insertion into the urethra; FIG. 8 is a cross-sectional view, taken along line 8--8 of FIG. 7, showing in more detail the obturator removably disposed therein; FIG. 9 is a cross-sectional view, illustrating a plastic manifold disposed at the proximal end of the dilatation catheter during the molding process; FIG. 10 is a cross-sectional view, taken along line 10--10 of FIG. 11, showing the lumen arrangement within the catheter shaft; FIG. 11 is a side view of a dilatation catheter, having a stylet removably inserted therein; FIG. 12 is a cross-sectional view, taken along line 12--12 of FIG. 11, showing the overlap of the shoulder of the locating balloon with the shoulder of the dilatation balloon; FIG. 13 is a side view of a dilatation balloon, in an inflated state, exhibiting a squared-off configuration at one end, and a tapered configuration at the opposite end thereof, in accordance with one embodiment of the present invention; FIG. 14 is a side view of a dilatation balloon, having both ends in a tapered configuration, in accordance with an alternative embodiment of the present invention; FIG. 15 is a side view of a calibration catheter, showing a partial cut away view of an inflation aperture for the expandable balloon; FIG. 16 is a magnified view of the marking disposed near the proximal end of the dilatation balloon showing clearance of the external sphincter muscle; and FIG. 17 is a cross-sectional view of the urethral dilatation catheter of the present invention operatively inserted within the male urinary tract. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to the drawings in detail, wherein like reference numerals designate like elements throughout the several views thereof, there is shown generally at 10 in FIG. 1, a dilatation catheter and sheath assembly embodying the present invention in a preferred form. The sheath 12 is advantageously a substantially rigid, axially elongate hollow shaft throughout most of its length, but having a flexible distal tip 14. The sheath 12 exhibits an inner surface 16 which is substantially ellipsoid in cross-section, and is adapted to receive and guide an axially elongate catheter 18 and an endoscope 20 longitudinally therethrough. Advantageously, the particular endoscope used is known as a cystoscope. In one embodiment of the invention, a cylindrical housing 22, disposed near the base of the sheath, exhibits a pair of grooves 24, formed upon two flattened surfaces 26 of the cylindrical housing 22, on opposite sides thereof. An end view of the cylindrical housing 22, as shown in FIG. 4, illustrates the ellipsoid shape of the inner walls 15 of the sheath 12, and the flattened side surfaces 26 thereof. A U-shaped clip 28 is integrally connected to the top of an inflation device 30 and is adapted to removably receive and retain the cylindrical housing 22 so as to enable the device 10 to be operated by one person, without the need for assistance. The removable attachment of the sheath 12 to the U-shaped clip 28 is illustrated in FIG. 2. A C-shaped clip 32 may also be provided on the body of the inflation device 30, to removably receive and retain the catheter therein and provide additional support for the proximal end of the device, thus controlling the catheter so it does not interfere with the eyepiece of the endoscope. Situated on the underside 36 of the cylindrical housing 22 is a drainage port 38, having a cock valve 40 secured therein. The cock valve 40 is adapted to allow back-flowing fluids to escape the sheath 12 when positioned in the "on" position, and to prohibit the release of such fluids when in the "off" position. The cylindrical housing 22 includes a hub portion 42, disposed at the proximal end thereof. A rubberized septum 44, preferably formed from a silicon rubber compound, is detachably placed onto the hub 42 of the cylindrical housing 22 so as to provide a seal therefor. As best seen in FIGS. 3 and 3a, the septum 44 is a circular cap 46, having a pair of boot sleeves 48, 50 integrally connected to the proximal end of the cap 46. In one embodiment, the septum 44 exhibits an outwardly extending boot sleeve 48 and inwardly extending boot sleeve 50. The boot sleeves 48, 50 are adapted to receive the cystoscope lens 20 and the dilatation catheter 18, and provide the septum 44 with elasticity at the point of contact therebetween. Without the presence of such sleeves, the rubberized septum 44 would itself deform if a force were applied to either the catheter 18 or cystoscope lens 20, thereby detracting from the septum's sealing ability. Further, the boot sleeves 48, 50 are adapted to readily adjust to and grip the outer diameter of the catheter 18 and lens 20 to yield a good seal therebetween. In an alternative embodiment, as shown in FIG. 3a, both of the boot sleeves 52, 54 extend outwardly from the septum cap 44. This embodiment is possible only when there exists sufficient room on the outside of the septum, such that a sharing of a common wall between the two sleeves is not necessitated. As best seen in FIGS. 11, the dilatation catheter 18 of the present invention comprises an axially elongate catheter shaft 56, having a tapered guiding end 58, and a plurality of parallel conduits disposed therein. Situated near the guiding end 58 of the catheter shaft 56 is a locating balloon 60. The locating balloon 60 is a small latex Foley-type balloon, adapted for inflation by a source of pressurized fluid. Adjacent the locating balloon 60 is a larger dilatation balloon 62, having a proximal shoulder 64 and a distal shoulder 66. A feature of this invention is that the distal shoulder 66 of the dilatation balloon 62 is overlapped by a portion of the locating balloon 60, such that, when the balloons are expanded, a minimal valley is left between the two balloons. Both of the balloons 60, 62 are bonded to the outer perimeter of the catheter shaft 56 by suitable adhesive or thermal process. While the overlap of the locating balloon 60 onto the shoulder 66 of the dilatation balloon 62 increases the area of dilatation by minimizing the distance between the locating balloon 60 and the dilatation balloon 62, suboptimal dilatation of the affected prostatic urethra 68 still exists due to the tapered nature of expandable balloons, commonly used in dilatation processes. To achieve optimal dilatation near the ends 70, 72 of the affected prostatic urethra 68, the dilatation balloon 62 can be molded with a steep, squared off end 74, as illustrated in FIG. 13. Depending on the nature of the affected area of the prostatic urethra 68, it may be desirable to enable urethral dilatation very close to the bladder neck 72 or the external sphincter muscle 70. Accordingly, either end of the dilatation balloon 62, neither end, or both ends may be provided with a substantially vertical configuration as illustrated in FIGS. 13, 14 and 17. A material which is well adapted to construction of the dilatation balloon 62 of the present invention is polyethylene terephthalate (PET), such as KODAK's 9921. Preferably, the balloon 62 is extruded in a straight pipe configuration and then stretched and blown under high temperature and pressure to yield the desired shape 74. This type of technique is commonly applied in the making of angioplasty balloons. It should be noted that the PET material used to construct the dilatation balloon exhibits superior tensile strength characteristics to that of materials used in manufacturing other types of dilatation balloons, for example older angioplasty balloons. The PET material used to construct the dilatation balloon of the present invention has a tensile strength of between 20,000 to 50,000 psi, and is rated to withstand at least 3 atmospheres of pressure, and as much as 5 atm. If a rubberized latex material were used to fabricate the dilatation balloon of the present invention, the walls of the balloon would necessarily be much thicker in order to withstand the exceedingly high pressures required for adequate dilatation of the affected prostatic urethra. Thus, the PET material, by virtue of its superior strength, allows a thinner balloon to be utilized. The thinness of the balloon thus formed, makes possible a dilatation balloon 62 which, in an uninflated state, conforms to the external walls of the catheter shaft 56, thereby providing a dilatation catheter 18 having substantially the same size and shape as the unstretched lumen. However, the increased strength of the material also dictates a balloon which is somewhat stiff and substantially less pliable than a latex balloon. Consequently, when negative pressure is applied to collapse the dilatation balloon 62 made of the PET material, sharp ridges may form on the exterior surface thereof. Advantageously, the distal tip 14 of the introduction sheath 12 is formed of a flexible material, which readily deforms to the gross contours of the deflated dilatation balloon 62, so as to coerce the balloon 62 into the introduction sheath 12 prior to the withdrawal of the catheter 18 from the urethra. Preferably, the tip 14 is formed from a substantially malleable Poly Vinyl Chloride (PVC) compound, which is RF welded to rigid shaft portion 12 of the sheath. To ensure that the catheter 18 is fully within the introduction sheath 12 prior to the withdrawal thereof, visual indicia, such as the marking 78 on the exterior shaft 56 of the catheter 18 is provided. As the catheter shaft 56 and deflated dilatation balloon 62 are gradually withdrawn from the urethra, the indicia 78 will be advanced out of the sheath 12. When the designated indicia 78 becomes visible, the catheter 18 is fully retracted within the sheath 12, and the device 10 may be withdrawn, without causing undue trauma to the urethral lumen. As best seen in cross-section in FIG. 10, the catheter shaft 56 houses a pair of circular inflation conduits 80, 82 and an irrigation conduit 84. The inflation conduit 80 having an aperture 86 underlying the locating balloon 60 exhibits a tubular passageway which permits pressurized fluid to be transmitted into the chamber enclosed by the locating balloon 60, so as to selectively inflate the balloon 60 to a suitable level. Likewise, the inflation conduit 82 having a pair of inflation apertures 90, 92 underlying the dilatation balloon 62 allows pressurized fluid to selectively fill the balloon 62 to a desired level. To facilitate inflation of the locating balloon 60, a simple fluid valve 94 may be connected to the proximal end of the conduit 80. This valve 94 is integrally connected to the inflation conduit 80 and may be easily manipulated to allow quick sealing of the conduit 80 and maintain the pressurized fluid within the balloon chamber 60 and the conduit 80. The locating balloon 60 may be pressurized by inserting a hypodermic syringe (not shown) into the valve 94, with the valve 94 in its open condition. By forcing fluid into the conduit 80, the locating balloon 60, at the distal end of the inflation conduit will be inflated. The valve 94 may then be closed, and the hypodermic syringe removed, leaving the locating balloon 60 in an inflated state. Since inflation of the dilatation balloon 62 is more critical, the source of pressurized fluid 98 used to inflate the dilatation balloon 62 is connected to a pressure gauge 100. Preferably, the inflation device 98 includes a syringe barrel 102 having a threaded rod and ratchet mechanism 104 which replaces the conventional plunger. This configuration allows fine tuning of the pressure amassed within the dilatation balloon 62 by screw turning the threaded rod 104. It has been determined that an intra-balloon pressure of approximately 3 atm., or 45 p.s.i.g. is sufficient to force the prostate away from the urethral lumen to relieve the obstruction and reestablish normal micturition. Proximate to the proximal end of the dilatation balloon 62, and encircling the proximal shoulder 64 thereof, is a heavy black line 106. Prior to inflating the dilatation balloon 62, care should be taken to ensure that the black line 106 does not extend onto any portion of the external urethral sphincter muscle 108. This is vitally important as accidental dilatation of the sphincter 108 may cause the patient to lose voluntary control over micturition, especially if the sphincter experiences plastic deformation, i.e., the inability to return to its original shape. An important feature of this invention is the provision of an irrigation system. As described below, the system provides the dual features of both flushing blood away from the lens of the cystoscope to aid in the viewing of the external sphincter muscle and the black line 106 on the shoulder 64 of the dilatation balloon 62 and inhibiting coagulation of blood within the urethra. This flushing system includes a plurality of irrigation ports 110 disposed along the exterior shaft 56 of the catheter 18, proximate to the line 106 are provided. The irrigation ports 110 are adapted to continuously flush fluid, for example, saline, from the irrigation conduit 84, which extends through the center of the catheter shaft 56. The irrigation conduit 84 is provided with a coupling device 112 at the proximal end thereof, adapted to receive a source of flushing fluid, which, for example, can be a hanging container of saline (not shown), having a length of flexible tubing extending therefrom, for connection to the coupling device 112. The source of fluid is elevated and allowed to flow by gravity through the irrigation conduit 84 and out the irrigation ports 110, so as to flush blood away from the lens 20 and allow the urologist an unobstructed view of the external sphincter muscle 108 and the line 106 encircling the proximal shoulder 64 of the dilatation balloon 62. In addition to permitting an unobstructed view of the proximal shoulder 64 of the balloon 62, the flushing of blood inhibits coagulation, and therefore substantially eliminates clotting within the urethral lumen. Back-flowing flushing fluid and blood is drained from the urethra through introduction sheath 12 by gravity flow. A drainage reservoir (not shown) is connected to the cock valve 40 which, when in its open position, allows the back-flowing fluids to drain, by gravity flow, into the reservoir and subsequently disposed of. Alternatively, the flushing fluid can be supplied through the sheath 12 to flush blood away from the cystoscope lens 20. In this embodiment, the irrigation ports 110 of the irrigation conduit 84 function as influent ports to drain the flushing fluid and blood out of the urethra. Located at the proximal end of the catheter shaft 56, and integrally connected thereto, is a Y-shaped plastic manifold 118. The manifold 118 is adapted to define and separate the trio of conduits 80, 82, 84 disposed within the body of the catheter shaft 56. Preferably, the manifold 118 is preformed in the Y-shaped configuration and is adapted to connect to the catheter shaft 56 and trio of conduits at the proximal end thereof. The catheter shaft 56 should be bent and cut to expose the inflation conduits 80, 82 respectively. The irrigation conduit 84 need not be exposed in this manner, as the manifold 118 includes a substantially straight portion in which the proximal end of the irrigation conduit 84 will reside. As shown in FIG. 9, during the molding process flexible core pins 122, 124 are inserted into the exposed inflation conduits 80, 82 to respectively maintain the openings into the inflation conduits and provide support therefor during the molding process. In a similar manner, a straight core pin 126 is inserted into the irrigation conduit 84, and the catheter 18 is set into the preformed plastic manifold 118. Plastic is then injected into the manifold 118 to form a tight seal, and the core pins 122, 124, 126 are removed after the plastic has hardened. Method of Using the Dilatation Catheter Prior to dilating the obstructed urethral lumen, the length of the affected prostatic urethra 68 should be measured. This may be accomplished by the use of a calibration catheter 128, as illustrated in FIG. 15. The calibration catheter 128 is an axially elongate shaft 130, having an expandable balloon 132 located near the distal end 134 thereof, and an inflation conduit (not shown) which extends substantially the entire length of the shaft 130. The expandable balloon 132 is adapted to be inflated through an inflation aperture 136, extending from the inflation conduit by a source of pressurized fluid (not shown). A plurality of graduated markings 138 extend along the exterior shaft 130 of the catheter 128, commencing near the proximal end 140 of the expandable balloon 132, and are adapted to be read from the distal end 134 of the catheter 128 to the proximal end 142. The calibration catheter 128 is adapted to be received into the sheath of a standard cystoscope, and the cystoscope inserted into the urethra through the penile meatus. Once the distal end 134 and expandable balloon 132 of the calibration catheter 128 enters the bladder 144, the expandable balloon 132 may be inflated, and the catheter 128 slowly withdrawn from the urethra until the balloon 132 becomes lodged within the bladder neck 72. Graduated markings 138, inscribed on the exterior shaft 130 of the catheter 128 can be used to measure the distance between the bladder neck 72 and the lower end 70 of the affected prostatic urethra 68. Once such a measurement has been determined, the expandable balloon 138 may be deflated, and the catheter 128 withdrawn. An introduction sheath 12, as illustrated in FIGS. 7 and 8 is then readied for insertion through the external urethral opening. An obturator 146, as shown in FIGS. 6, 7 and 8, having a smooth, tapered end 148 with no sharp edges is inserted into the sheath 12, and secured to the hub 42 of the cylindrical housing 22 by chamfered clips 150. The flexible tip 14 of the sheath 12 tapers inwardly, so as to grip the extending portion of the obturator 146 and provide a fairly smooth surface continuation of the introduction sheath. This mild transition between the obturator 146 and sheath 12 is instrumental in reducing damage and trauma to the tender urethral lumen. Once the sheath 12 has been fully inserted within the urethral lumen, the chamfered clips 150 may be released, and the obturator 146 withdrawn. A catheter shaft 56, having a dilatation balloon 62 with a length approximately equivalent to that measured by the calibration catheter 128, is then inserted through one 48 of two boot sleeves of the septum 44, until at least that portion of the catheter shaft 56 to which the expansible balloons 60, 62 are attached extends therethrough. The septum 44 is then friction fit onto the hub 42 of the cylindrical housing 22 such that the catheter 18 is in alignment with the larger diameter ellipsoid section 152 of the sheath 12. The cystoscope lens 20 is then inserted into the other boot sleeve 50, and is then urged through the sheath 12 and into the urethra after placement of the catheter 18. To provide support for the catheter 18, an elongate stylet 154 may be inserted into the irrigation conduit 84, as illustrated in FIG. 11. The stylet 154 facilitates the ease With which the catheter 18 may be inserted into the urethra, and may remain within the irrigation conduit 84 until the locating balloon 60 is disposed within the bladder 144, at which time the stylet 154 should be removed. Once the locating balloon 60 is within the bladder 144, the inflation conduit 80 may be coupled to a source of pressurized fluid so as to inflate the locating balloon 60. The catheter 18 is then gradually withdrawn from the bladder 144 until the balloon 60 is lodged within the bladder neck 72. When the locating balloon 60 is properly positioned within the neck 72 of the bladder 144, a seal is formed therebetween which prohibits fluids accumulating within the bladder 144 from travelling down the urethra and also prohibits fluids from flowing into and filling up the bladder from the urethra. Once the catheter 18 has been properly situated with respect to the upper end 72 of the affected prostatic urethra 68, the irrigation conduit 84 may be connected to a source of flushing fluid. The flushing fluid is gravity fed through the irrigation conduit 84 and out the irrigation ports 110, so as to wash existent blood away from the cystoscope lens 20 and provide the urologist with an unobstructed view of the proximal shoulder 64 of the dilatation balloon 62, and adjacent organs. Looking through the cystoscope, the urologist can manipulate the catheter 18 to confirm that the dilatation balloon 62 is clear of the external urethral sphincter muscle 108, so as to ensure that the sphincter 108 will not inadvertently be dilated. Upon properly positioning the dilatation balloon 62 with respect to both the bladder neck 72 and the sphincter 108, the inflation conduit 82 for the dilation balloon 62 may be connected to a source of pressurized fluid 98. As described above, the inflation source 98 should enable a accurate, progressive dilation under constant control of the pressure being applied within the dilatation balloon 62. The device remains within the affected prostatic urethra 68, until sufficient pressure dilatation has been achieved. Subsequent to attaining adequate pressure dilation of the prostatic urethra, and eliminating the urinary outflow obstruction, the balloons 60, 62 may be deflated, releasing the pressurized fluid therefrom. As the dilatation balloon 62 is deflated, sharp ridges may form on the outer surface thereof, due to the stiffness of the material from which it was formed. As shown in FIG. 5, the flexible tip 14 of the introduction sheath 12 readily deforms and flares, so as to coerce the dilatation balloon 62 back into the sheath 12. When the marking 78, indicative of the time at which the dilatation balloon 62 is completely within the sheath 12 becomes visible, the device may be withdrawn from the urethra. In view of the medical treatment to be administered in using the device of the present invention, it is necessary that the device be aseptically clean. Accordingly, the dilatation catheter and sheath can be cleansed and sterilized readily and easily either prior to use thereof, or packaged in this condition, available for immediate use. Further, both the catheter and sheath may be discarded after use, negating the need for recleaning and resterilization. It will be appreciated that certain structural variations may suggest themselves to those skilled in the art. The foregoing detailed description is to be clearly understood as given by way of illustration, the spirit and scope of this invention being limited solely by the appended claims.
Disclosed is an apparatus and method for the treatment of the symptoms of obstructive prostatism. The apparatus comprises an expandable dilatation catheter and an axially elongate sheath, adapted for transurethral insertion via the external opening of the urethra. The sheath is ellipsoid in cross-section, and provides an initial path through which the catheter and a standard cystoscope lens is guided. Disposed near the proximal end of the expandable dilation portion of the catheter is a plurality of irrigation ports. A saline solution travels through an irrigation conduit and is secreted through the irrigation ports so as to flush away blood, etc., away from the lens of a cystoscope and provides the urologist with an unobstructed view of the dilation catheter and external urethral sphincter muscle. Once the catheter has been properly positioned with respect to both the bladder neck and the sphincter, the dilation balloon may be inflated to force open the affected prostatic urethra and eliminate the obstruction.
0
CROSS REFERENCE TO RELATED APPLICATIONS This application is a 371 of PCT/IB95/00285, filed Apr. 24, 1995, which, in turn, is a continuation-in-part in of U.S. patent application Ser. No. 08/259,707, filed Jun. 14, 1995 and now abandoned. BACKGROUND OF THE INVENTION The present invention relates to novel pharmacologically active benzimidazolone derivatives and their acid addition salts. The compounds of this invention exhibit central dopaminergic activity and are useful in the treatment of central nervous system (CNS) disorders. They act preferentially on the D4 dopamine receptor. It is generally accepted knowledge that dopamine receptors are important for many functions in the animal body. For example, altered functions of these receptors participate in the genesis of psychosis, addiction, sleep, feeding, learning, memory, sexual behavior, regulation of immunological responses and blood pressure. Since dopamine receptors control a great number of pharmacological events and, on the other hand, not all of these events are presently known, there is a possibility that compounds that act preferentially on the D4 dopamine receptor may exert a wide range of therapeutic effects in humans. European Patent Application EP 526434, which was published on Feb. 3, 1993, refers to a class of substituted benzimidazolones that contain 1-(aryl and heteroaryl)-4-propyl piperidine substituents. These compounds were found to exhibit an affinity for the 5HT 1A and 5HT 2 serotonin receptors. German Patent Application DE 2714437, which was published on Oct. 20, 1977, refers to a series of 1- 3-(4-benzhydryl)piperazin-1-yl!propyl-2,3-dihydro-1H-benzimidazol-2-ones and reports that such compounds exhibited antihistamine activity when tested in mice. German Patent Application DE 2017265, which was published on Oct. 15, 1970, refers to a class of substituted 1- 3-(4-phenyl)piperazin-1-yl!propyl-2-methyl-1H-benzimidazoles that were found to exhibit bronchodilating effects in mice. European Patent Application EP 511074A1, which was published on Oct. 28, 1992, refers to benzimidazolone derivatives that are 5HT 2 serotonin receptor antagonists useful in the treatment of a variety of CNS disorders. The present invention relates to several substituted 1- 3-(4-heteroaryl)piperazin-1-yl)propyl!2,3-dihydro-1H-benzimidazol-2-ones that posess central dopaminergic activity and which have been found to have a preference for the D4 dopamine receptor. SUMMARY OF THE INVENTION This invention relates to compounds of the formula I ##STR2## wherein X 1 , X 2 and X 3 are independently selected from carbon and nitrogen; R 0 , R 1 and R 2 are independently selected from hydrogen, halo (e.g., chloro, fluoro, bromo or iodo), (C 1 -C 6 )alkyl optionally substituted with from one to three fluorine atoms and (C 1 -C 6 )alkoxy optionally substituted with from one to three fluorine atoms; R 3 is hydrogen, (C 1 -C 6 )alkyl or benzyl, wherein the phenyl moiety of said benzyl group may optionally be substituted with from one or more substituents, preferably with from one to three substituents, independently selected from halo (i.e., chloro, fluoro, bromo or iodo), cyano, (C 1 -C 6 )alkyl optionally substituted with from one to three fluorine atoms, (C 1 -C 6 )alkoxy optionally substituted with from one to three fluorine atoms, (C 1 -C 6 )alkylsulfonyl, (C 1 -C 6 )alkylamino, amino, di-(C 1 -C 6 )alkylamino and (C 1 -C 6 )carboxamido; R 4 , R 5 and R 6 are independently selected from hydrogen, halo (e.g., chloro, fluoro, bromo or iodo), cyano, (C 1 -C 6 )alkyl optionally substituted with from one to three fluorine atoms, (C 1 -C 6 )alkoxy optionally substituted with from one to three fluorine atoms, (C 1 -C 6 )alkylsulfonyl, (C 1 -C 6 )acylamino, (phenyl) (C 1 -C 6 )acyl!amino, amino, (C 1 -C 6 )alkylamino and di-(C 1 -C 6 )alkylamino; and the dashed line represents an optional double bond; with the proviso that when X 3 is nitrogen, R 2 is absent. The compounds of formula I that are basic in nature are capable of forming a wide variety of salts with various inorganic and organic acids. The acids that may be used to prepare pharmaceutically acceptable acid addition salts of those compounds of formula I that are basic in nature are those that form non-toxic acid addition salts, i.e., salts containing pharmacologically acceptable anions, such as the hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate, bisulfate, phosphate, acid phosphate, isonicotinate, acetate, lactate, salicylate, citrate, acid citrate, tartrate, pantothenate, bitartrate, ascorbate, succinate, maleate, gentisinate, fumarate, gluconate, glucuronate, saccharate, formate, benzoate, glutamate, methanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate and pamoate i.e., 1,1'-methylene-bis-(2-hydroxy-3-naphthoate)! salts. This invention also relates to the pharmaceutically acceptable acid addition salts of compounds of the formula I. The term "one or more substituents", as used herein, includes from one to the maximum number of substituents possible based on the number of available bonding sites. The term "alkyl", as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight, branched or cyclic moieties or combinations thereof. The term "alkoxy", as used herein, unless otherwise indicated, refers to radicals having the formula --O--alkyl, wherein "alkyl" is defined as above. Preferred compounds of this invention include compounds of the formula I, wherein R 1 is bromine and X 2 is nitrogen. Other preferred compounds of this invention include compounds of the formula I, wherein R 1 is chlorine and X 2 is nitrogen. Examples of specific preferred compounds of this invention include the following: 1- 3-(4-pyridin-2-yl-piperazin-1-yl)-propyl!-1,3-dihydro-benzoimidazol-2-one; 1-{3- 4-(5-trifluoromethyl-pyridin-2-yl)-piperazin-1-yl!-propyl}-1,3-dihydro-benzoimidazol-2-one; 1-{3- 4-(5-chloro-pyridin-2-yl)-piperazin-1-yl!-propyl}-1,3-dihydro-benzoimidazol-2-one; 1-{3- 4-(5-bromo-pyridin-2-yl)-piperazin-1-yl!-propyl}-1,3-dihydro-benzoimidazol-2-one; 1- 3-(2,3,5,6-tetrahydro- 1,2'!bipyrazinyl4-yl)-propyl!-1,3-dihydro-benzoimidazol-2-one; and 1-{3- 4-(6-chloro-pyridazin-3-yl)-piperazin-1-yl!-propyl}-1,3-dihydro-benzoimidazol-2-one. Other embodiments of this invention include: compounds of the formula I wherein X 2 is carbon, X 3 is nitrogen and R 1 is hydrogen or substituted or unsubstituted alkoxy; compounds of the formula I wherein X 2 and X 3 are both carbon and R 1 is hydrogen or substituted or unsubstituted alkoxy; compounds of the formula I wherein X 1 is carbon; compounds of the formula I wherein X 2 and X 3 are both carbon and each of R 0 , R 1 and R 2 is other than a fluoroalkyl group; and compounds of the formula I wherein X 1 is nitrogen. Other compounds of this invention include the following: 1- 2-cyano-3-(2,3,5,6-tetrahydro- 1,2'!bipyrazinyl-4-yl)-propyl!-1,3-dihydro-benzoimidazol-2-one; 1- 5-methyl,3-(2,3,5,6-tetrahydro- 1,2'!bipyrazinyl-4-yl)-propyl!-1,3-dihydro-benzoimidazol-2-one; 1- 6-cyano,3-(2,3,5,6-tetrahydro- 1,2'!bipyrazinyl-4-yl)-propyl!-1,3-dihydro-benzoimidazol-2-one; 1-{3- 4-(5-fluoro-pyridin-2-yl!-propyl!-3-methyl-1,3-methyl-1,3-dihydro-benzoimidazol-2-one; 1{3- 4-(3-cyano-pyridin-2-yl)-piperazin-1-yl!-propyl!-1,3-dihydro-benzoimidazol-2-one; 1-(3- 4-(4-cyano-pyridin-2-yl)-piperazin-1-yl!-propyl!-1,3-dihydro-benzoimidazol-2-one; 1-{3- 4-(6-trifluoromethyl-pyridin-2-yl)-piperazin-1-yl!-propyl}-1,3-dihydro-benzoimidazol-2-one; 1-{3- 4-(5-fluoro-pyridin-2-yl)-piperazin-1-yl!-propyl}-5-fluoro-1,3-dihydro-benzoimidazol-2-one; and 1-{3- 4-(5,fluoro-pyridin-2-yl)-piperazin-1-yl!-propyl}-5,6-difluoro-1,3-dihydro-benzoimidazol-2-one. The compounds of formula I above may contain chiral centers and therefore may exist in different enantiomeric forms. This invention relates to all optical isomers and all other stereoisomers of compounds of the formula I and mixtures thereof. Formula I above includes compounds identical to those depicted but for the fact that one or more hydrogens or carbon atoms are replaced by isotopes thereof. Such compounds are useful as research and diagnostic tools in metabolism pharmacokinetics studies and in binding assays. This invention also relates to a pharmaceutical composition for treating or preventing a condition selected from sleep disorders, sexual disorders (including sexual dysfunction), gastrointestinal disorders, psychosis, affective psychosis, nonorganic psychosis, personality disorders, psychiatric mood disorders, conduct and impulse disorders, schizophrenic and schizoaffective disorders, polydipsia, bipolar disorders, dysphoric mania, anxiety and related disorders, obesity, emesis, bacterial infections of the CNS such as meningitis, learning disorders, memory disorders, Parkinson's disease, depression, extrapyramidal side effects from neuroleptic agents, neuroleptic malignant syndrome, hypothalamic pituitary disorders, congestive heart failure, chemical dependencies such as drug and alcohol dependencies, vascular and cardiovascular disorders, ocular disorders, dystonia, tardive dyskinesia, Gilles De La Tourette's syndrome and other hyperkinesias, dementia, ischemia, Parkinson's disease, movement disorders such as akathesia, hypertension and diseases caused by a hyperactive immune system such as allergies and inflammation in a mammal, including a human, comprising an amount of a compound of the formula I, or pharmaceutically acceptable salt thereof, that is effective in treating or preventing such condition, and a pharmaceutical acceptable carrier. The present invention also relates to a method of treating or preventing a condition selected from sleep disorders, sexual disorders (including sexual dysfunction), gastrointestinal disorders, psychosis, affective psychosis, nonorganic psychosis, personality disorders, psychiatric mood disorders, conduct and impulse disorders, schizophrenic and schizoaffective disorders, polydipsia, bipolar disorders, dysphoric mania, anxiety and related disorders, obesity, emesis, bacterial infections of the CNS such as meningitis, learning disorders, memory disorders, Parkinson's disease, depression, extrapyramidal side effects from neuroleptic agents, neuroleptic malignant syndrome, hypothalamic pituitary disorders, congestive heart failure, chemical dependencies such as drug and alcohol dependencies, vascular and cardiovascular disorders, ocular disorders, dystonia, tardive dyskinesia, Gilles De La Tourette's syndrome and other hyperkinesias, dementia, ischemia, Parkinson's disease, movement disorders such as akathesia, hypertension and diseases caused by a hyperactive immune system such as allergies and inflammation in a mammal, including a human, comprising administering to said mammal an amount of a compound of the formula I, or pharmaceutically acceptable salt thereof, that is effective in treating or preventing such condition. The present invention also relates to a pharmaceutical composition for treating or preventing a condition selected from sleep disorders, sexual disorders (including sexual dysfunction), gastrointestinal disorders, psychosis, affective psychosis, nonorganic psychosis, personality disorders, psychiatric mood disorders, conduct and impulse disorders, schizophrenic and schizoaffective disorders, polydipsia, bipolar disorders, dysphoric mania, anxiety and related disorders, obesity, emesis, bacterial infections of the CNS such as meningitis, learning disorders, memory disorders, Parkinson's disease, depression, extrapyramidal side effects from neuroleptic agents, neuroleptic malignant syndrome, hypothalamic pituitary disorders, congestive heart failure, chemical dependencies such as drug and alcohol dependencies, vascular and cardiovascular disorders, ocular disorders, dystonia, tardive dyskinesia, Gilles De La Tourette's syndrome and other hyperkinesias, dementia, ischemia, Parkinson's disease, movement disorders such as akathesia, hypertension and diseases caused by a hyperactive immune system such as allergies and inflammation in a mammal, including a human, comprising a dopaminergic effective amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier. The present invention also relates to a method of treating or preventing a condition selected from sleep disorders, sexual disorders (including sexual dysfunction), gastrointestinal disorders, psychosis, affective psychosis, nonorganic psychosis, personality disorders, psychiatric mood disorders, conduct and impulse disorders, schizophrenic and schizoaffective disorders, polydipsia, bipolar disorders, dysphoric mania, anxiety and related disorders, obesity, emesis, bacterial infections of the CNS such as meningitis, learning disorders, memory disorders, Parkinson's disease, depression, extrapyramidal side effects from neuroleptic agents, neuroleptic malignant syndrome, hypothalamic pituitary disorders, congestive heart failure, chemical dependencies such as drug and alcohol dependencies, cardiovascular and ocular disorders, dystonia, tardive dyskinesia, Gilles De La Tourette's syndrome and other hyperkinesias, dementia, ischemia, Parkinson's disease, movement disorders such as akathesia, hypertension and diseases caused by a hyperactive immune system such as allergies and inflammation in a mammal, including a human, comprising an administering to said mammal a dopaminergic effective amount of a compound of the formula I, or pharmaceutically acceptable salt thereof. This invention also relates to a pharmaceutical composition for treating or preventing a disease or condition, the treatment or prevention of which can be effected or facilitated by altering dopamine mediated neurotransmission in a mammal, including a human, comprising a dopaminergic effective amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier. This invention also relates to a method of treating or preventing a disease or condition, the treatment or prevention of which can be effected or facilitated by altering dopamine mediated neurotransmission in a mammal, including a human, comprising administering to said mammal a dopaminergic effective amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof. The present invention also relates to a pharmaceutical composition for treating or preventing a condition selected from sleep disorders, sexual disorders (including sexual dysfunction), gastrointestinal disorders, psychosis, affective psychosis, nonorganic psychosis, personality disorders, psychiatric mood disorders, conduct and impulse disorders, schizophrenic and schizoaffective disorders, polydipsia, bipolar disorders, dysphoric mania, anxiety and related disorders, obesity, emesis, bacterial infections of the CNS such as meningitis, learning disorders, memory disorders, Parkinson's disease, depression, extrapyramidal side effects from neuroleptic agents, neuroleptic malignant syndrome, hypothalamic pituitary disorders, congestive heart failure, chemical dependencies such as drug and alcohol dependencies, vascular and cardiovascular disorders, ocular disorders, dystonia, tardive dyskinesia, Gilles De La Tourette's syndrome and other hyperkinesias, dementia, ischemia, Parkinson's disease, movement disorders such as akathesia, hypertension and diseases caused by a hyperactive immune system such as allergies and inflammation in a mammal, including a human, comprising a D4 receptor binding effective amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier. The present invention also relates to a method of treating or preventing a condition selected from sleep disorders, sexual disorders (including sexual dysfunction), gastrointestinal disorders, psychosis, affective psychosis, nonorganic psychosis, personality disorders, psychiatric mood disorders, conduct and impulse disorders, schizophrenic and schizoaffective disorders, schizoaffective disorder, polydipsia, bipolar disorders, dysphoric mania, anxiety and related disorders, obesity, emesis, bacterial infections of the CNS such as meningitis, learning disorders, memory disorders, Parkinson's disease, depression, extrapyramidal side effects from neuroleptic agents, neuroleptic malignant syndrome, hypothalamic pituitary disorders, congestive heart failure, chemical dependencies such as drug and alcohol dependencies, vascular and cardiovascular disorders, ocular disorders, dystonia, tardive dyskinesia, Gilles De La Tourette's syndrome and other hyperkinesias, dementia, ischemia, Parkinson's disease, movement disorders such as akathesia, hypertension and diseases caused by a hyperactive immune system such as allergies and inflammation in a mammal, including a human, comprising an administering to said mammal a D4 receptor binding effective amount of a compound of the formula I, or pharmaceutically acceptable salt thereof. This invention also relates to a pharmaceutical composition for treating or preventing a disease or condition, the treatment or prevention of which can be effected or facilitated by altering dopamine mediated neurotransmission in a mammal, including a human, comprising a D4 receptor binding effective amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier. This invention also relates to a method of treating or preventing a disease or condition, the treatment or prevention of which can be effected or facilitated by altering dopamine mediated neurotransmission in a mammal, including a human, comprising administering to said mammal a D4 receptor binding effective amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof. The term "dopaminergic effective amount", as used herein, refers to an amount sufficient to inhibit the binding of dopamine to a dopamine receptor. The term "altering dopamine mediated neurotransmission", as used herein, includes but is not limited to increasing or decreasing D4 dopamine receptor mediated neurotransmission. DETAILED DESCRIPTION OF THE INVENTION The preparation of compounds of the formula I are described below. In the reaction schemes and discussion that follows, X 1 , X 2 , X 3 , R 0 , R 1 , R 2 , R 3 , R 4 1 , R 5 , and the dashed line are defined as above. ##STR3## Referring to scheme 1, a compound of the formula II, wherein L is an appropriate leaving group, is reacted with a compound of the formula III to form the corresponding desired compound of the formula I. Examples of suitable leaving groups "L" include chloro, bromo, iodo, --O--(C 1 -C 4 )alkylsulfonyl, and --O- phenylsulfonyl. This reaction is generally carried out in an inert polar solvent such as a lower alcohol, a cyclic or acyclic alkylketone (e.g., ethanol or acetone), an alkylester (e.g., ethylacetate), a cyclic or acyclic mono or dialkylamide (e.g., N-methylpyrrolidin-2-one or dimethylformamide (DMF)), a cyclic or acyclic alkyl ether (e.g., tetrahydrofuran (THF) or diisopropyl ether), or a mixture of two or more of the foregoing solvents, at a temperature from about 0° C. to about 150° C. It is preferably carried out in ethanol at a temperature from about 0° C. to about the reflux temperature. Alternatively, compounds of the formula I wherein X 1 is nitrogen can be prepared by the method illustrated in scheme 2. Referring to scheme 2, compounds of the formula I may be formed by reacting a compound of the formula IV with the appropriate compound of the formula V, wherein L is defined above. Suitable solvents and temperatures for this reaction are similar to these described above for the reaction of compounds of the formulae II and Ill. Preferably, this reaction is conducted in DMF at about the reflux temperature. Scheme 3 and 4 illustrate the synthesis of compounds of the formulae III and IV, respectively, which are used as reactants in the processes of schemes 1 and 2. As depicted in scheme 3, a compound of the formula V is reacted with a compound of the formula VI, wherein L' is a suitable nitrogen protecting group, to form the corresponding compound of the formula VlI, from which the protecting group is then removed to form the corresponding desired compound of the formula III wherein X 1 is nitrogen and the ring that contains X 1 is saturated. Examples of suitable nitrogen protecting groups include benzyl, benzyloxycarbonyl, t-butoxycarbonyl and trityl (triphenylmethyl). When L' is one of the foregoing named protecting groups, it may be conveniently removed by either hydrogenation, acidic conditions or both. Other conventionally used protecting groups may be introduced and removed using methods well known to those skilled in the art. Compounds of the formula IlIl wherein X 1 is other than nitrogen and the ring containing X 1 is saturated may be prepared as described in the literature. (See Tetrahedron Letters, 23, 285 (1982) and J. Amer. Chem. Soc., 78, 1702 (1956). The foregoing literature references are incorporated herein by reference on their entireties. Compounds of the formula III wherein the ring containing X 1 is unsaturated may be prepared from the corresponding compounds wherein the ring containing X 1 is unsaturated by using conventional hydrogenation methods that are well known to those skilled in the art (e.g., reacting such compounds with hydrogen gas under a pressure of about 2 atmospheres in the presence of a catalyst such as an oxide or complex containing platinum, palladium, rhodium or nickel). The above reaction may be carried out using solvents or solvent mixture similar to those described above for formation of compounds of the formula I. It may also be carried out over the same temperature range (ie., from about 0° C. to about 150° C.). Preferably, this reaction is carried out in DMF at about the reflux temperature. As indicated above, scheme 4 illustrates the preparation of compounds of formula IV wherein X 1 is nitrogen and the ring containing X 1 is saturated. Referring to scheme 4, the desired compound of formula IV can be prepared by reacting a compound of the formula VI, wherein L' is a leaving group, as defined above, with the appropriate compound of the formula II, wherein L is a leaving group, as defined above. Suitable solvents and temperatures for this reaction are the same as those described for the preparation of compounds of the formula I. The preferred solvent is ethanol and the preferred temperature is about the reflux temperature. Compounds of the formula II, which are used as reactants in the process of scheme 1, are either commercially available or can be prepared as described in J. Org. Chem., 38, 3498-502 (1973) and in European Patent Application EP 0526434, referred to above. Both these references are incorporated herein by reference in their entireties. The preparation of other compounds of the formula I not specifically described in the foregoing experimental section can be accomplished using combinations of the reactions described above that will be apparent to those skilled in the art. In each of the reactions discussed or illustrated in schemes 1 to 4 above, pressure is not critical unless otherwise indicated. Pressures from about 0.5 atmospheres to about 4 atmospheres are generally acceptable, and ambient pressure, i.e., about 1 atmosphere, is preferred as a matter of convenience. The novel compounds of the formula I and the pharmaceutically acceptable salts thereof (hereinafter "the therapeutic compounds of this invention") are useful as dopaminergic agents, i.e., they possess the ability to decrease dopamine mediated neurotransmission in mammals, including humans. They are therefore able to function as therapeutic agents in the treatment of a variety of conditions in mammals, the treatment or prevention of which can be effected or facilitated by altering dopamine mediated neurotransmission. Such conditions include sleep disorders, sexual disorders (including sexual dysfunction), gastrointestinal disorders, psychosis, affective psychosis, nonorganic psychosis, personality disorders, psychiatric mood disorders, conduct and impulse disorders, schizophrenic and schizoaffective disorders, polydipsia, bipolar disorders, dysphoric mania, anxiety and related disorders, obesity, emesis, bacterial infections of the CNS such as meningitis, learning disorders, memory disorders, Parkinson's disease, depression, extrapyramidal side effects from neuroleptic agents, neuroleptic malignant syndrome, hypothalamic pituitary disorders, congestive heart failure, chemical dependencies such as drug and alcohol dependencies, vascular and cardiovascular disorders, ocular disorders, dystonia, tardive dyskinesia, Gilles De La Tourette's syndrome and other hyperkinesias, dementia, ischemia, Parkinson's disease, movement disorders such as akathesia, hypertension and diseases caused by a hyperactive immune system such as allergies and inflammation. The compounds of the formula I that are basic in nature are capable of forming a wide variety of different salts with various inorganic and organic acids. Although such salts must be pharmaceutically acceptable for administration to animals, it is often desirable in practice to initially isolate a compound of the formula I from the reaction mixture as a pharmaceutically unacceptable salt and then simply convert the latter back to the free base compound by treatment with an alkaline reagent and subsequently convert the latter free base to a pharmaceutically acceptable acid addition salt. The acid addition salts of the base compounds of this invention are readily prepared by treating the base compound with a substantially equivalent amount of the chosen mineral or organic acid in an aqueous solvent medium or in a suitable organic solvent, such as methanol or ethanol. Upon careful evaporation of the solvent, the desired solid salt is readily obtained. The desired acid salt can also be precipitated from a solution of the free base in an organic solvent by adding to the solution an appropriate mineral or organic acid. The therapeutic compounds of this invention can be administered orally, transdermally (e.g., through the use of a patch), parenterally, intranasally, sublingually, rectally or topically. Oral administration is preferred. In general, these compounds are most desirably administered in dosages ranging from about 0.5 mg to about 1000 mg per day, preferably from about 0.1 to about 250 mg per day, in single or divided doses, although variations may occur depending on the weight and condition of the person being treated and the particular route of administration chosen. In some instances, dosage levels below the lower limit of the aforesaid range may be more than adequate, while in other cases still larger doses may be employed without causing any harmful side effect, provided that such larger doses are first divided into several small doses for administration throughout the day. The therapeutic compounds of the invention may be administered alone or in combination with pharmaceutically acceptable carriers or diluents by either of the two routes previously indicated, and such administration may be carried out in single or multiple doses. More particularly, the novel therapeutic compounds of this invention can be administered in a wide variety of different dosage forms, i.e., they may be combined with various pharmaceutically acceptable inert carriers in the form of tablets, capsules, lozenges, troches, hard candies, powders, sprays, creams, salves, suppositories, jellies, gels, pastes, lotions, ointments, elixirs, syrups, and the like. Such carriers include solid diluents or fillers, sterile aqueous media and various non-toxic organic solvents, etc. Moreover, oral pharmaceutical compositions can be suitably sweetened and/or flavored. For oral administration, tablets containing various excipients such as microcrystalline cellulose, sodium citrate, calcium carbonate, dicalcium phosphate and glycine may be employed along with various disintegrants such as starch (and preferably corn, potato or tapioca starch), alginic acid and certain complex silicates, together with granulation binders like polyvinylpyrrolidone, sucrose, gelatin and acacia. Additionally, lubricating agents such as magnesium stearate, sodium lauryl sulfate and talc are often very useful for tabletting purposes. Solid compositions of a similar type may also be employed as fillers in gelatin capsules; preferred materials in this connection also include lactose or milk sugar as well as high molecular weight polyethylene glycols. When aqueous suspensions and/or elixirs are desired for oral administration, the active ingredient may be combined with various sweetening or flavoring agents, coloring matter or dyes, and, if so desired, emulsifying and/or suspending agents as well, together with such diluents as water, ethanol, propylene glycol, glycerin and various like combinations thereof. For parenteral administration, solutions of a compound of the present invention in either sesame or peanut oil or in aqueous propylene glycol may be employed. The aqueous solutions should be suitably buffered if necessary and the liquid diluent first rendered isotonic. These aqueous solutions are suitable for intravenous injection purposes. The oily solutions are suitable for intra-articular, intramuscular and subcutaneous injection purposes. The preparation of all these solutions under sterile conditions is readily accomplished by standard pharmaceutical techniques well known to those skilled in the art. Additionally, it is also possible to administer the compounds of the present invention topically when treating inflammatory conditions of the skin and this may preferably be done by way of creams, jellies, gels, pastes, ointments and the like, in accordance with standard pharmaceutical practice. The D4 dopaminergic activity of the compounds of the present invention may be determined by the following procedure. The determination of D4 dopaminergic activity has been described by Van Tol et al., Nature, vol. 350, 610 (London, 1991). Clonal cell lines expressing the human dopamine D4 receptor are harvested and homogenized (teflon pestle) in a 50 mM Tris:HCl (pH 7.4 at 4° C.) buffer containing 5 mM EDTA, 1.5 mM calcium chloride (CaCl 2 ), 5 mM magnesium chloride (MgCL 2 ), 5 mM potassium chloride (KCl) and 120 mM sodium chloride (NaCl). The homogenates are centrifugated for 15 min. at 39,000 g, and the resulting pellets resuspended in a buffer at a concentration of 150-250 μg/ml. For saturation experiments, 0.25 ml aliquots of tissue homogenate are incubated in duplicate with increasing concentrations of 3 H! Spiperone (70.3 Ci/mmol; 10-3000 pM final concentration) for 30-120 minutes at 220° C. in a total volume of 1 ml. For competition binding experiments, assays are initiated by the addition of 0.25 ml of membrane and incubated in duplicate with the indicated concentrations of competing ligands (10 -14 -10 -3 M) and 3 H!Spiperone (100-300 pM) in either the absence or presence of 200 uM GPP(NH) P (5'/guanylylimidodiphosphate), where indicated, for 60-120 min at 220° C. Assays are terminated by rapid filtration through a Titertek cell harvester and the filters subsequently monitored for tritium as described by Sunahara, R. K. et al., Nature, 347, 80-83 (1990). For all experiments, specific 3 H!Spiperone binding is defined as that inhibited by 1-10 μM (+) Butaclamole or 1 μM Spiperone. Both saturation and competition binding data are analyzed by the non-linear least square curve-fitting program Ligand run on a digital Micro-PP-11 as described by Sunahara et al. In an assay similar to the one described above, each of the title compounds of Example 1, 4 and 6-9 exhibited an 1C 50 for the D4 receptor less than or equal to 0.11 μM and an lC 50 for the D2 receptor greater than 1.0 μM and less than 3.3 μm. The present invention is illustrated by the following examples. It will be understood, however, that the invention is not limited to the specific details of these examples. EXAMPLE 1 1-{3- 4-(5-Chloro-pyridin-2-yl)-piperazin-1-yl!-propyl}-1,3-dihydro-benzoimidazol-2-one A mixture of 1.14 gm of 2-piperazino 5-chloro pyridine, 1.35 gm of 1-(3-chloro propyl)-2,3-dihydro-1H-benzimidazol-2-one (available from Janssen) and 1.49 gm of diisopropylethylamine in 3 ml DMF and 30 ml toluene is kept for 12 hours at 110° C. Upon cooling to ambient temperature, 30 ml water is added and the mixture is extracted with chloroform (CHCl 3 ) and the extract is collected, washed with 20 ml water and dried over sodium sulfate (Na 2 SO 4 ). The crude product (2.5 gm) which is obtained after removing the solvents is purified using chromatography: solid phase (SiO 2 ; 40 μm; Baker); eluant 2% methanol (CH 3 OH) in methylene chloride (CH 2 Cl 2 ). A sample of this purified material (1.2 gm) was transferred into its hydrochloride (mp: 200° C.) by treating an ethanolic suspension of this material with a mixture of ethyl ether/HCl. EXAMPLE 2 4- 3-(2-Oxo-2,3-dihydro-benzoimidazol-1-yl)-propyl!-piperazine-1-carboxylic acid tert-butyl-ester A mixture of 5.0 gm of 1-t-butoxycarbonyl piperazine, 6.26 gm of 1-(3-chloro propyl)-2,3-dihydro-1H-benzimidazol-2-one (available from Janssen) and 4.16 gm diisopropylethylamine in 150 ml ethanol is kept for 12 hours at 80° C. Upon cooling to ambient temperature, 100 ml water is added and the mixture is extracted with chloroform (CHCl 3 ) and the extract is collected, washed with 20 ml water and dried over Na 2 SO 4 . After removing the solvents, 10 gm of a yellowish oil is obtained which is used without further purification. EXAMPLE 3 1- 4-(3-piperazine-1-yl)propyl!-2,3-dihydro-1h-benzimidazol-2-one A saturated solution hydrochloric acid in 2 ml methanol and of 0.43 gm of 1- 4-(3-)t-butoxycarbonyl)piperazine-1-yl)propyl!-2,3-dihydro-1H-benzimidazol-2-one is kept for 1 hour at 50° C. Upon cooling to ambient temperature, the solvent is removed, and the residue is suspended in 10 ml water made basic with aqueous ammonium hydroxide solution. The aqueous layer is extracted with CHCl 3 . The CHCl 3 extract is collected, washed with 20 ml water and dried over Na 2 SO 4 . After removing the solvents, 0.207 gm of a yellowish oil is obtained which is used without further purification. EXAMPLE 4 1-{3- 4-(5-Trifluoromethyl-pyridin-2-yl)-piperazine-1-yl!-propyl}-1,3-dihydro-benzoimidazol-2-one A mixture of 0.054 gm of 2-chloro 5-trifluoromethyl pyridine, 0.115 gm of 1- 4-(3-piperazine-1-yl)propyl!2,3-dihydro-1H-benzimidazol-2-one and 0.194 gm of diisopropylethylamine in 1.0 ml of 1-methyl-2-pyrrolidinone is kept for 3 hours at 150° C. Upon cooling to ambient temperature and addition of 10 ml water the mixture is acidified with concentrated hydrochloric acid and extracted 2×5 ml ethyl ether. The aqueous layer is then neutralized with aqueous ammonium hydroxide solution and extracted with ethyl acetate. The ethyl acetate extract is collected, washed with 20 ml water and dried over Na 2 SO 4 . The crude product (0.085 gm) obtained after removing the solvents is purified using chromatography: solid phase (SiO 2 ; 40 μm; Baker); eluent 2% CH 3 OH in CHCl 3 . A sample of this purified material (0.015 gm) was transferred into its hydrochloride (mp: 183° C.) by treating an ethanolic suspension of this material with a mixture of ethyl ether/HCl. EXAMPLE 5 1-(5-Bromo pyrid-2-yl) piperazine A mixture of 5.0 g of 1-t-butoxycarbonyl piperazine, 6.36 gm of 2,5-dibromopyridine and 10.4 gm diisopropylethylamine in 50 ml of 1-methyl-2-pyrolidinone is kept for 12 hours at 150° C. Upon cooling to ambient temperature and addition of 10 ml water, the mixture is acidified with concentrated hydrochloric acid heated for 15 minutes and upon cooling extracted 2×5 ml ethyl ether. The aqueous layer is then neutralized with aqueous ammonium hydroxide solution and extracted with ethyl acetate. The ethyl acetate extract is collected, washed with 20 ml water and dried over Na 2 SO 4 . The crude product (4.3 gm) obtained after removing the solvents solidifies upon standing. This material is used without further purification. The title compounds of Example 6-9 were prepared using a procedure similar to those of Examples 1 and 4. EXAMPLE 6 1-{3- 4-(6-(6-Chloro-pyridazin-3-yl)-piperazin-1yl!-propyl}-1,3-dihydro-benzimadazol-2-one mp: 242°-245° C. EXAMPLE 7 1- 3-(2,3,5,6-Tetrahydro- 1,2'bipyrazinyl-4-yl)-propyl!-1,3-dihydro-benzimidazol-2-one mp: 262°-264° C. EXAMPLE 8 1-{3- 4-(5-Bromo-pyridin-2-yl)-piperazin-1-yl!-propyl}-1,3-dihydro-benzimidazol-2-one mp: 201°-202° C. EXAMPLE 9 1- 3-(4-Pyridin-2-yl-piperazin-1-yl)propyl!-1,3-dihydro-benzimidazol-2-one mp: 186° C.
This invention relates to novel, pharmaceutically active benzimidazolone derivatives of the formula ##STR1## wherein the dashed line, R 0 through R 6 and X 1 through X 3 are defined as in the specification. These compounds exhibit central dopaminergic activity and are u in the treatment of CNS disorders.
2
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to an improved method and apparatus for cooking starch that is to be used in a commercial laundry application. Even more particularly, the present invention relates to an improved commercial starch cooking method and apparatus wherein a recirculating flow line reticulates the cooking starch solution through a recirculating pump at velocities of flow not previously achieved in starch cooking apparatus which promotes a more uniform heating of the starch batch and breaks up lumps in the starch. In the preferred embodiment of the invention, the starch is caused to exit the cooker at high velocity through a strainer in the form of a standpipe in the bottom center of the cooker vessel by a high velocity centrifugal circulating pump which discharges back into the vessel through a spray nozzle adjacent the periphery of the vessel thereby establishing a high velocity circulation of fluid in the vessel causing a vortex to be exhibited around the discharge standpipe to continually mix and homogenize the starch, and clean the vessel wall. [0003] 2. General Background of the Invention [0004] During the cooking of starch two phenomena take place. Naturally occurring starch granules undergo considerable physical change, usually “swelling,” until they are complete disintegrated, and the starch molecules are hydrolyzed into smaller particles. The resulting modified starch material depends upon processing conditions that are very important in determining the physical characteristics of the final starch solution. The swelling or hydrolyzed modification of starch, if precisely controlled, allows starch to be useful as a size or adhesive. [0005] A compact cooker, reliably and consistently operable by a relatively unsophisticated individual, would be desirable. At a minimum, the cooker should bring the water and starch charge to a workable temperature and maintain the mix in a status for dispensing into the laundry apparatus For effective starching of clothing, it is essential that the starch be a homogenous mix of water and starch, that is, without lumps or other concentrations of starch which present an uneven texture or appearance to the fabric of the washed and starched garment. It is customary in “cooking starch” for laundry purposes to utilize temperatures in the 165° Fahrenheit thru 190° Fahrenheit range (preferably between 180° F. to 190° F.). At higher temperatures, i.e., above 212° F., the chemical and physical make up of the starch continues to change in such that the starch molecules begin to swell causing the volume of slurry to increase. As temperatures continue to rise, the starch molecules “burst” and the starch slurry no longer has the desirable properties as a sizing or adhesive. [0006] The cooker must repeatedly perform the fill, cook and empty tasks with precision and regularity inherent in the design and operation of the machine and thus, without say sort of individual monitoring of the progress of the cooking procedure. [0007] Several patents have issued for starch cooking devices. Some of the suggested patented systems require the use of a tank float device (e.g., U.S. Pat. No. 5,437,169 to Mitchell) to open and close the water supply valve via a solenoid. The float is immersed or partially immersed in the aqueous slurry of starch Immersed operating components in starch solutions are a source of operating trouble. If the float becomes coated with starch, it fails to function, and presents overflow risks. [0008] Some existing starch cookers (e.g., U.S. Pat. No. 5,437,169 to Mitchell; U.S. Pat. No. 2,730,468 to F. H. Martin; and U.S. Pat. No. 1,418,320 to E. W. Miller) use direct steam injection both to cook the starch and to agitate the starch solution. Existing cookers that use steam both to agitate and to cook often create starch solutions having lumps. It is believed that the concentrated heat of the steam directly on the starch solution causes localized heating and a temperature above that which the starch will remain stable as described above. These starch lumps cause uneven starching of the garments and a build up of starch on the press covers when the garments are pressed. Furthermore, direct steam induction results in sediment from within the boiler and or steam line to be mixed with the starch solution resulting in contamination (granular inclusions) and discoloration of the garments. [0009] Other existing starch cookers (e.g., U.S. Pat. No. 5,437,169 to Mitchell, U.S. Pat. No. 2,940,876 to N. E. Elsas; and U.S. Pat. No. 2,516,884 to G. J. Kyame) use a plurality of valves to direct the contents of the containment tank either to the output conduit or the tank circulation. Problems have resulted from starch building up on such valves, including a failure of the valve to function. [0010] Further problems with existing starch cookers involve the use of microprocessors to control a plurality of relays and process signals from various controlled communications. Microprocessors are particularly susceptible to heat and moisture, both of which are abundantly present in commercial laundries. When microprocessors are exposed to only minute amounts of moisture and/or heat they often cease to function. Thus, it would is desirable to provide a starch cooker which does not have the aforesaid susceptibility to heat and moisture. [0011] Some large laundries use large vats of hot starch solutions and manually transfer hot starch from the vat to the washer. The manual transfer presents a danger of spillage and burning the operator. Another problem with this method is the large size of the vats and the consequently large quantities of starch. If the entire amount of starch is not used the same day it is prepared, the residual will frequently spoil and impart an unpleasant odor to the garments. [0012] Other unsuccessful approaches at effective starch cookers are illustrated in U.S. Pat. No. 5,964,950 to Boling, the present inventor, wherein an external stand pipe is utilized to determine the fluid level within the vessel which, once the batch of starch is cooked and the slurry removed from the tank, residue of the slurry remains within the standpipe and creates an additional impediment to refill water rise in the pipe and erroneous readings occur. The patent also recites the inclusion of a gear pump for recirculating the slurry theorized to materially contribute to the break up of lumps. In operation, it has been found that the gear pump was only marginally effective in the breaking up of starch lumps and also exhibited a tendency to clog. In this previous cooker, it was theorized the use of a gear pump would blend the starch using the gears of the pump as a grinder. Through further operation, it has been found that with the use of gears, the starch revolved around the gears using the gears like paddles around the interior of the body when it was anticipated that the starch would be drawn through the center of the gears and therefore the meshing gear teeth would break up any lumps that had formed in the starch. [0013] Through further evaluation it has been determined that the circulation of the starch with this particular prior art pump was approximately 3 gal per minute. When using straight water in the cook tank, prior to the adding starch, one would observe significant movement of the water in the tank Once starch was added to this water, the movement due to the viscosity of the liquid slowed down considerably, more so than expected. The gear pump demonstrated the ability to pump on a free flow a maximum rate of 4 gal per minute with a liquid that was very thin such as water. [0014] According to the present invention, the flow rate of the combined mix of starch and water, by using a centrifugal pump of about a ⅓ HP rating, with an inlet size of 1″ and an outlet size of ¾″, which will pump on free flow about forty gallons per minute using a liquid such as water can provide the flow rate necessary for a thorough mix. Likewise, in the present invention, the inlet and outlet lines of the circulation pump are preferably copper and a minimum of ¾″ in diameter. Additionally, an upright filter is installed on the interior floor of the cook tank, extending into the tank, to further assist in the break-up of starch lumps and continual mixing. The filter is also preferably made of copper and stands approximately 6 inches high from the bottom of a 5 gallon mixing tank, a relatively common size of starch cooker. It has been determined that the filter for the 5 gallon tank should contain approximately 30 holes of about ⅛″ diameter over its surface to permit sufficient flow, yet break up any concentrations of starch. It has been discovered that with the inventive combination of vortex flow in the tank and the central filter, when water is being mixed into the tank that pump pulls the water off the center bottom of the tank through the filter and back through the side wall of the tank and across the heating coil with a flow of approximately 9 gallons per minute. This flow rate of the centrifugal pump together with the discharge of the heated mixture through the nozzle tangentially to the upper wall of the tank produces a strong vortex through to the center of the cook tank. It is preferable that the pump flow rate establish a vortex swirl around the internal perimeter of the tank with a depth that extends close to, but not below the top of the filter, i.e., such that the filter (and all of the holes) remains covered. [0015] Once starch has been added to this tank, in a normal usage range of from one cup of starch per five gallons of water to 7 cups of starch per five gallons of water (the cup measure is by volume and not be weight) that the variance of mix and the viscosity of these mixtures made little change in the vortex in the center of the cook tank. All of the tests shown each test were in one-cup increasing increment of added starch and shows that there was little change in the depth or angular speed of the vortex in the center of the tank. The importance of this vortex serves many purposes in cooking starch. By radially circulating the starch from the center of the tank and it being drawn across the heating coil at higher rates of speed than conventional cookers, it keeps the heating coil clean, avoiding uneven heating that can occur if starch builds up on the coil. Reliable heating coil operation eliminates any need to subject the starch and water to direct steam injection, and thereby avoiding the troubles induced by such heating. The use of live steam injection not only causes deterioration of the starch water mixture, introduces boiler residue into the mix, but also may be hazardous to the operator. Therefore, it is significant improvement to enable the reliable and uniform heating of the starch by the inventive pumping of the mixture across the self-cleaning heating surface. In earlier such attempts of direct heating, the use of a coil in starch as a heat source failed because the coil did not experience a sufficient flow rate of the starch/water mixture over it and the coil would get coated with starch and the starch would act as an insulator and the coil would cease to transfer heat the starch mixture. [0016] Another advantage of the vortex circulation is found in the effective way any lumps that may form in the starch mixture are pulled to and through the filter in the bottom center of the tank. Lumps are forcibly broken up and the starch dissolved, due to the circulation of the pump continually forcing the mixture past the pump impeller as well as by the draw of the stream through the filter, pulling the lumps through the many small holes in the filter. Also, with this aggressive circulation in a vortex fashion, the starch is now heated evenly throughout the tank without any cold spots. If cold spots are allowed to occur in a cook tank below 180 degrees, there is a danger that the mix will lose its homogeneity and “highlighting” could occur in the garments, resulting in light spots of improperly mixed and cooked starch. [0017] With the selected centrifugal pump used being capable of pumping about forty gallons per minute on free flow, the pump may be adapted by putting approximately 40 lb. of head pressure from a reduced outlet pipe such that the pump the rate drops to 9 gallons per minute. Accordingly, this same pump may be used on smaller starch cookers, such as the described 5 -gallon capacity as well as the larger starch cooker being of 14 gallons capacity. This may be accomplished by merely changing the line size from the tank to the pump inlet to change the flow of starch to properly size to the tank capacity. On both tanks a ¾ inch size inlet is preferably used. On the smaller cookers, a ½ inch diameter size outlet is used (contrasted to the larger cooker using a ¾ inch diameter size outlet. Tests of the smaller tanks show that by using ½ inch as an outlet size on the larger cooker that the gallons per minute drop to where the vortex is only slightly visible where on the smaller size cooker, the vortex is maintained relatively as with the larger outlet on the larger cooker. Once the line size had been properly sized for the volume in the tank the vortex was extremely strong and able to disperse any lumps that have appeared in the tank during the test. Once test was over and starch was drained there were no signs of any build up in the tank or on the filter. [0018] On filling, it is common practice to allow water to fill in the tank approximately 6 inches so that starch will not lump or clump against the bottom of the tank due to the tank being hot or any hot starch that my have been left in the bottom of the tank between batches. During testing of the present invention, approximately 2 inches of hot starch was left in the bottom of the cook tank when the “start” button was pressed for the new batch, and at the same time there was added a pre-measured amount of starch into the tank to increase the risk of lumps and during the cooking process. Surprisingly, there were no lumps or clumps visible after the tank was later emptied, due to the strength of the vortex and the capacity of the filter to remove theses lumps and clumps with the high velocity flow which creates the vortex. [0019] Accordingly, the effect of using a centrifugal pump, an immersed heating coil, and a pump strainer, pulling the starch off the bottom center of the tank and injecting it across the coil to form a strong forceful vortex achieve the following: [0020] Removal of lumps and clumps from a starch mixture [0021] Mixing of starch uniformly without cold spots throughout the tank; [0022] Heating the starch mixture, without any fear of exposure to an operator by using methods of directs steam injection; [0023] Heating starch quickly: by injecting the starch mixture across the coil, which keeps the coil free of starch build up. [0024] The present invention thus more quickly and completely cooks a quantity of starch solution required for multiple fills of starch cookers and expeditiously transfers a desired quantity of well cooked, smooth starch reliably to selected cookers than any in the prior art. BRIEF SUMMARY OF THE INVENTION [0025] An object of the present invention is to provide a new and improved apparatus wherein starch solution may be thoroughly cooked without the liability of forming lumps or solid masses in such a manner to produce a complete homogeneous mixture. [0026] Another object of the present invention is to provide a starch cooking and dispensing apparatus wherein the starch product may be maintained within close limits at the proper temperature for obtaining the best results as to penetration of the garments and the quality of sizing. [0027] Another object of the present invention is to provide a starch cooking/dispensing apparatus that allows commercial laundries to use dry, or uncooked starch which is more economical than other forms of starch and nearly eliminates any waste of starch. [0028] Another object of the present invention is to provide a starch cooking/dispensing apparatus that automatically transfers the hot starch solution directly into a commercial washer. This eliminates the dangerous practice of manual transfer and exposure to burns. [0029] It is yet another object of the present invention to provide a starch cooking/dispensing apparatus that is self-cleaning. The present invention provides an improved apparatus for cooking a starch solution and then dispensing that cooked solution to a commercial laundry washer. [0030] The apparatus includes a vessel with an interior surrounded by a wall for holding a volume of liquid. [0031] A water supply inlet supplies water to the vessel interior for use in making the starch solution. [0032] The vessel provides an open top into which dry starch can be added for making the starch solution. [0033] A steam supply inlet is provided for adding steam to the vessel interior via a header that separates the steam from the solution so that the volume of liquid within the vessel can be heated. [0034] A level controller controls the level of fluid within the vessel in between minimum and maximum fluid levels. [0035] A recirculation flow line provides an inlet and an outlet that each communicate with the vessel interior. A pump mounted in the recirculation flow line pumps fluid from the inlet to the outlet during a recirculation of the fluid within the vessel interior. [0036] In the preferred embodiment, the pump includes a geared impeller that breaks up starch lumps flowing in the recirculation flow line. [0037] A discharge flow line is provided for transmitting the heated slurry of starch and water from the vessel interior to the laundry washer. [0038] In the preferred embodiment, a discharge pump dispenses the heated solution of starch and water from the discharged flow line to the laundry washer, wherein the discharge pump has a geared portion that breaks up starch lumps flowing therethrough. BRIEF DESCRIPTION OF THE DRAWINGS [0039] For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein: [0040] [0040]FIG. 1 is a sectional elevational view of the preferred embodiment of the apparatus of the present invention; [0041] [0041]FIG. 2 is a top plan view of the preferred embodiment of the apparatus of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0042] [0042]FIGS. 1 and 2 show generally the preferred embodiment of the apparatus of the present invention designated generally by the numeral 10 . Starch cooking apparatus 10 includes a vessel 11 having an interior 12 for containing water and dry or liquid starch that is added to the vessel through the open top, for example. The vessel 11 provides an interior 12 surrounded by side wall 13 and bottom wall 14 . Vessel 11 may be fabricated of a variety of materials suitable for forming a container however, stainless steel or another corrosion resistant material is preferred. The vessel 11 may also be insulated to conserve heating requirements and to reduce the heat lost to the surrounding laundry area. Lid 15 is attached to side wall 13 at hinge 16 so that when the lid 15 is open, starch can be added through the open top portion at the open lid 15 . The lid 15 may be provided with a handle 17 to aid in opening and closing the lid 15 . [0043] A water supply line 18 supplies fluid to inlet jet 19 when control valve 20 is opened. Preferably, water supply line includes a check valve 21 preventing the back flow of water in the line. Heating coil 22 is a steam header (e.g., ⅜″ copper conduit) that tracks in a generally circular path approximately adjacent to side wall 13 as shown in FIG. 2. This heating coil 22 receives steam transmitted to vessel 11 via steam inlet line 23 . Steam control valve 24 controls the flow of steam through line 23 to heating coil 22 . A steam return line 25 is provided for exiting steam from heating coil 22 , the return line 25 being provided with steam trap 26 . [0044] After a starch solution has been cooked within the interior 12 of vessel 11 , that starch solution can be transmitted to a commercial washer (not shown) via flow line 28 . Discharge port 27 communicates with discharge flow line 28 so that the starch solution can be drained from the vessel 11 at discharge port 27 . A pump 31 is provided in discharge flow line to assist in the transport of the mixed starch to the commercial washer. In the illustrated embodiment, a Dayton model 7P087 pump and motor is utilized, however those skilled in the art recognize that a pump of similar capacity by another manufacturer will suffice. A motor drive 32 is included to power pump 31 during the transfer of the starch mix to the washer. [0045] A recirculation line 35 is provided to continuously recirculate the starch and water mixture in vessel 11 , to initially mix the starch and water combination and to heat the starch to bring it to the necessary useful temperature and homogeneity, and thereafter to prevent the starch from developing any clumps or lumps, keeping it continually ready to be discharged into the commercial washer. Recirculation line 35 terminates in the vessel 11 in the center of the bottom wall 14 , at outlet 36 , to which is attached filter 30 . Filter 30 is a stand of pipe of a noncorosive material, such as stainless steel, which in the preferred embodiment of a cooker having a capacity of 5 gallons the filter is of a diameter of three-quarters of an inch and stands approximately 6 inches above the bottom all 14 of vessel 11 . For the standard size cooker being described, the filter has approximately 30 substantially evenly distributed holes which have a diameter of approximately ⅛th inch in diameter, numbering 30, though the height of the filter. The number and size of holes 30 ′ in filter 30 may be varied so long as the flow rate through the filter is essentially equal to the flow rate of the mixture out of the outlet 39 . In the described preferred embodiment, pump 37 generates a flow rate of approximately 12 gallons per minute though the system, including through filter 30 , through recirculating line 35 and out of discharge nozzle 39 into vessel 11 . As may be better noted on FIG. 2, nozzle 39 is disposed adjacent the vertical wall 13 of vessel 11 such that the velocity of the starch and water mixture exiting the nozzle 39 facilitates the vortex set up in vessel 11 . Nozzle 39 is immediately adjacent heating coil 22 disposed around and adjacent to vessel wall 13 in the lower region of the vessel 11 . By such placement and the vortex assisting action of the discharge of nozzle 39 , the starch and water mixture is evenly heated by the continuing flow of starch and water over the heating coil 22 . Providing the volume of starch and water flow through filter 30 , nozzle 39 and over coil 22 is centrifugal pump 37 , disposed in recirculating line 35 immediately below discharge opening 36 . In the preferred embodiment, pump 37 is a Dayton model 4RH41 centrifugal pump which provides a flow rate of approximately 12 gallons per minute flow through recirculating line which is approximately ¾ inches in diameter. As previously described, pump 37 operating at rated capacity provides the flow in the recirculating line 35 and out of nozzle 39 into vessel 11 , causing the load of the mixture of starch and water to swirl in the direction of flow out of nozzle 39 to a degree that filter 30 , at the center of the vortex created, stands approximately 6 inches above the bottom wall 14 of vessel 11 and is barely covered by the mixture of starch and water. For those smaller sized starch cookers described above, the capacity of recirculating pump 37 and the vortex created out of nozzle 39 causes the swirl of the starch and water mixture to bottom just above of the shorter filter 30 for the reduced capacity cooker 10 . [0046] As described earlier, nozzle 39 projects the stream of recirculating starch and water generally tangentially of vessel wall 13 across the heating coil 22 to produce the strong vortex which pulls any lumps or clumps of starch into filter 30 , causing them to break-up and dissolve as the starch and water mixture transits holes 30 ′ and enters into inlet 36 and pump 37 . Projection of the stream of starch and water out of nozzle 39 onto the vessel wall 13 establishes the circular, vortex action which injects the continuous mixing action and impacts the lumps and clumps of starch, to the degree that any persist, against filter 30 , forcing them through holes therein. The continuous circular injection of the starch and water mixture tangentially at vessel wall 13 and the extraction of the mixture centrally at filter 30 further inhibits any stagnation of starch in the vicinity of either the steam heating coil 22 or at the bottom of vessel 11 , particularly in the region of the outlet port 27 . The combination of the described actions ensures a well-mixed homogeneous mixture of starch and water at a uniform temperature selected to provide the best action of starching garments in the commercial washer to which the cooker 10 is connected. [0047] As indicated above, the description is specific to a vessel 11 with a capacity of about 5 gallons. Starch cookers 10 are also commonly constructed with a 14 gallon vessel 11 . Other than the size of the vessel 11 , the only other adjustment which is made to establish a vortex of sufficient vigor and depth for the above described degree of mixing and heating is by increasing of the size of the outlet on centrifugal pump 37 to ¾ inches compared to the 12 inch size utilized for the 5 gallon vessel. By increasing the flow capacity out of nozzle 39 , the described vortex is made to bottom out just above the top of filter 30 . [0048] Thermostat 40 regulates the temperature of the starch solution contained within vessel 11 during the cooking period. Thermostat 40 is controlled by control panel 41 illustrated in FIGS. 1 and 2. The Control panel 41 has a start switch 42 to begin operation of cooker 10 and a stop switch 43 to cease operation. A direct transfer switch 44 is provided for initiating the transfer of the contents of the starch solution in vessel 11 to the commercial washer, via flow line 28 . Light indicator 45 illuminates when the starch solution has reached the requisite temperature (preferably 180° F. To 190° F.) and the requisite degree of mixing during the cooking operation. Once the operating temperature is reached, timer 48 starts operating and is set to allow mixing for 5 minutes to ensure adequate mixing of the starch and uniformity of temperature in the batch. Once the 5 minutes of continued mixing expire, a ready light 45 illuminates showing that the starch mixture is ready for dispensing. [0049] In the usual cycle for mixing and dispensing a starch and water mixture to a washing machine, the pressing of start switch 42 will start the flow of water into vessel 11 through line 18 . The volume of water added is preferably enough to reach a quantity of about five gallons in vessel 11 . The fill level is controlled in the preferred embodiment by stand pipe 29 , subsequently described. Once vessel 11 is filled to the predetermined level, the user adds from about 8 to about 38 ounces of uncooked (dry) starch. Once the water level reaches the predetermined level as set in water level switch 47 , solenoid 20 turns off the supply of water and the steam valve 24 begins supplying steam to coil 22 for the heating of the starch and water mixture. Concurrently, circulation pump 37 is actuated to begin recirculating the liquid in vessel 11 so that the action of the starch and water mixture keeps the heating coil 22 clear of starch build-up and circulation of the mixture through filter 30 breaks up any lumps or clumps of starch. Until the temperature of the starch and water mixture reaches the preselected range, steam solenoid 24 continues the supply of steam to heating coil 22 . In the illustrated embodiment, after the mixture has come to the 180-190° F. range, and five minutes have elapsed, the starch and water have become properly mixed and the ready light 45 will illuminate signaling that the mixture is ready for discharge to a washer. Circulation pump 37 will continue circulating the mixture as described and steam valve 24 continues the supply of steam to coil 22 until the commercial washer signals the supply of starch to the washer. At that point, transfer pump 31 begins the transfer of the mixture to the washer. [0050] Cleaning of the cooker 10 is affected in a manner similar to the preparation of a mixture of starch and water, with the exception that the starch is not added. Water is added to the vessel 11 to the predetermined level and is preferably (though not necessarily) heated to the predetermined temperature. The water is circulated as with the mixture since the vortex circulation provides such an effective cleaning action that all of the operative parts are stripped of the previous mixture, and when the cleaning is completed (as with the time it takes for the water to come to the preset temperature and is circulated for the 5 minute period), the water is dumped and the vessel is clean. [0051] The present invention includes an improved water level control which much more effectively and accurately controls the level of water (and the starch mixture) in the vessel 11 . Prior versions of cookers have utilized metallic inverted stand pipes 29 within the vessel 11 which operate in conjunction with a pressure switch 47 which senses the level of water in the vessel by means of the pressure exerted on the air trapped within pipe stand 29 . It has been discovered that as the level of starch that accumulates upon the exterior of conventional metallic stand pipes affects the coefficient of heat conductance of the stand pipe, and frequently remains there after conventional cleaning. Hence, when a new supply of water is added to the mixer, the rising temperature of the water does not get conducted through the stand pipe 29 and the header of air trapped therein is not heated, as with a clean pipe stand, and therefore the pipe stand gives a level reading (allows overfilling since the air in the tube is not heated and expanded as with the clean pipe) inconsistent with a clean stand pipe. The present invention incorporates a stand pipe 29 fabricated of schedule 80 PVC plastic pipe. By using the selected material (selected because it does not readily conduct heat), the conductance of the heat of the water in the tank is insufficient to change the temperature of the air contained within the pipe stand 29 and therefore, the readings from batch to batch are consistent from one filling to the next since the temperature of the air is essentially constant (i.e., unchanged) and prompts a reliable, repeatable reading. [0052] The following table lists the parts numbers and parts descriptions as used herein and in the drawings attached hereto. PARTS LIST Part Number Description 10 starch cooking apparatus 11 vessel 12 interior 13 side wall 14 bottom wall 15 lid 16 hinge 17 handle 18 water supply line 19 inlet jet 20 control valve 21 check valve 22 heating coil 23 steam inlet line 24 steam control valve 25 steam return line 26 steam trap 27 discharge port 28 discharge conduit 29 inverted pipe stand 30 strainer 31 transfer pump 32 motor drive 33 pump inlet 34 pump outlet 35 recirculation line 36 outlet 37 circulation centrifugal pump 38 motor drive 39 inlet 40 thermostat 41 control panel 42 start switch 43 stop switch 44 direct transfer switch 45 light indicator 46 line 47 water level switch [0053] The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims.
A method and apparatus for cooking a starch solution and then dispensing that cooked starch solution to a commercial laundry washer provides a vessel with an interior surrounded by a wall for holding a volume of liquid, a water supply inlet for supplying water to the vessel interior, an opening for adding dry starch to the vessel interior, and a steam supply inlet for adding steam to the vessel interior so that the volume of liquid within the vessel can be heated. A level controller controls the level of fluid within the vessel in between the minimum and maximum levels that is fabricated of a generally low or non-heat conductive material. A recirculation flow line has an inlet and outlet that each communicate with the vessel interior. A centrifugal pump mounted in the recirculation flow line pumps fluid from the inlet to the outlet in a recirculating fashion, the pump having a filter disposed on the inlet side within the vessel that breaks up starch lumps flowing in the recirculation flow line. A discharge flow line transmits the heated starch solution from the vessel interior to the commercial laundry washer.
3
FIELD OF INVENTION [0001] The present invention relates generally to the field of audio system performance, and more particularly, to a loudspeaker assembly capable of pivoting the low-frequency and high-frequency transducers to provide directional sound and to avoid hindrance of sound waves by the loudspeaker frame itself. BACKGROUND OF THE INVENTION [0002] The home audio industry places great emphasis on convenience, and sound quality. In-wall and in-ceiling audio speakers are at the height of their popularity. While floor speakers may at times, provide superior sound quality, the aesthetic appeal of in-wall speakers and their ability to deliver high-quality sound without the need to rearrange one's living room to make space for the speakers, have created a significant demand for quality in-wall speakers that deliver the hi-fidelity sound of floor speakers. [0003] Unfortunately, traditional in-wall speakers are mounted in a wall and therefore cannot simply be turned to redirect the sound as can be done with floor speakers, absent a great deal of effort and expense. One possible solution to such a dilemma is to make the transducers that comprise the in-wall speaker movable, so that the sound emanating from the transducers can be redirected without repositioning the entire speaker assembly. [0004] Such designs, however, face a number of inherent difficulties. One difficulty is that a speaker designed to allow transducers to rotate may inhibit the sound emanating from the transducers, thereby causing diffraction of the sound waves. In particular, when the transducer rotates, a portion of the transducer rises above the baffle surface, while naturally the opposing portion recedes within and below the surface of the baffle. The inner “wall” created by the transducer's receding below the baffle, reflects sound emanating from the transducer. This reflection causes diffraction of the sound waves resulting in reduced quality of sound reproduction. Another difficulty is that once a speaker is mounted in the wall or in the ceiling, it is very difficult to service and/or swap the speaker out for other speakers. [0005] As discussed above, pivotable and/or rotatable, together “swiveling,” in-wall transducers would be an advantage over those which cannot be swiveled to maximize the sonic “sweet spot.” A farther advantage could be found in the ability interchange various speaker configurations. Ideally, the transducers should be rotatable and pivotable without causing sound diffraction. [0006] Previous attempts have been made to provide speakers with components to direct sound for optimal listening such as are described in U.S. Pat. No. 6,101,262 to Haase et al. (the '262 patent); U.S. Pat. No. 6,070,694 to Burdett et al. (the '694 patent); U.S. Pat. No. 5,960,095 to Chang (the '095 patent); U.S. Pat. No. 5,402,502 to Boothroyd et al. (the '502 patent); U.S. Pat. No. 5,400,407 to Cassity et al. (the '407 patent); U.S. Pat. No. 5,319,364 to Shen (the '364 patent); U.S. Pat. No. 5,133,428 to Perrson (the '428 patent); U.S. Pat. No. 4,917,212 to Iwaya (the '212 patent); U.S. Pat. No. 4,884,655 to Freadman et al. (the '655 patent); U.S. Pat. No. 4,811,406 to Kawachi (the '406 patent); U.S. Pat. No. 4,553,630 to Ando (the '630 patent); U.S. Pat. No. 4,445,228 to Bruni (the '228 patent); U.S. Pat. No. 4,441,577 to Kurihara (the '577 patent); U.S. Pat. No. 4,139,734 to Fincham (the '734 patent); U.S. Pat. No. 4,182,429 to Senzaki (the '429 patent); and U.S. Pat. No. 3,976,838 to Stallings, Jr. (the '838 patent). [0007] The '262 patent describes a panel mount speaker system including a housing having flange and wall portions, a locating portion defining a primary support surface as a concave annular spherical segment, a secondary support member defining a secondary support surface as a concave spherical segment opposite a main pivotal point; a main speaker mount having an outwardly facing primary support surface; a main speaker unit coaxially mounted to the main speaker mount; a secondary mount member fastened to the stator element of the main speaker unit and having an outwardly facing secondary engagement surface slidably engaging the secondary support surface; an auxiliary speaker; a grill structure pivotally supporting the auxiliary speaker forwardly of the main speaker unit; a crossover network connected to the main speaker unit and the auxiliary speaker; a circuit panel mounting elements of the crossover network oriented and supported perpendicular to the housing axis, the panel flexing in response to axial loading of the secondary support member for preloading sliding engagement of the main speaker axis. However, the '262 patent suffers from a number of disadvantages. For example, the main speaker unit is set very deeply into the housing, thereby causing sound distortion when in a highly pivoted position. Another disadvantage is the size of the '262 speaker system. The main speaker unit and the main speaker mount are composed of two separate pieces, this is disadvantageous relative to a speaker system that integrates the pivoting structure (main speaker mount) with the main speaker. A similarly sized pivoting speaker to the '262, that is only one piece, could occupy less space and reduce the overall size of the system. [0008] The '694 patent, assigned to the assignee of the present application, describes a loudspeaker assembly with a transducer capable of being swiveled to direct the sound to a convenient point thereby allowing the listener to select the optimal direction of sound. [0009] The '095 patent describes a loudspeaker assembly including a base, a supporting plate, a casing, and a loudspeaker. The supporting plate is securely mounted to the base and includes a jointing member formed on a side thereof. The casing has a first end securely engaged with the supporting plate and a second end. The loudspeaker has a first end extending beyond a second end of the casing and a second end with a planar bottom side in a universal joint connection with the jointing member on the supporting plate. The loudspeaker has a section, which is slidable relative to an inner periphery of the casing to allow adjustment of an orientation of the loudspeaker relative to the supporting plate. [0010] The '502 patent describes sound output system comprised of a baffle, a plurality of sound drivers, and a sound mirror. The sound mirror reflects a beam of sound from the sound driver horizontally and vertically while maintaining generally consistent amplitude. One disadvantage of the '502 patent is that it requires a sound mirror to deflect sound waves rather than having the sounds waves emanating from the loudspeakers directly. [0011] The '407 patent describes a tilt adjuster for a speaker which adjusts the position of a speaker recessed in a wall. The tilt-adjuster, preferably assembled with a speaker cover, is a wedge-shaped frame with an open central portion for receiving the speaker housing; a front side including a flattened perimeter from making abutting engagement with the speaker's housing; and a back side which attaches to the speaker's support frame. Although the '407 enables some modicum of control over the directional sound of a speaker, it is not highly adjustable, and further does not provide for a pivoting tweeter or interchangeability. [0012] The '164 patent describes a speaker holder including a hollow, open holder body which receives a speaker within an inward top flange thereof, a bottom plate fastened to the holder body at the bottom to hold a spring-supported ball in a center hole on an upright center rod thereof for permitting the speaker to be balanced on the ball, and a mounting plate detachably fastened to the bottom plate through hooked joints for mounting the speaker holder on a supporting surface. [0013] The '428 patent shows a direction-adjustable speaker system comprised of a sound driver disposed within a rotatable mount positioned within a housing. The mount swivels within the housing to direct the sound to a desired location. [0014] The '212 patent describes a speaker supporting unit which includes a base and a substantially disc-shaped spacer. The spacer includes a half-round groove through which a screw can be inserted to secure the spacer to the base. The first surface of the spacer, which determines the orientation of the speaker is determined by a combination of the inclined surface of the base and the second surface of the spacer, which is varied by the relative angle between the base and the spacer. One disadvantage of the '212 patent is that it requires a spacer to determine the direction of sound projection and is not adjustable without removing the speaker and inserting a new spacer. [0015] The '655 patent describes a speaker cabinet having a pair of front wall segments and adjacent to the ends of the cabinet, and an intermediate forwardly opening cavity extending between the upper and lower front wall segments, a pair of large subwoofer speakers in the upper and lower front wall segments; and a swiveled movable center subcabinet having a woofer, mid-range speaker and a pair of tweeters. The subcabinet has a range of swivel movement horizontally about a vertical axis. The '655 patent suffers from its inability to rotate to reposition the speaker. It merely swivels thereby creating possible sound distortion when at its furthest position from center. In addition, the unit is bulky and would be difficult to mount in an automobile, wall or ceiling. [0016] The '406 patent describes a compound speaker system comprising a woofer, a squawker, a tweeter, and a super tweeter. The squawker, tweeter and super tweeter are attached to a plate and this assembly is rotatably positioned within the cone of the woofer. The system can be designed where the tweeter and super tweeter are at an elevated position with respect to the squawker when the assembly is rotated within the cone of the woofer. One disadvantage of the '406 patent is that it does not provide for a woofer capable of variably directing sound. The '406 patent also does not provide for interchangeable speaker configurations within a wall, ceiling, or vehicle setting. [0017] The '630 patent describes a speaker with a tweeter angle adjusting device. The tweeter can change direction by use of horizontal and vertical adjusting knobs and which are secured to horizontal shaft and vertical shafts, respectively, through the use of interlocking mechanisms. One disadvantage of the '630 patent is that it rotates the tweeter only, it does to describe a rotating woofer as well. In addition, the position means is through twisting knobs which require more effort than a simple pivot. [0018] The '228 patent shows a stereo audio system for a motorcycle including a housing for a radio receiver and speaker-mirror assemblies, mounted on base-socket assemblies, and threaded over mounting posts screwed into holes in the handlebars. This patent is specifically tailored for use in motorcycles and only pivots in one direction to provide sound while the motorcycle is in motion. [0019] The '577 patent describes a direction-variable speaker system for car-audio devices comprising two speaker cases containing speaker units for different reproduction bands, and an intermediate case interposed between the two speaker cases. A first pivotal shaft and a rising angle setting mechanism connect the first speaker case with the intermediate case. Between the second speaker case and the intermediate case is a second pivotal shaft as well as a twisting angle setting mechanism. By using the rising angle and twisting angle mechanisms, both speaker cases can be varied with respect to their angles in rising amount and twisting amount. The '577 includes multiple speakers but these speakers are not mounted in the same axis for sound projection. Additionally, there is no provision for interchangeability of configurations and the woofer is incapable of variable directional sound. [0020] The '734 patent describes a pivoting loudspeaker with a plurality of enclosures, wherein at least one of the enclosures is pivotably mounted with respect to another of the enclosures, and a light emitting device which is visible through an aperture only when a listener is in correct listening position. The '734 patent suffers from raised speaker sound diffraction and also cannot pivot the low frequency speaker without moving the entire system. [0021] The '429 patent shows a loud-speaker system particularly suitable for use in car stereo systems, comprising at least a tweeter, with a woofer arranged coaxially to the tweeter wherein the tweeter is adjustably mounted to the woofer in order to allow manual regulation of the position of the tweeter to that of the woofer. [0022] The '838 patent describes a sound reproduction system comprised of a plurality of speakers, said system being mounted in a wall. [0023] None of the devices mentioned above describe a loudspeaker assembly with a swiveling high frequency transducer capable of rotating and pivoting in any direction in combination with a pivoting low frequency transducer, and interchangeable with various other speaker configurations. [0024] Therefore, there is a need in the art for a loudspeaker assembly with a swiveling high frequency transducer capable of rotating and pivoting in any direction in combination with a pivoting low frequency transducer to obtain optimal dispersion control after installation of the speaker. [0025] There is a further need in the art for a loudspeaker assembly which can be mounted in the baffle of an in-wall speaker and direct the sound to obtain the “sweet spot” without any diffraction or distortion of sound caused by the sound waves radiating off the sharp inner edge of the baffle created by the swiveling of the transducers. [0026] There is a further need in the art for a loudspeaker assembly that can allow a listener to swivel the transducers to obtain optimal dispersion control after installation of the speaker within a vehicle. [0027] There is a further need in the art for a loudspeaker assembly having the features of the present invention whereby the loudspeaker assembly is a free-standing floor speaker. [0028] There is a further need in the art for a loudspeaker assembly that can be easily replaced by a speaker assembly of an alternate configuration. SUMMARY OF THE INVENTION [0029] The present invention fills these needs by providing an interchangeable loudspeaker assembly capable of providing unobstructed directional sound. [0030] In a preferred embodiment, what is provided is a loudspeaker assembly, comprising a frame for removably attaching transducer assemblies; a tweeter assembly; means to rotate and pivot the tweeter assembly, such that the tweeter assembly rotates and pivots without causing sound diffraction by the frame for removably attaching transducer assemblies; a woofer assembly; and means to rotate and pivot the woofer assembly, such that the woofer assembly rotates and pivots without causing sound diffraction by the frame for removably attaching transducer assemblies. [0031] In an alternate embodiment, the loudspeaker assembly comprises a frame for removably attaching transducer assemblies; a tweeter assembly, comprising a tweeter post, a retaining spring, a tweeter post cap, a tweeter ball bottom, a high frequency transducer, and a tweeter ball top; means to rotate and pivot said tweeter assembly, such that the tweeter assembly rotates and pivots without causing sound diffraction by the frame for removably attaching transducer assemblies; a woofer assembly, comprising a woofer frame retainer, a woofer frame, and a twist lock baffle; means to rotate and pivot said woofer assembly, such that the woofer assembly rotates and pivots without causing sound diffraction by the frame for removably attaching transducer assemblies; and, grilles for protection and appearance. [0032] Accordingly, it is an object of the present invention to provide a loudspeaker assembly with a swiveling high frequency transducer capable of rotating and pivoting in any direction in combination with a pivoting low frequency transducer to obtain optimal dispersion control after installation of the speaker. [0033] It is another object of the present invention to provide a loudspeaker assembly which can be mounted in the baffle of an in-wall speaker and direct the sound to obtain the “sweet spot” without any diffraction or distortion of sound caused by the sound waves radiating off the sharp inner edge of the baffle created by the swiveling of the transducers. [0034] It is another object of the present invention to provide a loudspeaker assembly that can allow a listener to swivel the transducers to obtain optimal dispersion control after installation of the speaker within a vehicle. [0035] It is another object of the present invention to provide a loudspeaker assembly having the features of the present invention whereby the loudspeaker assembly is a free-standing floor speaker. [0036] It is another object of the present invention to provide a loudspeaker assembly that can be easily replaced by a speaker assembly of an alternate configuration. [0037] This and other objects, features and advantages of the present invention may be better understood and appreciated from the following detailed description of the embodiments thereof, selected for purposes of illustration and shown in the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0038] [0038]FIG. 1A is a front perspective view of a preferred embodiment of the speaker assembly according to the invention. [0039] [0039]FIG. 1B is a rear perspective view of a preferred embodiment of the speaker assembly according to the invention. [0040] [0040]FIG. 2 is a cross-sectional view of a preferred embodiment of the speaker assembly according to the invention. [0041] [0041]FIG. 3 is a front perspective, exploded view of a preferred embodiment of the speaker assembly according to the invention. [0042] [0042]FIG. 4 is a side, exploded view of a preferred embodiment of the speaker assembly according to the invention. [0043] [0043]FIG. 5 is an exploded view of a preferred embodiment of the spring retained transducer assembly according to the invention. [0044] [0044]FIG. 6 is a side view of a preferred embodiment of the speaker assembly according to the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0045] Referring initially to FIG. 1A of the drawings, in which like numerals indicate like elements throughout the several views, in a preferred embodiment what is provided is a loudspeaker assembly 1 that allows for a pivoting low-frequency transducer to be used in combination with a spring retained, pivoting high-frequency transducer 12 . In this perspective view, the entire loudspeaker assembly 1 is illustrated. The positional relationship between the tweeter assembly 2 (comprising elements 10 - 16 , 44 , and 46 ) and the woofer assembly 4 (comprised of elements 18 - 42 ) is illustrated in further detail in FIG. 3. A side view can be seen in FIG. 6. Although a pivoting high frequency transducer 12 and a pivoting low frequency transducer (comprising elements 24 - 38 ) are described, alternate embodiments could include a non-pivoting high frequency transducer and a pivoting low frequency transducer in combination or vice-versa, such that only one of the pair of transducers pivots. [0046] [0046]FIG. 1B illustrates the twisting lock style fastening baffle 18 and the frame 20 in operation. The tweeter assembly 2 and the woofer assembly 4 can be removed from the frame 20 and replaced with a different loudspeaker configuration by simply twisting them until the locking arms of the twist lock baffle 18 can pass through the insertion holes in the frame 20 . The effectiveness of the locking arms of the twist lock baffle can be enhanced by biasing the arms such that, in the locked position, the locking arms exert themselves into fastening holes located on the frame 20 . The transducer assemblies 2 , 4 could also alternatively be removably mounted using snap-in clips or other similar means known to those who are skilled in the art of loudspeaker assembly, installation and mounting. [0047] Referring now to FIG. 2, a perspective, cross-sectional view of the loudspeaker assembly 1 illustrates the tweeter assembly 2 mounted in the woofer assembly 4 . The retaining spring 44 is shown holding the tweeter ball bottom 14 in place within the tweeter post 16 . The woofer frame 32 abuts the woofer frame retainer 40 and the twist lock baffle 18 . A compression fit allows for pivoting of the woofer assembly 4 and the high frequency transducer 2 assembly mounted thereon. The high frequency transducer 12 can be pivoted separately using the friction fit, caused by the downward force exercised on the tweeter ball bottom 14 by the retaining spring 44 , between the tweeter ball bottom 14 and the tweeter post 16 . [0048] [0048]FIG. 3 illustrates the positional relationship between all the component parts of the present invention 1 . The PCB Assembly 42 directs high frequency signals to the high frequency transducer and low frequency signals to the low frequency transducer. The PCB Assembly is secured to the woofer frame retainer 40 , the woofer frame retainer holding in place the purely cosmetic back plate plug 39 , the back plate 38 , the magnet 36 , the top plate 34 and the woofer frame 32 . The back plate 38 is shaped so that the pole section fits through a circular hole cut out of the middle of the magnet 36 . The woofer frame 32 holds in position the low frequency transducer, which is comprised of a debris screen 31 , a coil 30 , a spider 28 (used in conjunction with the surround 24 to suspend the cone 26 at top and bottom). The twist lock baffle 18 is fastened to the woofer frame retainer 40 , and the woofer assembly 4 is removably attachable to the frame 20 . The twist lock baffle 18 and the frame 20 are positioned such that, in the maximally pivoted position, sound waves emitted from the low frequency transducer are not distorted. The frame 20 is ideally attached to a wall, for example in a home, using dogleg clamps 22 and dogleg clamp retainers 23 . The frame 20 can also be used in automobile or incorporated into a freestanding loudspeaker. Attached to the woofer assembly 4 , is the tweeter assembly 2 . The tweeter assembly 2 is comprised of elements 10 - 16 , 44 and 46 . The tweeter post 16 is connected to the back plate 38 . Within the tweeter post is the retaining spring 44 , the spring being held in place by the tweeter post cap 46 . The spring 44 extends the length of the tweeter post 16 attaching to the underside of the tweeter ball bottom 14 . The tweeter ball bottom 14 holds the high frequency transducer 12 in place. The tweeter ball top 10 is attached to the tweeter post 16 and holds the High frequency transducer 12 and the tweeter ball bottom 14 within the cavity formed by the post 16 and the top 10 . The upper portion of the post 16 is formed like a cup, and the tweeter ball bottom 14 is formed to match that shape. The fit between the ball bottom 14 and the post 16 , in addition to the downward pull applied by the spring 44 on the ball bottom 14 , allow the high frequency transducer 12 to be pivoted, where it will remain until being repositioned. In addition, the present invention provides movement of the high frequency transducer 12 such that there is no sound distortion caused by the tweeter ball bottom 14 or the frame 20 as the transducer 12 is at its maximally pivoted position. Capping off the assembly 1 are perforated metal grilles, 6 , 8 which serve the dual purpose of protecting the assembly 1 and providing an aesthetic appearance. FIG. 4 illustrates all these component parts from a side view. [0049] Turning to FIG. 5, the protrusion 50 at the bottom of the tweeter post 16 passes through the bottom loop of the retaining spring 44 . The spring 44 is maintained in place by securing the open end of the protrusion 50 with the tweeter post cap 46 . The retaining spring proceeds through the central hollow portion of the tweeter post 16 , where it attaches its uppermost loop to a cross-member 52 in the tweeter ball bottom 14 . The retaining spring 44 pulls the tweeter ball bottom 14 towards the upper surface of the tweeter post 16 . The tweeter ball bottom is shaped like a cup and fits within the slightly larger cup shape of the tweeter post 16 . There is enough downward force exerted by the retaining spring 44 , that if the tweeter ball bottom 14 is pivoted, it remains in a pivoted position until moved again. Inside the tweeter ball bottom 14 rests the high frequency transducer 12 . The tweeter assembly 2 is capped by a tweeter ball top 10 , which is secured to the tweeter post 16 . [0050] Accordingly, it will be understood that the preferred embodiment of the present invention has been disclosed by way of example and that other modifications and alterations may occur to those skilled in the art without departing from the scope and spirit of the appended claims.
An interchangeable loudspeaker assembly capable of pivoting the low-frequency and high-frequency transducers to provide directional sound while avoiding hindrance of sound waves by the loudspeaker frame.
7
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. provisional application 60/853,712, filed Oct. 23, 2006, which is incorporated herein by reference. This application claims the benefit as a continuation-in-part of U.S. patent application Ser. No. 11/311,060, filed Dec. 19, 2005, which is incorporated herein by reference. [0002] This application is related to the following applications, each of which is incorporated herein by reference: [0003] Backup Electrical Power System for Solid-State Aircraft Power Distribution Systems, U.S. patent application ______, filed on the same date hereof; [0004] Aircraft Electrical System Evaluation, U.S. patent application ______, filed on the same date hereof; [0005] Aircraft Exhaust Gas Temperature Monitor, U.S. patent application ______, filed on the same date hereof; [0006] Variable Speed Flap Retraction and Notification, U.S. patent application ______, filed on the same date hereof. FIELD OF THE INVENTION [0007] This invention relates to the field of aircraft control, and more specifically to assisting of pilots in the management of emergency conditions. BACKGROUND OF THE INVENTION [0008] The present invention relates to control of aircraft. Modern commercial/private aircraft, as well as older aircraft, include a myriad of instrumentation panels associated with electronic devices having controls, displays, and software applications, which are used to present information to pilots and/or copilots during flight. The electronic devices, controls, displays and applications are interfaced together to form avionics equipment within the aircraft. Pilots (where “pilot” includes copilots and any other controller of the aircraft) access one or more interface devices of the avionics equipment prior to and during the flight. Some of this information presented monitors the status of equipment on the aircraft, while other switches and knobs are used to control functions of the aircraft such as throttles (engine speed), switches (lights, radios, etc), levers (landing gear and flaps), and controls for navigation, for example. [0009] Avionics are important because they enable the pilot to control the aircraft, monitor and control its systems, and navigate the aircraft. Avionics systems today are generally manual: the pilot must manually select the proper switch, knob, etc. to control a certain function in response to aircraft and environmental conditions. This action can be the result of normal activities, and is usually read from a checklist so as not to miss anything; or can be the result of a warning display, at which time the pilot must react accordingly. Pilot error, in the form of not knowing what to do or reacting improperly, leads to increased accident and death rates. Crashes can also result from pilots being distracted by an emergency and not maintaining control of the aircraft because they are busy troubleshooting or reacting to the problem. Such actions have the possibility to distract the pilot's awareness from the surrounding situation, or the state of the aircraft in flight. [0010] General aviation accident statistics show that the accident rate for single pilot, non professionally flown aircraft is significantly greater than that for dual-pilot professionally flown aircraft. Accordingly, there is a need for methods and apparatuses that reduce pilot workload and increase the performance and efficiency of the pilot's control of the aircraft through automation. This ensures both a proper response to certain emergencies, and allows the pilot to focus on flying the aircraft. SUMMARY OF THE INVENTION [0011] The present invention provides methods and apparatuses that reduce pilot workload and increase the performance and efficiency of the pilot's control of the aircraft. The present invention comprises methods and apparatuses for determining the presence and type of an emergency condition, for example by detecting corresponding sensor outputs or by accepting input from a pilot or a combination thereof; and then responding to that emergency by initiating a pre-determined set of actions specific to the determined emergency. Embodiments of the invention can include the ability to monitor engine conditions as well as control electrical functions such as the fuel boost pump, alternator field, battery contactor and other important electrical devices. Some examples described below assume a single-engine piston aircraft for ease of illustration. The invention can also be applied to multi engine and turbine powered aircraft as well. [0012] A graphical display, such as a liquid crystal display, a heads up display, or other visual communication technology, can be provided for the pilot. Relevant information, such as checklists relating to an emergency, and the status of engine parameters and devices can be readily communicated to the pilot using the graphical display. [0013] In some embodiments, the pilot can indicate an emergency condition by an input to the system: a pushbutton labeled “Emergency”, for example. In some embodiments, the system can detect an emergency automatically and respond automatically. In some embodiments, both pilot input and automatic detection can be provided, and in some embodiments can be selectively enabled or disabled. After the system determines (automatically or from pilot input) that an emergency exists, the system can then determine what type of emergency is occurring, again from sensor outputs, pilot input, or a combination. In the example illustrated in FIG. 6 , the pilot can select from the following: Engine Failure, Engine Fire, Alternator Failure, Electrical Fumes, or Manual Control button. These emergencies are typical of single engine aircraft; other emergency types can be used in connection with other types of aircraft. [0014] Once the type of emergency is determined, the system can display an appropriate checklist for that emergency on the graphical display. A pre-configured sequence of events can be carried out by the system. Additionally, additional pilot input can be accepted, for example using programmable soft keys in connection with the graphical display, with functions as shown in FIG. 6 . This can provide additional control and functionality for the pilot. The system can exit the emergency operation after determining that the emergency no longer exists or that the pilot does not desire the assistance of the system. The system can determine that the emergency no longer exists or that the pilot does not desire the assistance of the system by sensor outputs, pilot input, or a combination. BRIEF DESCRIPTION OF THE DRAWINGS [0015] FIG. 1 is a schematic illustration of an example method according to the present invention. [0016] FIG. 2 is a schematic illustration of an example apparatus according to the present invention. [0017] FIG. 3 is a flow diagram of an example method according to the present invention. [0018] FIG. 4 is a flow diagram of an example method according to the present invention. [0019] FIG. 5 is a schematic illustration of a display suitable for use with some embodiments of the present invention. [0020] FIG. 6 is a flow diagram of an example method according to the present invention. [0021] FIG. 7 is a flow diagram of an example method of managing an alternator failure according to the present invention. [0022] FIG. 8 is a flow diagram of an example method of managing an alternator failure according to the present invention. [0023] FIG. 9 and FIG. 10 are schematic illustrations of buss architectures accommodated by example embodiments of the present invention. [0024] FIG. 11 is a schematic block diagram of an example embodiment of the present invention. [0025] FIG. 12 is a schematic illustration of an example embodiment of the present invention. [0026] FIG. 13 is a schematic illustration of computer software suitable for implementing an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0027] The present invention provides methods and apparatuses for assisting a pilot in identifying and managing emergency conditions in an aircraft. FIG. 1 is a schematic illustration of an example method according to the present invention. An indication of an emergency condition is accepted 101 . The indication can be determined automatically from sensor information, or can be determined by pilot input such as a pilot pressing an “emergency” button or giving a voice command that indicates an emergency condition. A specific emergency condition is then determined from a plurality of possible emergency conditions 102 . The determination can be performed automatically from sensor information, or can be determined from pilot input such as a pilot pressing a button corresponding to a specific emergency, providing a voice command that identifies the emergency, or providing a series of such inputs, for example by providing responses to prompts from an automated emergency identification system. A plurality of aircraft operating parameters is then controlled as indicated for the specific emergency condition 103 . The emergency condition can be determined to be complete after completion of the parameter control, after an input from a pilot, based on sensor information related to the emergency, or a combination thereof. After the emergency condition is complete, the aircraft can be returned to its pre-emergency operating state, or can be left with operating parameters as controlled for the emergency state, or set in a control state defined as the post-emergency state for the determined emergency, or a combination thereof 104 . [0028] FIG. 2 is a schematic illustration of an apparatus suitable for use with the present invention. A controller 201 , such as a single board computer, is connected to operating systems of an aircraft such that the controller can control the connected operating systems, according to a method such as those described in the example embodiments disclosed herein. The controller 201 optionally also accepts input from one or more sensors indicative of the status or performance of aircraft systems. The controller 201 communicates with a pilot output system 202 , for example with a video display or with an audio generator, or a combination thereof. The controller 201 also communicates with a pilot input system 203 , for example with a touch-sensitive display screen, buttons or knobs, and audio input system, or other input system. [0029] In operation, the controller 201 can determine the existence of an emergency condition from sensor information or by input from a pilot via the pilot input system 203 . The controller 201 can determine a specific emergency condition from a plurality of defined emergency conditions, for example from sensor information that can indicate aircraft systems or combinations of systems that correspond to a specific emergency condition, or from pilot input via the pilot input system 203 , by direct specification by the pilot or confirmation by the pilot of an emergency condition from a set of possible emergency conditions presented to the pilot via the pilot output system 202 . The controller 201 can have stored a set of operating parameters that correspond to each of several emergency conditions. The stored set can also be augmented or customized by sensor information, for example, an operating parameter can be stored as an absolute control setting or as a relative change to a control setting (e.g., “set parameter to half the previous value”), and as a conditional change (e.g., “if sensor exceeds a threshold, then set parameter”), or combinations thereof. After the specific emergency condition is identified, the set of operating parameters can be used to control the aircraft. The control can be done automatically upon determination of the specific emergency condition, or can be done after confirmation from the pilot of specific actions or sets of actions, or a combination thereof. The control can establish fixed parameter settings, or can vary operating parameters in a predetermined or in response to sensor information. If the specific emergency condition can be terminated or ended, then the controller 201 can determine the end of the condition by sensor information, lapse of time, or pilot input via the pilot input system 203 . The controller 201 can set aircraft control parameters at the end of the emergency condition according to the specific emergency condition, pilot input, or sensor information (e.g., if the emergency was a persistent failure of an aircraft system, the operating parameters might need to remain as set in the emergency condition control, while an emergency condition that can be cured might allow operating parameters to be returned to their pre-emergency condition). [0030] FIG. 5 is a schematic illustration of a display and input apparatus 501 suitable for use with the present invention. The apparatus comprises a visible display screen 502 , such as those in contemporary use in computers, phones, and the like. The display screen 502 can be used to communicate information to a pilot, such as the current state of various aircraft operating parameters, and information relative to an emergency condition. A physical input device such as a rotary knob 504 can mount near the display screen 502 , for example to allow a pilot to adjust an operating parameter over a range, or select from a range of options displayed on the screen 502 . A plurality of physical input devices such as push buttons 503 can mount near the screen 502 . Each button can correspond to a specific pilot input communication; for example, one button can be used by a pilot to indicate the presence of an emergency condition. The correspondence of buttons to input communications can also be determined based on the current communications desired. For example, the screen 502 can display information near each button, where the information provides a pilot with a specification of the action indicated by pressing that button. The information displayed and the corresponding actions can thereby be customized to the information most relevant to the current communication with the pilot, allowing a small number of buttons to be used for a wide variety of communications. [0031] FIG. 3 is a flow diagram of an example embodiment of the present invention, illustrating several possible types of emergency conditions. In the example, a pilot can initiate an emergency condition response by pressing a button 301 . A display screen 302 and pilot input can then be used to allow the pilot to specify a particular emergency condition. The emergency conditions communicated to the pilot can be a complete list of possible emergency conditions, or can be selected from sets of conditions most likely based on the current aircraft operation (e.g., taxi or climb) or current sensors (e.g., engine temperature). The example shows three possible emergency conditions; the number of conditions can be more or less than three. Selecting the first condition in the example initiates an automatic setting of various aircraft control parameters to values predetermined for that emergency condition 303 . The first emergency condition is of a sort that allows a pilot to indicate that the emergency had ended 304 , after which the operating parameters are returned to the pre-emergency settings 305 . Selecting the second emergency condition initiates an automatic setting of various aircraft control parameters to values predetermined for that emergency condition 306 . The second emergency condition is of a sort that allows the pilot to indicate whether the change in aircraft control parameters 307 has resolved the emergency 307 . If it has, then the operating parameters are restored to their pre-emergency conditions 310 . If not, then a second level of emergency response control parameters are applied 308 . Selecting the third emergency condition initiates an automatic setting of various aircraft control parameters to values predetermined for that emergency condition 309 . The third emergency condition is of a sort that does not have an automatic recovery or end, and so the operating parameters are left in the settings predetermined as appropriate for response to that emergency condition. [0032] FIG. 4 is a flow diagram of an example embodiment of the present invention. In the example embodiment, an emergency condition can be determined 401 from sensor information. The emergency condition can be confirmed 402 by communication with a pilot, for example by displaying information concerning the sensor information and the possible emergency condition. If the pilot does not confirm the emergency condition (because it does not exist, or because the pilot does not desire automated assistance in managing it), then the aircraft can be returned to normal operations. If the pilot confirms the emergency condition, then suggested settings to the aircraft operating parameters can be communicated to the pilot 403 . The suggested settings can be specific to the determined emergency condition, and can also be derived from sensor information related to the emergency condition. The suggested settings can be applied automatically, or can be suspended until confirmed by the pilot. For example, the pilot can confirm each suggested setting by pushing a button, a region on a touch-sensitive screen, or supplying a voice command. The suggested settings can also be modified by the pilot in similar ways. The confirmed operating parameter settings can then be applied to the operation of the aircraft 404 . [0033] FIG. 6 is a flow diagram of an example embodiment of the present invention. A pilot can indicate that an emergency condition is current, for example by pressing an input button 601 like those described in connection with FIG. 5 . A plurality of possible specific emergency management functions can be displayed to the pilot, and the pilot allowed to select one, for example by displaying the emergency management functions on a display screen and using input buttons like those described in connection with FIG. 5 . In the example of FIG. 6 , the possible emergency management functions are Engine Failure 602 , Engine Fire 603 , Alternator Failure 604 , Electrical Fumes 605 , and Manual Control 606 . [0034] If the pilot selects the Engine Failure management function, then a checklist relevant to an engine failure condition can be displayed 607 . The boost can be automatically set to on 608 ; the engine ignition system can be automatically set to on 609 , the alternator can be automatically set to on 610 , and an input button set to correspond to activation of the starter 610 . The pilot can then start the engine by pressing the button, with the relevant operating parameters already set. [0035] If the pilot selects the Engine Fire management function, then a checklist relevant to an engine fire can be displayed. The boost can be automatically turned off 613 , the alternator can be automatically turned off 614 , and an input button set to correspond to turning off all engine systems 615 . [0036] If the pilot selects the Electrical Fumes management function, then a checklist relevant to a condition generating electrical fumes can be displayed 616 . The weather conditions can be determined 617 , for example by sensors, reading a switch, sensing a soft button configured by the system, or accepting a voice or similar input from the pilot. The electrical loads on the aircraft's electrical system can be turned off, isolated, or otherwise shed 618 . The particular loads shed can be dependent on the weather conditions, with different load shed parameters used depending on the result of the IMC/VMC determination. An input button can be set to correspond to turning off all electrical systems 619 . [0037] If the pilot selects the Manual Control management function, the input buttons can be set to correspond to control adjustments likely to used in various emergency conditions. The crosstie can be toggled between on and off by a button 620 . The alternator can be cycled responsive to a button 621 . The Bus A can be toggled between on and off by a button 622 . The Bus B can be toggled between on and off by a button 623 . The started can be engaged responsive to a button 624 . [0038] Selection of the Alternator Failure button can initiate various courses of action, depending on the specific design of the aircraft electrical system. Examples are discussed in connection with FIG. 7 and FIG. 8 . [0039] After each of the emergency management functions, the pilot can indicate either Restore 626 or Emergency 627 . If Restore is indicated, then the operating parameters adjusted during the emergency management function are restored to their settings before the adjustments. If Emergency is indicated, then the operating parameters are left as they were adjusted, and the emergency management system completed 629 . [0040] FIG. 9 is a schematic illustration of a first example bus architecture. A Main Bus 901 is in electrical communication with a Battery Contactor 904 . The Battery Contactor 904 is in electrical communication with a Primary Alternator 902 and a Backup Alternator 903 , and with a Battery 905 . FIG. 7 is a flow diagram of an Alternator Failure emergency management function suitable for use with such a bus architecture. The function can be initiated by a pilot indicating an Alternator Failure 701 . A checklist relevant to an alternator failure can be communicated to the pilot 702 . The primary alternator can be turned on 701 , and a suitable amount of time allowed to elapse 704 . The bus voltage can then be sensed 705 ; if the bus voltage exceeds the minimum threshold, then the emergency condition can be ended 715 (this situation can arise, for example, if the primary alternator had been inadvertently turned off). If the bus voltage does not exceed the minimum threshold, then The weather conditions can be determined 706 , for example by sensors, reading a switch, sensing a soft button configured by the system, or accepting a voice or similar input from the pilot. Load is then shed from the system, with the particular loads shed determined from the results of the IMC/VMC determination 707 . The primary alternator is then turned off 708 and the secondary alternator turned on 709 . The pilot can indicate 712 that the pre-emergency conditions should be restored 710 , in which case all electrical devices are restored to their pre-emergency conditions except the alternators 713 . Alternatively, the pilot can indicate 714 that the emergency condition has ended, and the aircraft is operated with the electrical devices left in the state set during the emergency management function. [0041] FIG. 10 is a schematic illustration of a second example bus architecture. A first battery 1003 is in electrical communication with a first battery contactor 1006 . The first battery contactor 1006 is in electrical communication with a first alternator 1008 , a first main bus 1001 , and a cross tie connector 1007 . A second battery 1004 is in electrical communication with a second battery contactor 1005 . The second battery contactor 1005 is in electrical communication with a second alternator 1009 , a second main bus 1002 , and the cross tie connector 1007 . FIG. 8 is a flow diagram of an emergency management function suitable for use with such a bus architecture. A pilot can indicate an alternator failure 801 , for example by pressing a button as described before. A checklist relevant to an alternator failure can be communicated to the pilot 802 , for example by a display as described before. Both busses can be sensed to determine if either has a voltage less than a minimum threshold 806 . If both busses have voltages greater than the minimum threshold, then the emergency condition is ended 816 . Is a has a voltage less than the minimum threshold, then the weather conditions can be determined 807 , and load can be shed from the bus 808 (with the particular loads shed dependent on the result of the IMC/VMC determination), and the alternator on the low voltage bus turned off 809 . The cross tie contactor can be closed 810 , connecting the first and second battery contactors. The pilot can indicate 813 that the pre-emergency conditions should be restored 815 , in which case all electrical devices are restored to their pre-emergency conditions except the alternators 815 . Alternatively, the pilot can indicate 814 that the emergency condition has ended, and the aircraft is operated with the electrical devices left in the state set during the emergency management function. Example Embodiment [0042] FIG. 11 is a schematic block diagram of an example embodiment of the present invention. A Display Panel accommodates communication of information to a pilot. A Switch Panel accommodates communication of information from a pilot. A single or dual redundant controller(s) can be used to determine state, to set controls, to control the display, to accept input in between the sensors and the display/switch. Sensors corresponding to various attributes of aircraft, such as those discussed above, provide information to the controller. The controller determines the state of the aircraft from the attributes, for example as described above. The controller sends information to the display which accepts input based on the determined state. For example, the controller can accept input from one or more switches, where the switches are defined to have specific meanings depending on the determined state. The controller initiates control of various aircraft attributes, for example those described above, based on the determined state and on pilot input. While the controller and display functions are described separately for convenience, they can be integrated in a single system, or part of the controller can be integrated with the display while part is separate from the display. [0043] A suitable display panel can comprise appropriate technology for aircraft use. A width of no more than 6.25″ can allow the system to readily fit in a standard radio rack. The system can operate in all temperature ranges expected in the aircraft cockpit environment, for example, typically −30 deg C. to +70 deg C. The screen can be daylight readable, for example with a transflective screen or transmissive screen with a brightness greater than about 500 nits. A suitable switch panel can comprise a portion of a touch sensitive display configured by the controller for pilot input. It can also comprise discrete switches mounted near the display, voice recognition, or remotely mounted switches. Switches can have high quality, gold-plated contacts for desirable reliability. The sensor interface converts analog signals from commercially-available temperature, pressure, and other analog sensors to digital signals that can be processed by the microcomputer. The controllers can be implemented using commercially available switching devices and current sensing devices, with interfaces to the microcomputer. [0044] A suitable controller can be implemented with a conventional single board microcomputer, with discrete logic, with programmable logic, or application specific integrated circuits, or combinations thereof. A typical microprocessor is a Motorola HCS12 or comparable with built-in serial I/O and at least 256 KB of non-volatile memory. A programmable controller implementation can execute software developed using conventional programming techniques such as C programming language. [0045] FIG. 12 is a schematic illustration of an embodiment of the present invention. A Microcontroller is programmed to implement functionality such as that described in the examples described herein. The Microcontroller accepts Input from sensors and other systems, configured for access by the Microcontroller, if needed, by appropriate Input Conditioning. The Microcontroller also accepts input from the user via User Input Controls. The Microcontroller outputs signals to control a Display, mounted to communicate with the pilot. An Alternator Control system communicates with the Microcontroller and controls and senses operation of one or more alternators. The Alternators and Battery connect to an Electrical Bus. The Microcontroller controls various Switches (and senses their configuration by, for example, Current Sense). The Switches can control various Loads, such as various systems of the aircraft. [0046] FIG. 13 is a schematic illustration of computer software suitable for implementing an embodiment of the present invention. A User Input Monitor Loop monitors input from the user; a Sensor Monitor Loop monitors input from aircraft sensors. A State Determination function determines the state of the aircraft from the user input and the aircraft sensors. A Device Status Monitor Loop and a Discrete Switch Monitor Loop provide input to Device Status Logic, which can control devices (Device Control) in combination with a Fault Handling function. A Display Control function can combine information from the various other functions to control an Information Display. Those skilled in the art will appreciate various other implementations, including other software approaches, approaches using multiple processors, and other combinations of hardware and software. [0047] The particular sizes and equipment discussed above are cited merely to illustrate particular embodiments of the invention. It is contemplated that the use of the invention can involve components having different sizes and characteristics. It is intended that the scope of the invention be defined by the claims appended hereto.
The present invention provides methods and apparatuses that reduce pilot workload and increase the performance and efficiency of the pilot's control of the aircraft. The present invention comprises methods and apparatuses for determining the presence and type of an emergency condition, for example by detecting corresponding sensor outputs or by accepting input from a pilot or a combination thereof; and then responding to that emergency by initiating a pre-determined set of actions specific to the determined emergency. Embodiments of the invention can include the ability to monitor engine conditions as well as control electrical functions such as the fuel boost pump, alternator field, battery contactor and other important electrical devices. Some examples described below assume a single-engine piston aircraft for ease of illustration. The invention can also be applied to multi engine and turbine powered aircraft as well.
6
BACKGROUND OF THE INVENTION The present invention relates to a novel fermentation product referred to herein as difficol or oxydifficol and to a process for preparing, isolating and purifying said compounds. The term difficol refers to the compound of Formula I hereinbelow wherein R 1 is hydrogen and the term oxydifficol refers to the compound of Formula I wherein R is hydroxy. The novel fermentation products are prepared by microbiological cultivation of Bacillus subtilis MB 3575 and MB 4488 deposited with the American Type Culture Collection, Rockville, Md. under the designation ATCC 39374 and 39320 respectively. The novel fermentation products are useful as intermediates in the production of the broad spectrum antibiotics difficidin, oxydifficidin. These broad spectrum antibiotics and method of preparing them are disclosed in EPO Application No. 84106408.2, Publication No. 0128505--published Dec. 14, 1984. However, it is noted that this published application contains no suggestion that difficol is present in or recoverable from the cultivation of Bacillus subtilis microorganisms. DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention there is provided a compound of Formula I hereinbelow useful as an intermediate in the preparation of broad spectrum antibiotics of the difficidin and oxydifficidin type. ##STR3## wherein R 1 is hydrogen or hydroxy. Difficol is represented by the above formula when R 1 is hydrogen and oxydifficol is represented by the above formula when R 1 is hydroxy. It is unexpected to find that these macrocyclic alcohols are biologically inactive but when the hydroxyl group is phosphorylated to produce the corresponding difficidin or oxydifficidin, the resulting compounds are highly active broad spectrum antibacterials of the formula: ##STR4## wherein R 1 is H or OH. Difficol and oxydifficol may be prepared by microbiological cultivation of Bacillus subtilis, MB 3575 and MB 4488 deposited with the American Type Culture Collection, Rockville, Md., from which it is available without restriction under the accession numbers ATCC 39374 and 39320, respectively. The Bacillus, or its variants and mutants may be cultivated in accordance with well known microbiological processes, either on agar slant tubes, or under submerged conditions in Erlenmeyer flasks or fermentors, utilizing nutrient media or nutrient solutions generally employed for cultivating microorganisms. In the present invention, difficol and its hydroxy derivative are produced during cultivation of the microorganism, for example, Bacillus subtilis ATCC 39320 at a temperature of about 28° C., under aerobic conditions. The composition of the nutrient medium may be varied over a wide range. The essential assimilable nutrient ingredients are; a carbon source, a nitrogen source, a source of inorganic elements including phosphorus, sulfur, magnesium, potassium, calcium and chlorine. Cultivation is most productive under neutral pH conditions, preferably from about 6.0 to 7.0. Typical sources of carbon include glucose, dextrin, starches, glycerol and the like. Typical nitrogen sources include vegetable meals (soy, cottonseed, corn, etc.), meat flours or animal peptones, distillers solubles, casamino acids, yeast cells, various hydrolysates (casein, yeast, soybean, etc.), yeast nucleic acids and amino acids. Mineral salts such as the chlorides, nitrates, sulfates, carbonates and phosphates of sodium, potassium, ammonium, magnesium and calcium provide a source of essential inorganic elements. The nutritive medium may also contain a number of trace elements such as iron, copper, manganese, zinc and cobalt. If excessive foaming is encountered during the cultivation, antifoaming agents such as vegetable oils, lard oil and polypropylene glycol may be added to the fermentation medium prior to, or during the course of the fermentation. The maximum yield of difficol can be achieved within from about 20 to 120 hours, and is culture dependent. The inoculum for the fermentation can be provided from suspensions, slants, frozen cells or freeze-dried preparations. In addition to the conventional cultivation processes described above, there may also be employed continuous processes, such as that described in Methods in Microbiology, Vol. 2, Academic Press, London-New York, 1970, pp. 259-328. In such systems the bacillus can be maintained for extended periods of time in a steady state without spontaneous mutations or other degenerations becoming evident. It is to be understood that for the production of difficol and oxydifficol, the present invention is not limited to the use of Bacillus subtilis ATCC 39374 or 39320. It is especially desired and intended to include the use of natural or artificial mutants produced from the described organisms, or other variants of Bacillus subtilis ATCC 39374 or 39320 as far as they can produce difficol and oxydifficol. The artificial production of mutant Bacillus subtilis may be achieved by a conventional operation such as X-ray or ultraviolet (UV) radiation, or by the use of chemical mutagens such as; nitrogen mustards, nitrosoguanidine, camphor and the like, or by means of recombinant DNA technology. In another aspect of the present invention it has been found that the yield of oxydifficol is greatly increased by a two-step procedure which involves (1) cultivating strain MB 3575 preferably for a period of 5 days and (2) following the fermentation, adjusting the pH to 8.3-8.5 with buffer solution and adding magnesium chloride (0.2 M). The resulting mixture is then agitated for a period of about 24 hours at room temperature or about 25° C. The yield of oxydifficol product ranges from 40-60 μg/ml of treated fermentation broth which represents a substantial increase in yield compared to that obtained by extraction from the harvested broth without any subsequent treatment. MORPHOLOGICAL AND PHYSIOLOGICAL CHARACTERISTICS OF Bacillus subtilis ATCC 39320 The morphological and physiological properties of ATCC 39320 are as follows: Morphology: gram positive, non-vacuolated vegetative rods with rounded ends; average size 0.9×2.3-3.6μ; occurring singly. Rods are motile. Spores are produced under aerobic conditions. Spores are 0.5×1.0μ (average size), oval to cylindrical, predominantly central, sporangia not swollen. Colonial appearance: flat, round with irregular edge, surface dull, edge becoming opaque as colony ages. Dull, wrinkled entire pellicle on surface of broth. No pigmentation on trypticase soy agar. Growth at 28° C., 37° C., no growth at 60° C. Positive reactions: Catalase, Voges-Proskauer, gelatin, nitrate reduction, utilization of citrate, acid from glucose, arabinose, mannitol, xylose, sorbitol and sucrose, hydrolysis of starch. Negative reactions: urease, indole, utilization of propionate, arginine dihydrolase, acid from rhamnose and mellibiose, no growth in anaerobic agar (stabs or plates incubated in anaerobic jars), no growth in glucose broth or nitrate broth under anaerobic conditions. Comparison with culture descriptions in Bergey's Manual of Determinative Bacteriology, Eighth Edition, Williams & Wikins, 1974, and Gordon, R. E., Haynes, W. C. and Pang, C. H. (1973), The Genus Bacillus, Agriculture Monograph No. 427, U.S. Department of Agriculture, Washington, D.C., indicate that MB 4488/ATCC 39320 is a strain of known species Bacillus subtilis. MORPHOLOGICAL AND PHYSIOLOGICAL CHARACTERISTICS OF Bacillus subtilis ATCC 39374 The morphological and physiological properties of ATCC 39374 are the same as those indicated above for ATCC 39320, except with respect to the appearance of the colonies of the microorganism, which are as follows: Colonial appearance: At 24 hours, raised, round, mucoid. As colony ages, edge becomes dry, opaque and irregular. Central mucoid area continues to dry, becoming opaque and wrinkled. Dull, wrinkled entire pellicle on surface of broth. No pigmentation on trypticase soy agar. Growth at 28° C., 37° C., no growth at 60° C. PRODUCTION OF DIFFICOL AND OXYDIFFICOL A. A process for preparing difficol and its derivatives, involves the cultivation of microorganisms which belong to the strain of Bacillus subtilis ATCC 39320 at a temperature ranging from 20° to 40° C. for from 24 to 120 hours by means of an aqueous nutrient solution which contains a source of carbon, a source of nitrogen, nutrient salts and trace elements, until the nutrient solution contains difficol and oxydifficol after which the compounds are isolated from the culture. Isolation of the compounds is accomplished by extraction of the whole broth (supernatant and cells) with a solvent such as hexane followed by chromatographic purification. In an alternative method difficol or oxydifficol is produced by treatment of difficidin or oxydifficidin using an alkaline phosphatase enzyme which is present in most living cells and for economic reasons is readily isolated from calf intestinal mucosa. In addition oxydifficol may be obtained directly from fermentation broth containing oxydifficidin using the alkaline phosphatase enzyme produced in situ by fermentation. EXAMPLE 1 Difficol and Oxydifficol from Fermentation Culture Media are Prepared as Follows: ______________________________________Seed Medium:1. HSM-1Component Amount (g/l)______________________________________Yeast Extract 1.0Malt Extract 1.0Beef Extract 1.0Trypticase Peptone 2.5Trypticase Soy 0.1Glucose 5.0Soy Bean Oil 0.1Corn Steep Liquor 0.5Calcium Carbonate 10.0Sucrose 10.0Soy Bean Flour 10.0Soluble Starch 10.0______________________________________ The medium is prepared with distilled water. No pH adjustment is required. The medium is dispensed, 54 ml/250 ml three-baffle erlenmeyer flask. The flasks are sealed with cotton plugs and sterilized at 121° C. for 20 minutes. ______________________________________Fermentation Media:1. KRCComponent Amount (g/l)______________________________________Dextrin 40.0Solulac 7.0Yeast Extract 5.0CoCl.sub.2.6H.sub.2 O 0.10______________________________________ The medium is prepared with distilled water. The pre-sterile pH is adjusted to 7.3 by the addition of NaOH. The medium is dispensed, 44 ml/250 ml plain erlenmeyer flask. The flasks are sealed with cotton plugs and sterilized at 121° C. for 20 minutes. ______________________________________2. SyntheticComponent Amount (g/l)______________________________________Dextrin 50.0Diammonium citrate 3.0MgSO.sub.4.7H.sub.2 O 1.5Potassium phosphate 0.15dibasicCoCl.sub.2.6H.sub.2 O 0.10MOPSO buffer* 11.3Trace elements 5.0 ml/lsolution______________________________________ *MOPSO is 3(N--morpholino)2-hydroxypropanesulfonic acid The medium is prepared with distilled water. To improve cell growth, yeast extract (10 g/l) may also be added. The pre-sterile pH is adjusted to 6.7 by the addition of NaOH. The medium is dispensed, 44 ml/250 ml plain erlenmeyer flask. The flasks are sealed with cotton plugs and sterilized at 121° C. for 20 minutes. ______________________________________2a. Trace Elements SolutionComponent Amount (g/l)______________________________________MgSO.sub.4.7H.sub.2 O 61.0CaCO.sub.3 2.0FeCl.sub.3.6H.sub.2 O 5.4ZnSO.sub.4.7H.sub.2 O 1.4MnSO.sub.4.H.sub.2 O 1.1CuSO.sub.4.5H.sub.2 O 0.25CoCl.sub.2.6H.sub.2 O 0.28H.sub.3 Bo.sub.3 0.062Na.sub.2 MoO.sub.4.2H.sub.2 O 0.49______________________________________ The components are dissolved in 950 ml of distilled water. Concentrated HCl (50 ml) is then added. the solution is filtered through an 0.45 μm filter after preparation. ______________________________________3. PD MediumComponent Amount (g/l)______________________________________Dextrin 80.0Proflo 20.0Potassium phosphate 0.5dibasicLactic acid (85%) 1.8Polypropyleneglycol- 1.0 ml/l2000 (Dow)______________________________________ The medium is prepared with distilled water. The pre-sterile pH is adjusted to 7.3 by the addition of NaOH. The medium is dispensed, 44 ml/250 ml plain erlenmeyer flask. The flasks are sealed with cotton plugs and sterilized at 121° C. for 20 minutes. The fermentation is carried out as described below: 1. Seed Preparation HSM-1 seed medium is inoculated with any suitable source (spores or vegetative cells) of either MB 4488 or MB 3575. The culture is grown at 27° C. and 220 rpm for 12 hours. 2. Production Phase A seed culture prepared as described above is used to inoculate fermentation media as follows: ______________________________________Medium Amount Seed/Flask (ml)______________________________________KRC 2.0Synthetic 1.0PD 2.0______________________________________ The production flasks are incubated at 27° C. and 220 rpm from 22-120 hours as desired. A 125 ml portion of fermentation broth, preferably from KRC or synthetic medium, is extracted with hexane (2×100 ml). The hexane extracts are combined, dried and concentrated. The residue is purified by reverse phase chromatography. For example, under the following conditions oxydifficol had a retention time of 5.1 minutes and difficol had a retention time of 11.4 minutes. Column: Waters μ-Bondapak®, C-18 reverse phase, 4.5×25 cm. Eluent: Methanol (84):0.01M pH 7 potassium phosphate (16). Temp.: 26° C. Flow: 1.3 ml/minute. Detection: absorbance at 275 nm. The appropriate eluate fractions are combined and concentrated. The concentrated solutions are extracted with ethyl acetate. The ethyl acetate extracts are concentrated to afford difficol and oxydifficol. Alternatively, the broth extracts may be concentrated and the residue purified over silica gel using hexane:ethyl acetate mixtures as eluent. EXAMPLE 2 Preparation of Difficidin from Difficol To a solution of 44 mg difficol in 1.5 ml methylene chloride is added 31.5 mg 1,2-dibromo-1-phenylethylphosphonic acid. The suspension is stirred at room temperature while 35 μl diisopropylethylamine is added. A clear solution results. After 16 hours at room temperature the reaction is concentrated and the residue triturated with hexane. The hexane solution is discarded and the remaining residue is dissolved in methanol. Purification of the methanol soluble portion by reverse-phase chromatography using methanol-potassium phosphate buffer (0.01M, pH 7) as eluent affords difficidin. The synthetic product is identical by chromatographic and spectral analysis with difficidin isolated from fermentation sources. EXAMPLE 3 Preparation of Oxydifficidin from Oxydifficol Oxydifficol affords oxydifficidin using the conditions described in Example 2. EXAMPLE 4 Preparation of Difficol from Difficidin A solution of 500 mg of difficidin in 14 ml methanol and 77 ml of 0.1 M sodium glycinate (pH 9.5) is treated with about 5000 units of alkaline phosphatase (from calf intestinal mucosa). The reaction is stirred under nitrogen at 25° C. for 24 hours. Sodium chloride is then added and the reaction mixture is extracted with ethyl acetate (2×50 ml). The extracts are dried (Na 2 SO 4 ) and concentrated to an oil which is chromatographed on a C-8 reverse phase column using methanol (95):0.01M potassium phosphate, pH 7 (5) as eluent. The fractions containing difficol are concentrated and the residue taken up in ethyl acetate. The resulting solution is dried and reconcentrated to an oil which is chromatographed over silica gel using hexane (4):ethyl acetate (1) as eluent. The purified difficol is obtained as a clear oil. TLC (silica gel, 7 hexane:3 ethyl acetate): Rf=0.6. Spectral data: NMR (CDCl 3 , 200 MHz): δ1.08 (d, J=6 Hz, 3H); 1.37-1.95 (m, 8H); 1.82 (s, 3H); 1.86 (s, 3H); 2.04-2.78 (m, 8H); 3.05 (d of d, J=12 Hz, 2H); 4.78 (broad d, 1H); 4.88-5.27 (m), 5.3-5.5 (d of t), 5.63-5.9 (m), 5.9-6.35 (m), 6.35-6.70 (m), 4.88-6.70 (total 16H). Mass Spectrum: M + =464. UV Spectrum (Methanol): 282 nm, 272 nm, 261 nm, 234 nm. EXAMPLE 5 Preparation of Oxydifficol from Oxydifficidin A solution of 500 mg oxydifficidin in 14 ml methanol and 77 ml 0.1 M sodium glycinate (pH 8.5) is treated with about 5000 units of alkaline phosphatase (from calf intestinal mucosa). The reaction is stirred at 25° C. and the pH is maintained between 8.5 and 8.6 by addition of 2.14 M potassium hydroxide solution. After 2.5 hours sodium chloride is added to the reaction and it is extracted with ethyl acetate (2×50 ml). Purification is as described above for difficol. Spectral data: NMR (CDCl 3 , 400 MHz): δ1.1 (d, J=8 Hz); 1.18-1.80 (m); 1.68 (s); 1.74 (s); 1.86-2.56 (m); 2.98 (d); 3.15 (d); 4.20 (broad d); 4.70 (broad d); 4.8-5.3 (m); 5.42 (m); 5.74-5.84 (m); 5.9-6.18 (m); 6.25 (t); 6.4-6.58 (m); 6.75 (t). Mass Spectrum: M + =480. UV Spectrum (Methanol): 282 nm; 273 nm; 261 nm; 234 nm.
The subject disclosure discloses a chemical intermediate in antibiotic synthesis of the structure: ##STR1## wherein R 1 is H or OH and the asterisks indicate asymmetric carbon atoms. Compounds of this type may be obtained by fermentation with a strain of B. subtilis under aerobic conditions. Compounds of the above structure are biologically inactive but are converted by phosphorylation of the hydroxyl group to produce compounds of the structure: ##STR2## wherein R 1 is H or OH, which are useful antibacterial substances having a broad spectrum of antibacterial activity.
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This is a continuation of application Ser. No. 131,607 filed Dec. 11, 1987, abandoned. BACKGROUND OF THE INVENTION Partial combustion or gasification of coal involves reaction of the coal at elevated temperatures, and possibly elevated pressures, with a limited volume of oxygen, the reaction preferably being carried out in a reactor or reaction chamber or vessel by means of "burners" in the presence of additional agents such as steam, carbon dioxide, or various other materials. Gasification of coal produces a gas, known as synthesis gas, that contains mostly carbon monoxide and hydrogen. Also produced are varying minor quantities of other gases, such as carbon dioxide and methane, and, at least with some coals, various heavier materials, such as small sticky or molten particles. In some processes, the design of the gasifier or reactor is such that the sticky or molten particles are carried downward principally by the synthesis gas through a water quench area or zone, and thence to a slag recovery area. Remaining fine particles, now solidified, pass with the synthesis gas from the bottom of the quench zone or cyclones, where the particles are separated. In at least one other coal gasification process undergoing development, the design of the gasifier is such that a rough separation of the molten particles takes place in the gasifier vessel or chamber. That is, the heavy particles drop to the bottom of the gasifier vessel to a slag recovery area or bath, and lighter and molten particles are carried by the synthesis gas upward and out of the reactor chamber into a quench zone which is mounted generally above the gasifier, and wherein a cool quench gas is employed to quench the gas and particles. The particles carried upward, in the aggregate, tend to be of somewhat different chemical composition than the "slag" which falls to the bottom of the vessel, and are designated collectively herein as "flyslag." The solidified material, because it is derived from a "reducing" atmosphere, may be different in composition and properties from flyash normally associated with combustion boilers, wherein a fully oxidizing atmosphere is utilized. For example, the flyslag from processes for partial combustion of coal may contain elemental iron and sulphides, components not normally associated with boiler flyash. A significant concern in processes where the molten or sticky particles are transported up into the quench zone is the possibility that the flyslag particles will stick to the walls of the quench zone. Unlike the down-fired processes, where water may be present or injected to quench and help wash down the particles, a quench gas, such as a cool recycle gas, may be employed, along with indirect heat exchange, for quenching and cooling the synthesis gas and the sticky or molten particles. Sticking of the flyslag particles will cause loss of heat transfer, and, of greatest concern, possibly result in plugging of the quench zone. The invention addresses this problem. SUMMARY OF THE INVENTION Accordingly, the invention relates to a process for the gasification of coal in which particulate coal is partially oxidized in a gasification zone or gasifier, producing a hot synthesis gas containing sticky or molten flyslag particles. The hot synthesis gas containing the sticky or molten flyslag particles is then passed upward from the gasification zone to a quench zone where the gas is quenched, and the particles are solidified, the quench zone comprising an indirect heat exchange zone, the heat transfer surfaces of which indirect heat exchange zone in contact with the hot synthesis gas and through which heat is extracted from the hot gas to a coolant at least partly being composed of boron nitride. As used herein, the terms "surface" or "surfaces", in referring to the material in contact with the hot synthesis gas and the sticky or molten flyslag particles, refer either to a coating of the boron nitride on the quench zone heat exchanger wall or walls, or to a liner of boron nitride positioned between the synthesis gas and the flyslag and heat exchanger wall or walls (or tubes). The coating or liner may be fabricated according to techniques known to those skilled in the art. Coatings have the advantage that they may be readily applied to the walls of the exchanger, such as by spraying, vacuum application, or brushing, e.g., in the form of a dispersion, and may be applied in layers, while a liner will generally require fabrication offsite, hanging mechanism(s), and insertion in place. On the other hand, a liner may be fabricated with grooves or channels, for heat exchange fluids, such as steam, and may tend to last longer because of its greater thickness. In general, coatings will normally be applied in a thickness of up to 30 mils or so, preferably from 10 to 12 mils, while liners may range up to 1/4 to 1/2 inch, or even more, in thickness. In both cases, consideration must be taken of differences in the coefficients of expansion of the boron nitride coating or liner and the quench zone heat exchanger wall or walls. In the case of a coating, a pre-coating of the wall or walls with another material which absorbs some of the expansion differences or which enhances bonding may be employed, or the dispersion of the boron nitride may be formulated to provide some "flex", as understood by those skilled in the art. In the case of a liner, provision may be made in the mounting of the liner, and/or a coolant may be circulated in channels of the liner to regulate expansion. It is not necessary that all of the quench zone be coated or lined with boron nitride; preferably, however, at least the lower half of the vertically disposed zone is coated or lined. Preferably, the temperature of the surface of the boron nitride in contact with the hot synthesis gas and the flyslag should be below a certain temperature or temperature range. If the surface of the boron nitride is above a certain temperature or temperature range, a tendency for some particles to stick and accumulate may arise. The invention has the advantage that even if the temperature of the liner or coating is such that there is a tendency to stick, the "non-stick" character of the boron nitride coating or liner inhibits sticking. As used herein, the term "temperature at which particles tend to stick" is a range of temperatures, and will vary from coal to coal, depending on the composition of the matter which forms the particles. Accordingly, a precise number or range cannot be given, but simple testing will determine this temperature or range. For example, a testing procedure analogous to that described in the New York State Energy Research and Development Report 82-36 (12-1982) may be employed. In the case of most coals, particles may tend to stick at a boron nitride surface temperature (in contact with the gas and particles) which is above about 500° C. After the starting materials have been converted, the reaction product, which has a temperature of between about 1050° C. and about 1800° C., and which comprises hydrogen, carbon monoxide, carbon dioxide, and water, as well as the aforementioned impurities, is passed upward from the reactor. As will be evident, passing the hot synthesis-gas containing sticky particles upward from the reactor provides a separation of the synthesis gas and the particles, so that, in some instances, this separation, along with rapid quench and/or cooling, is sufficient to prevent deposition of the particles. In other cases, however, the sticky particles represent the problem mentioned, and the particles must be taken into account. By use of a coating or liner of boron nitride, as specified, with an appropriate liner temperature, the particles will proceed upward without sticking, or will fall back into the gasifier. The upward moving particles will then be solidified by the quench gas and indirect heat exchange, and the synthesis gas stream with solidified particles then passes on for further cooling and treatment. As indicated, a variety of elaborate techniques have been developed for quenching and cooling the gaseous stream, the techniques in the quench zone and primary heat exchange zone in general being characterized by the use of a quench gas and a boiler in which steam is generated with the aid of the waste heat. The walls of the quench zone, i.e., the external or wall surfaces not in contact with the synthesis gas, and those of the primary heat exchange zone, are cooled with boiling water or steam. DETAILED DESCRIPTION OF THE INVENTION The partial combustion of coal to produce synthesis gas, which is substantially carbon monoxide and hydrogen, and particulate flyslag, is well known, and a survey of known processes is given in "Ullmanns Enzyklopadie Der Technischen Chemie", vol. 10 (1958), pp. 360-458. Several such processes for the preparation of hydrogen and carbon monoxide, flyslag gases are currently being developed. Accordingly, details of the gasification process are related only insofar as is necessary for understanding of the present invention. In general, the gasification is carried out by partially combusting the coal with a limited volume of oxygen at a temperature normally between about 1050° C. and about 2000° C. If a temperature of between 1050° C. and 2000° C. is employed, the product gas may contain very small amounts of side products such as tars, phenols and condensable hydrocarbons, as well as the molten or sticky particles mentioned. Suitable coals include lignite, bituminous coal, subbituminous coal, anthracite coal, and brown coal. In order to achieve a more rapid and complete gasification, initial pulverization of the coal is preferred. Particle size is preferably selected so that 70% of the solid coal feed can pass a 200 mesh sieve. The gasification is preferably carried out in the presence of oxygen and steam, the purity of the oxygen preferably being at least 90% by volume, nitrogen, carbon dioxide and argon being permissible as impurities. If the water content of the coal is too high, the coal should be dried before use. The atmosphere will be maintained reducing by the regulation of the weight ratio of the oxygen to moisture and ash free coal in the range of 0.6 to 1.0, preferably 0.8 to 0.9. The specific details of the equipment and procedures employed form no part of the invention, but those described in U.S. Pat. No. 4,350,103, and U.S. Pat. No. 4,458,607, both incorporated herein by reference, may be employed. Although, in general, it is preferred that the ratio between oxygen and steam be selected so that from 0.1 to 1.0 parts by volume of steam is present per part by volume of oxygen, the invention is applicable to processes having substantially different ratios of oxygen to steam. The oxygen used is preferably heated before being contacted with the coal, preferably to a temperature of from about 200° C. to 500° C. The details of the gasification reactor system form no part of the present invention, and suitable reactors are described in British Pat. No. 1501284 and U.S. Pat. No. 4,022,591. The high temperature at which the gasification is carried out is obtained by reacting the coal with oxygen and steam in a reactor at high velocity. A preferred linear velocity is from 10 to 100 meters per second, although higher or lower velocities may be employed. The pressure at which the gasification can be effected may vary between wide limits, preferably being from 1 to 200 bar. Residence times may vary widely; common residence times of from 0.2 to 20 seconds are described, with residence times of from 0.5 to 15 seconds being preferred. BRIEF DESCRIPTION OF THE DRAWING In order to illustrate the invention more fully, reference is made to the accompanying schematic drawing. The drawing is of the process flow type in which auxiliary equipment, such as valves, pumps, holding vessels, etc., have been omitted therefrom. All values are merely exemplary or calculated. Accordingly, pulverulent coal is passed via line (1) into a coal dryer (2) where the coal is dried, suitably at a temperature of about 200° C. The dry coal is subsequently discharged through a line (3) and passed into a gasification reactor (4) where it is gasified at a temperature of about 1500° C. to about 2000° C., a pressure of about 35 atmospheres absolute, with oxygen, which is supplied through a line (5). The gasification produces a product or synthesis gas containing sticky molten particles which is removed from the upper portion (6) of the reactor, and a slag which is removed from the lower portion of the reactor via line (7). The gasification product is passed upward via conduit or quench zone (8) where it is quenched by cooled synthesis gas supplied via line (9) and indirect heat exchange with steam, and is then passed via duct (8a) through a boiler or heat exchange zone (10) where it is cooled to a temperature of about 200° C. The walls and tubes of quench zone (8) in contact with the synthesis gas are coated with boron nitride. In the heat exchange zone (10), water, which is supplied through line (11), is converted by indirect heat exchange to high pressure steam, the steam being discharged through a line (12). The cooled gasification product is passed through a line (13) to a series of cyclones (14) where the bulk of the the particulates (flyslag) is removed and sent via line (15) to storage. The synthesis gas then passes via line (16) to a series of purification steps designated as (17) where a final, cooled product synthesis gas is removed via line (18). A portion of the cooled gas is recycled via line (19) to quench zone (8) for quenching the hot gas from reactor (4). A partially cooled, impure gas is removed and utilized (not shown). While the invention has been illustrated with particular apparatus, those skilled in the art will appreciate that, except where specified, other equivalent or analogous units may be employed. The term "zone", as employed in the specification and claims, includes, where suitable, the use of segmented equipment operated in series, or the division of one unit into multiple units to improve efficiency or overcome size constraints, etc. For example, a series of scrubbers might be employed, with different aqueous solutions, at least the bulk of the "loaded" solutions being sent to one or more strippers. Parallel operation of units is, of course, well within the scope of the invention.
A process for the gasification of coal to produce synthesis gas is disclosed, the process being characterized by passage of product gas stream containing sticky or molten particles upward from the gasification zone and quenching of the product gas stream and particles in a quench zone coated or lined internally with boron nitride.
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TECHNICAL FIELD [0001] The present invention relates to the technical field of petroleum engineering deepwater drilling simulation technologies, and in particular, to a deepwater drilling condition based marine riser mechanical behavior test simulation system and test method. BACKGROUND ART [0002] Marine oil and gas resources have become an important part of the global energy strategy at present, and the deepwater areas will become the main territory for oil and gas resource exploration and development in the future. However, the deepwater areas have extremely adverse environmental condition, which places higher demands on deepwater drilling equipment. In the engineering of mining the marine oil and gas resources, a marine riser is a key device that connects a floor and a subsea wellhead, which needs to bear the coupling effects of the marine environments and drilling conditions, and is prone to such accidents as wear, fatigue fracture and the like. Major economic losses and environmental security problems due to marine riser accidents have been caused for multiple times at home and abroad. The marine riser isolates an oil well from the outside seawater, supports various control pipelines, provides a channel for circulation of drilling fluids, and offers guidance for the drilling work of a drilling rod from the drill floor to the subsea wellhead. Therefore, failure of the marine riser will cause damage to drilling vessel, subsea equipment and oil well to result in great economic losses. In addition, the leakage of the drilling fluids and oil will also cause severe environment contamination. [0003] Meanwhile, with the development of marine drilling towards deepwater and ultra-deepwater and ever-increasing slenderness ratio of the marine riser, the flexible features become more apparent, and the top tensions actually applied at the two ends of the marine riser in the engineering are increased therewith. In addition, the dynamic response of the marine riser to the self vibration thereof causes periodic changes to the axial forces born by the upper and lower boundaries of the marine riser. Therefore, the axial force bearing feature of the marine riser places higher demands on the axial intensity of the marine riser. The huge span of the marine riser on a direction vertical to the sea level makes the transverse modification of the marine riser be increased greatly under the joint action of wind waves and currents. Moreover, such vortex-induced vibration of the marine riser as ocean current, wave, wind load and the like are more important reason of the fatigue failure thereof. The seawater while flowing through the marine water will form alternate shedding vortex at the two sides of the marine riser body, thus inducing the periodic vibration of the marine riser, while the vibration of the marine riser will further disturb shedding of current field vortex. When the shedding frequency of the vortex is approximate to the natural frequency of the marine riser, a locking phenomenon will occur, and the structure of the marine riser resonates largely, thus accelerating the fatigue failure of the marine riser. [0004] Presently, studies on marine riser are approximately divided into three broad categories: test method, numerical method and semi-empirical formula. For the test method, the axial force bearing changes, the lateral load and force bearing changes as well as lateral displacement and real time strain changes of the marine riser are complicated and volatile change process. Moreover, the vortex-induced vibration caused by vortex shedding is a multi-physics coupling interacted complicated process. The more prominent for the petroleum engineering deepwater drilling is that: excluding such marine working conditions as wind, wave, current and the like, those drilling conditions as circulation of the drilling fluids in the annular part of the interior of the marine riser and the collision and friction between the rotation of a drill stem and the marine riser also have a great impact on the mechanical behavior of the marine riser. Therefore, a set of complete physical test scheme and precise test instruments that can synchronously observe all related machine models is needed to truly test and study the mechanical property of the marine riser during the actual production process, so as to determine the joint effect thereof. It is usually very difficult for a physical test to provide the instantaneous change data of the fluids at the same time. Therefore, to comprehensively and truly simulate the working condition of the marine riser is the premise for the credibility of the test, and to monitor the instantaneous change of the marine riser and the surrounding current field is the key for the success of the test. [0005] Presently, most studies on the failure of the marine riser at home and abroad focus on the vortex-induced vibration of the marine riser, but neglect that the deepwater drilling process is, an engineering having a shorter period. The fatigue failure doe cause damage to the service life of the marine riser; however, compared with the failure caused by mutations of such load as wind waves and currents, the fatigue failure caused by the vortex-induced vibration of the marine riser has already played second fiddle. Even for the vortex-induced vibration, the studies on the failure of marine riser at home and abroad have carried out vortex-induced vibration tests on the marine risers having different marine working conditions, different slenderness ratios and different materials. The tests on the vortex-induced vibration of the marine riser or riser conducted by most scholars at home and abroad focus the test emphasis on the changes of incoming current types and slenderness ratios as well as span of Reynolds number. For example: Chaplin developed a test on the vortex-induced vibration of a flexible riser under a step current in 2005. Trim et al conducted a test in a Marintek marine towing basin in 2006, obtaining high-quality data under different water current conditions and high mobility response conditions. Zhang Jianqiao from Dalian University of Technology conducted a test on the vortex-induced vibration of a flexible riser at the nonlinear wave tank of the State Key Laboratory of Coastal and Offshore Engineering of Dalian University of Technology in 2009, and the like. However, studies related to the complicated working conditions for the vortex-induced vibration of the marine riser having a big slenderness ratio during the marine drilling process are still insufficient. In 2008, Guo Haiyan on the basis of the original test, optimized the test design, taking the influences of such factors as different tension forces, internal current rates, mass ratios and the like, on the vortex-induced vibration response of the riser into consideration. In 2011, Guo Haiyan further conducted a vortex-induced vibration response test on the riser under the effects of different internal currents, external currents and top tensions in the “Wind-Wave-Flow” Joint Tank of Ocean University of China. The several tests taking the internal current of the riser into consideration cannot simulate the actual working condition of the marine riser in true marine drilling process more comprehensively yet although the simulation about the drilling condition of the marine riser is further improved. Therefore, the studies on the mechanical behavior of the marine riser marine riser are not comprehensive yet. SUMMARY OF THE INVENTION [0006] The object of the present invention lies in overcoming the defects of the prior art and providing a deepwater drilling condition based marine riser mechanical behavior test simulation system capable of comprehensively and accurately simulating the mechanical behavior of the marine riser under a deepwater drilling condition. [0007] The present invention is emboded by the follow technical solution: A deepwater drilling condition based marine riser mechanical behavior test simulation system, comprising: an upper sliding guide, a lower sliding guide, an upper trailer connecting plate, a lower trailer connecting plate, a top tension applying mechanism, a drill pressure regulating mechanism, a submersible pump, an air compressor, a frequency converter, a servo motor encoder, an internal current flowmeter and a control cabinet, wherein the frequency converter and the servo motor encoder are arranged in a watertight caisson, the upper trailer connecting plate is connected onto the upper sliding guide, the lower trailer connecting plate is connected onto the lower sliding guide, and an upper three-component dynamometer, an upper connecting structure, a marine riser, a lower connecting structure and a lower three-component dynamometer connected in sequence are arranged between the upper trailer connecting plate and the lower trailer connecting plate along a direction from top to bottom; [0008] the upper connecting structure comprises a motor support, a corrugated pipe, an upper tee fitting, an upper bearing cap, a plate A and an upper barb fitting, the lower end of the three-component dynamometer fixedly connected onto the upper trailer connecting plate is connected to the motor support through a connecting piece, a driving device is fixedly mounted on the motor support, an output shaft of the driving device is connected to an upper chucking cutter bar through a coupler, an upper fixed supporting seat is also arranged on the motor support, the upper chucking cutter bar is rotatably mounted in the shaft hole of the upper fixed supporting seat and positioning of the upper chucking cutter bar along the axis direction of the upper fixed supporting seat is realized through a locking screw, the lower end of the upper fixed supporting seat is sequentially connected to the corrugated pipe and the upper tee fitting, the lower end of the upper chucking cutter bar stretches into the corrugated pipe, a dynamic seal structure is arranged between the upper fixed supporting seat and the corrugated pipe, the lower end opening of the upper tee fitting is fixedly connected to the upper bearing cap, the interior of the upper bearing cap is provided with a recess A for containing an upper knuckle bearing, an upper pipe adapter communicated with the recess A is arranged on the upper bearing cap, the upper pipe adapter is connected to the upper tee fitting, the upper knuckle bearing is mounted in the recess A of the upper bearing cap, and is clamped and fixed by the plate A fixedly connected to the upper bearing cap, and the lower end of the upper barb fitting penetrates through the upper knuckle bearing and is fixed through an upper end flange structure; [0009] the top tension applying mechanism comprises a guide block A fixedly connected to the upper trailer connecting plate and a sliding block A driven by a cylinder mechanism A, a vertical sliding rail is arranged on the guide block A, the sliding block A is arranged on the vertical sliding rail in a sliding way and is driven to slide by the cylinder mechanism A, a plate C is fixedly connected onto the sliding block A, two sensors for measuring top tension are fixedly arranged on the plate C, one end of the sensor is fixedly mounted onto the plate C, the other end of the sensor is fixedly mounted onto the upper bearing cap, and the two sensors are symmetric around the axis of the upper barb fitting; [0010] the lower connecting structure comprises a lower fixed supporting seat, a lower tee fitting, a lower bearing cap, a plate B and a lower barb fitting, a lower chucking cutter bar is rotatably mounted in the shaft hole of the lower fixed supporting seat and positioning of the lower chucking cutter bar along the axis direction of the lower fixed supporting seat is realized through a locking screw, the upper end of the lower chucking cutter bar stretches into the lower tee fitting, the lower end opening of the lower tee fitting is provided with a dynamic seal structure, the upper end opening of the lower tee fitting is connected to the lower bearing cap, the interior of the lower bearing cap is provided with a recess B for containing a lower knuckle bearing, a lower pipe adapter communicated with the recess A is arranged on the lower portion of the lower bearing cap, the lower pipe adapter is connected to the lower tee fitting, the lower knuckle bearing is mounted is mounted in the recess B of the lower bearing cap, and is clamped and fixed by the plate B fixedly connected to the lower bearing cap, the upper end of the lower barb fitting penetrates through the lower knuckle bearing and is fixedly connected to the upper end of the lower three-component dynamometer through a connecting piece, and the lower end of the lower three-component dynamometer is fixedly connected to the lower trailer connecting plate; [0011] the drill pressure regulating mechanism comprises a guide block B fixedly connected to the lower trailer connecting plate and a gliding block B driven by a cylinder mechanism B, a vertical sliding rail is arranged below the guide block B, the gliding block B is arranged on the vertical sliding rail in a sliding way and is driven to slide by the cylinder mechanism B, and the gliding block B is fixedly connected to the lower fixed supporting seat; [0012] the upper end of the marine riser is connected to the upper barb fitting, the lower end of the marine riser is connected to the lower barb fitting, the drill stem is arranged in the marine riser, the upper end of the drill stem is mounted onto the upper chucking cutter bar, and the lower end of the drill stem is mounted onto the lower chucking cutter bar; [0013] a shunt valve is mounted at the air outlet of the air compressor, the shunt valve is connected to the cylinder mechanism A through a pipeline A, a five-position three-way valve A is mounted on the pipeline A, the shunt valve is connected to the cylinder mechanism B through a pipeline B, and a five-position three-way valve B is mounted on the pipeline B; [0014] the submersible pump is communicated to the third end opening of the lower tee fitting through a water duct, and the third end opening of the upper tee fitting is connected to a turbine flowmeter; and [0015] the frequency converter is connected with the submersible pump through a cable, and the servo motor encoder is connected with the driving device through a cable; the frequency converter, the servo motor encoder, the turbine flowmeter, the sensors, the five-position three-way valve A and the five-position three-way valve B are all connected with the control cabinet through cables. [0016] The driving device comprises a servo motor and a reducer connected to the servo motor, and the servo motor encoder is connected with the servo motor through a cable. [0017] A test method employing the deepwater drilling condition based marine riser mechanical behavior test simulation system, it comprises the following steps of: [0018] S 1 , regulating a top tension: a controller regulates an atmospheric pressure conveyed to a cylinder mechanism A of an air compressor through a five-position three-way valve A to drive a sliding block A to move along a vertical sliding rail on a guide block A, and the sliding block A drives an upper bearing cap to move upwards or downwards, the upper end of a marine riser is fixedly connected to the upper bearing cap, the lower end of the marine riser is fixedly connected to a plate B; since the plate B is fixedly connected to a lower trailer connecting plate through a lower three-component dynamometer, the top tension of the marine riser can be regulated through the upward or downward, movement of the bearing cap, the top tension is measured through a sensor and is fed back to a control cabinet in real time, thus implementing pressure regulating on a five-position three-way valve A through the controller so as to apply a top tension needed by the test; [0019] S 2 , regulating a drill pressure: the controller regulates an atmospheric pressure conveyed to a cylinder mechanism B of the air compressor through a five-position three-way valve B to drive a gliding block B to move along a vertical sliding rail on a guide block B, and the sliding block A drives a lower fixed supporting seat to move upwards or downwards, since the upper end of a drill stem is connected to an upper chucking cutter bar, the upper chucking cutter bar is axially positioned by an upper fixed supporting seat, the axial position of the upper fixed supporting seat is fixed, the lower end of the drill stem is connected to a lower chucking cutter bar, and the lower chucking cutter bar is axially positioned by the lower fixed supporting seat, the upper end of the drill stem is fixed, the lower end of the drill stem is supported by the lower fixed supporting seat, and the drill pressure of the drill stem can be regulated through the upward or downward movement of the lower fixed supporting seat; [0020] S 3 , regulating the rotational speed of the drill stem: the rotational speed of a servo motor is directly inputted through the control cabinet, and the control cabinet transmits a control signal to a servo motor encoder, so as to control a drive motor of a driving device to work at a set rotational speed, thus regulating the rotational speed of the drill stem; and [0021] S 4 , regulating circulation of drilling fluids: the drilling fluids outputted by a submersible pump enter the interior of the marine riser through a lower tee fitting, flow upwards, and finally flow out from the water outlet of an upper tee fitting, a turbine flowmeter connected to the water outlet of the upper tee fitting measures and feeds back a flow to the control cabinet, and the voltage output frequency of a frequency converter is changed through the control cabinet to control the output flow of the submersible pump in real time, thus implementing the function of controlling the flow of the drilling fluids in real time. [0022] The present invention has the following advantages that: the present invention provides a testing apparatus which can simulate the mechanical behavior of a marine riser under deepwater drilling condition and marine environment coupling effect comprehensively and accurately, and the apparatus can simulate ocean current environment, apply top tension to the marine riser, simulate circulation of internal drilling fluids at different flow rates, simulate rotation of the drill stem at different rotational speeds and apply different drill pressures. [0023] In the steric configuration of the entire testing apparatus, a marine riser model is vertically placed, and an upper mechanism actually represents the boundary conditions of the marine riser in an actual production process, a top tension applied is adjustable, and a lower end is connected to a submersible pump to simulate the circulation of drilling fluids inside the marine riser; moreover, the delivery capacity of the drilling fluids is monitored through the cooperative use of the submersible pump and a frequency converter; a lower mechanism applies an adjustable drill pressure, and the rotational speed of a drill stem can be conveniently regulated through a controller; visual control of the rotational speed of the motor and the delivery capacity of the drilling fluids are implemented; a three-component dynamometer monitors the forces of the marine riser on three directions in real time, and truly represents the connection situations of the marine riser. Winds, waves and currents simulated through a test tank are acted on the testing apparatus, or the overwater and underwater portions of the testing apparatus move synchronously on trailers at the upper end and the lower end of the tank, thus being capable of conducting a test on the mechanical behavior of the marine riser under drilling condition and marine environment coupling effect. The apparatus is stable and reliable, can simulate various drilling parameters in the test tank comprising the density of the drilling fluids, the delivery capacity of the drilling fluids, the rotational speed of the drill stem, the tension, the pull of the drill stem and the mechanical behavior of the marine riser under the effects of the winds, waves and currents as well as combinations thereof. BRIEF DESCRIPTION OF THE DRAWINGS [0024] FIG. 1 is a structure schematic view of the present invention. [0025] FIG. 2 is a structure schematic view of connection of a marine riser of the present invention. [0026] FIG. 3 is a structure schematic view of a lower fixed supporting seat of the present invention. [0027] FIG. 4 is a structure schematic view of connection of the lower fixed supporting seat and a lower chucking cutter bar of the present invention. [0028] FIG. 5 is a structure schematic view of cooperation of a gliding block B and a guide block B of the present invention. [0029] In the figures, 1 -upper slide guide, 2 -lower slide guide, 3 -upper trailer connecting plate, 4 -lower trailer connecting plate, 5 -submersible pump, 6 -air compressor, 7 -frequency converter, 8 -servo motor encoder, 9 -internal current flowmeter, 10 -control cabinet, 11 -watertight caisson, 12 -upper three-component dynamometer, 13 -marine riser, 14 -lower three-component dynamometer, 15 -motor support, 16 -corrugated pipe, 17 -upper tee fitting, 18 -upper bearing cap, 19 -plate A, 20 -upper barb fitting, 21 -driving device, 22 -upper fixed supporting seat, 23 -upper chucking cutter bar, 24 -dynamic seal structure, 25 -recess A, 26 -upper pipe adapter, 27 -upper knuckle bearing, 28 -sliding block A, 29 -guide block A, 30 -plate C, 31 -lower fixed supporting seat, 32 -lower tee fitting, 33 -lower bearing cap, 34 -plate B, 35 -lower barb fitting, 36 -lower chucking cutter bar, 37 -recess B, 38 -lower pipe adapter, 39 -lower knuckle bearing, 40 -gliding block B, 41 -guide block B, 42 -drill stem, 43 -shunt valve, 44 -pipeline A, 45 -five-position three-way valve A, 46 -pipeline B, and 47 -five-position three-way valve B. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0030] The present invention will be further described hereinafter by reference to the accompanying drawings; however, the protection scope of the present invention is not limited to the following descriptions. As shown in FIG. 1 and FIG. 2 , a deepwater drilling condition based marine riser mechanical behavior test simulation system comprises an upper slide guide 1 , a lower sliding guide 2 , an upper trailer connecting plate 3 , a lower trailer connecting plate 4 , a top tension applying mechanism, a drill pressure regulating mechanism, a submersible pump 5 , an air compressor 6 , a frequency converter 7 , a servo motor encoder 8 , an internal current flowmeter 9 and a control cabinet 10 . The frequency converter 7 and the servo motor encoder 8 are arranged in a watertight caisson 11 , the upper trailer connecting plate 3 is fastened and connected onto the upper sliding guide 1 through a bolt, the lower trailer connecting plate 4 is fastened and connected onto the upper slide guide 1 through a bolt; in this way, the upper and lower supports of an entire test bed are formed by the trailer connecting plates and the sliding guides. An upper three-component dynamometer 12 , an upper connecting structure, a marine riser 13 , a lower connecting structure and a lower three-component dynamometer 14 connected in sequence are arranged between the upper trailer connecting plate 3 and the lower trailer connecting plate 4 along a direction from top to bottom for conveniently measuring the forces born by the marine riser 13 and a drill stem 42 on three directions in space. Both the upper trailer connecting plate 3 and the lower trailer connecting plate 4 are rectangular stainless steel plates. Four through holes are evenly distributed on a circle having a diameter of 36 mm. Through the holes, the upper and lower three-component dynamometers are positioned in a manner of set screw, and are locked on the corresponding trailer connecting plates. [0031] The upper connecting structure comprises a motor support 15 , a corrugated pipe 16 , an upper tee fitting 17 , an upper bearing cap 18 , a plate A 19 and an upper barb fitting 20 . The upper end of the upper three-component dynamometer 12 is fixedly connected to the upper trailer connecting plate 3 , and the lower end of the upper three-component dynamometer 12 is connected to the motor support 15 through a connecting piece. A driving device 21 is fixedly mounted on the motor support 15 , and an output shaft of the driving device 21 is connected to an upper chucking cutter 23 through a coupler. An upper fixed supporting seat 22 is also arranged on the motor support 15 . A shaft hole matched with the upper chucking cutter bar 23 is arranged in the upper fixed supporting seat 22 . The upper chucking cutter bar 23 penetrates through the shaft hole of the upper fixed supporting seat 22 and positioning of the upper chucking cutter bar 23 along the axis direction of the upper fixed supporting seat is realized through a locking screw and screw threads processed by the cutter bar. The upper chucking cutter bar 23 is rotatably matched with the shaft hole of the upper fixed supporting seat 22 ; that is, the outside diameter of the upper chucking cutter bar 23 is equal to the inside diameter of the upper fixed supporting seat 22 , and the upper chucking cutter bar can rotate freely in the upper fixed supporting seat 22 along the circumferential direction. The lower end of the upper fixed supporting seat 22 is sequentially connected to the corrugated pipe 16 and the upper tee fitting 17 , and the lower end of the upper chucking cutter bar 23 stretches into the corrugated pipe 16 . A dynamic seal structure 24 which seals the upper end opening of the corrugated pipe 16 and allows the rotation of the upper chucking cutter bar 23 is arranged between the upper fixed supporting seat 22 and the corrugated pipe 16 . The lower end opening of the upper tee fitting 17 is fixedly connected to the upper bearing cap 18 , the interior of the upper bearing cap 18 is provided with a recess A 25 for containing an upper knuckle bearing 27 , an upper pipe adapter 26 communicated with the recess A 25 is arranged on the upper bearing cap 18 , and the upper pipe adapter 26 is connected to the upper tee fitting 17 . The upper knuckle bearing 27 is mounted in the recess A 25 of the upper bearing cap 18 , and the plate A 19 arranged at the lower portion of the bearing is fixedly connected to the upper bearing cap 18 . The upper knuckle bearing 27 is clamped and fixed by the upper bearing cap 18 and the plate A 19 , the lower end of the upper barb fitting 20 penetrates through the upper knuckle bearing 27 and is fixed through an upper end flange structure, and a given-way hole for the upper barb fitting 20 to penetrate out is arranged on the plate A 19 . [0032] The top tension applying mechanism comprises a guide block A 29 fixedly connected to the upper trailer connecting plate 3 and a sliding block A 28 driven by a cylinder mechanism A. A vertical sliding rail is arranged on the guide block A 29 , the sliding block A 28 is arranged on the vertical sliding rail in a sliding way and is driven to slide by the cylinder mechanism A. a plate C 30 is fixedly connected onto the sliding block A 28 , two sensors for measuring top tension are fixedly arranged on the plate C 30 , one end of the sensor is fixedly mounted onto the plate C 30 , the other end of the sensor is fixedly mounted onto the upper bearing cap 18 , and the two sensors are symmetric around the axis of the upper barb fitting 20 . [0033] The lower connecting structure comprises a lower fixed supporting seat 31 , a lower tee fitting 32 , a lower bearing cap 33 , a plate B 34 and a lower barb fitting 35 . A shaft hole matched with a lower chucking cutter bar 36 is arranged in the lower fixed supporting seat 31 . As shown in FIG. 3 and FIG. 4 , the lower chucking cutter bar 36 penetrates through the shaft hole of the lower fixed supporting seat 31 and positioning of the lower chucking cutter bar 36 along the axis direction of the lower fixed supporting seat is realized through a locking screw and screw threads processed by the cutter bar. The lower chucking cutter bar 36 is rotatably matched with the shaft hole of the lower fixed supporting seat 31 ; that is, the outside diameter of the lower chucking cutter bar 36 is equal to the inside diameter of the lower fixed supporting seat 31 , and the lower chucking cutter bar can rotate freely in the lower fixed supporting seat 31 along the circumferential direction. The upper end of the lower chucking cutter bar 36 stretches into the lower tee fitting 32 , the lower end opening of the lower tee fitting 32 is provided with a dynamic seal structure 24 which seals the lower end opening of the lower tee fitting 32 and allows the rotation of the lower chucking cutter bar 36 . The upper end opening of the lower tee fitting 32 is connected to the lower bearing cap 33 , the interior of the lower bearing cap 33 is provided with a recess B 37 for containing a lower knuckle bearing 39 , a lower pipe adapter 38 is arranged on the lower portion of the lower bearing cap 33 , and the lower pipe adapter 38 is connected to the lower tee fitting 32 . The lower knuckle bearing 39 is mounted in the recess B 37 of the lower bearing cap 33 , and the plate B 34 arranged on the upper portion of the bearing is fixedly connected to the lower bearing cap 33 . The lower knuckle bearing 39 is clamped and fixed by the lower bearing cap 33 and the plate B 34 , the upper end of the lower barb fitting 35 penetrates through the lower knuckle bearing 39 and is fixed through an upper end flange structure, and a given-way hole for the lower barb fitting 35 to penetrate out is arranged on the plate B 34 . The plate B 34 is fixedly connected to the upper end of the lower three-component dynamometer 14 through a connecting piece, and the lower end of the lower three-component dynamometer 14 is fixedly connected to the lower trailer connecting plate 4 . [0034] The drill pressure regulating mechanism comprises a guide block B 41 fixedly connected to the lower trailer connecting plate 4 and a gliding block B 40 driven by a cylinder mechanism B. A vertical sliding rail is arranged below the guide block B 41 , the gliding block B 40 is arranged on the vertical sliding rail in a sliding way and is driven to slide by the cylinder mechanism B. As shown in FIG. 5 , the gliding block B 40 is fixedly connected to the lower fixed supporting seat 31 . [0035] The upper end of the marine riser 13 is connected to the upper barb fitting 20 , the lower end of the marine riser 13 is connected to the lower barb 35 and fixed by a hoop, the drill stem 42 is arranged in the marine riser 13 , the upper end of the drill stem 42 is mounted onto the upper chucking cutter bar 23 , and the lower end of the drill stem 42 is mounted onto the lower chucking cutter bar 36 . When mounting the drill stem 42 , after the drill stem 42 is inserted into a cutter bar core at the end portion of the chucking cutter bar, a cutter bar cap is locked tightly through a knob. [0036] A shunt valve 43 is mounted at the air outlet of the air compressor 6 , the shunt valve 43 is connected to the cylinder mechanism A through a pipeline A 44 , a five-position three-way valve A 45 is mounted on the pipeline A 44 , the shunt valve 43 is connected to the cylinder mechanism B through a pipeline B 46 , and a five-position three-way valve B 47 is mounted on the pipeline B 46 . After being pressed one portion of pressed gas is connected to the cylinder mechanism A through the five-position three-way valve A 45 for applying a top tension, and another portion of the pressed gas is connected to the cylinder mechanism B through the five-position three-way valve B 47 for applying a drill pressure. [0037] In order to comprehensively simulate the demands of the drilling condition of the marine riser 13 on the flow rates of the interior fluids, the third end opening of the lower tee fitting 32 is communicated through a water duct, and the connecting part infixed through a hoop. The marine riser 13 itself is taken as an interior flow path for the drilling fluids, waterflow is sucked in from the lower tee fitting 32 , passes through the upper barb fitting 20 and discharged through the upper tee fitting 17 , and the third end opening of the upper tee fitting 17 is connected to the turbine flowmeter. [0038] The frequency converter 7 is connected to the submersible pump 5 through a cable. In order to comprehensively simulate the demands of the drilling condition of the marine riser 13 on the rotational speeds of the interior fluids, the servo motor encoder 8 is connected to the servo motor of the driving device 21 through a cable. [0039] The frequency converter 7 , the servo motor encoder 8 , the turbine flowmeter, the sensors, the five-position three-way valve A 45 and the five-position three-way valve B 47 are all connected with the control cabinet 10 through cables. The frequency converter 7 and the servo motor encoder 8 are arranged in the watertight caisson 11 , and the watertight caisson 11 is connected to the control cabinet 10 through a communication line so as to implement real time visual control of the flow rates of the drilling fluids and the rotational speeds of the drill stem 42 . [0040] The upper three-component dynamometer 12 and the lower three-component dynamometer 14 are respectively used for measuring the forces born by the drill stem 42 and the marine riser 13 on three directions in space. [0041] The trailer connecting plates are connected onto the sliding guides. The upper trailer connecting plate 3 and the lower trailer connecting plate 4 are synchronously driven by the servo motor to slide along the sliding guides, which can accurately simulate the flow rate of an ocean current. [0042] The driving device 21 comprises the servo motor and a reducer connected to the servo motor. [0043] The motor support 15 comprises an upper contact plate, a lower contact plate and a connecting part connecting the upper contact plate and the lower contact plate, approximating to a “ ” shape. The upper contact plate is fixedly connected to the connecting plate fixedly arranged on the lower end face of the upper three-component dynamometer 12 . The upper contact plate is provided with a through hole and the aperture of the hole is the spigot diameter of the reducer. The servo motor after being connected to the reducer is connected onto the upper contact plate through a bolt. The contact surface of the upper contact plate and the reducer is provided with a hole. The output shaft of the reducer is connected to the coupler through the hole. The other end of the coupler is connected to the upper chucking cutter bar 23 . The face of the lower contact plate parallel to the vertical face is connected to the fixed supporting seat to ensure excellent verticality and centration of the drill stem 42 . [0044] Both the interior of the upper bearing cap 18 and the interior of the lower bearing cap 33 are designed with two-stage steps. The recess formed by the first-stage step is used for the plate to conduct axial positioning on a centripetal knuckle bearing. The inside diameter of the bearing cap is in interference fit with the centripetal knuckle bearing to conduct circumferential positioning on the bearing and ensures the leak tightness at the same time. The recess formed by the second-stage step is used for providing a space condition for the barb fitting penetrating the bearing to rotate around the bearing during the test. The barb fitting penetrates through the inside diameter of the knuckle bearing and is positioned through a self flange structure. The bearing cap and the plate are connected through a bolt and are preferably sealed through an O ring in the bearing cap. The plate A 19 and the plate B 34 are rectangle aluminum plates having a thick of 5 mm, provided with a bolt hole, and also provided with a through hole for the barb fitting to pass through. The flange structure at the top end of the bearing cap is connected to the tee fitting at the corresponding side in a manner of hoop. The upper tee fitting 17 is connected to the corrugated pipe 16 and the dynamic seal structure 24 similarly in a manner of hoop for ensuring the tightness of the entire drilling fluids circulation path. [0045] The submersible pump 5 is a 220V single-phase submersible pump 5 . When in use, the starting capacitance of the pump is removed, and the output terminals w, u and v of the frequency converter 7 are directly connected to the three wires of a wire connecting box of the pump. The object of changing the delivery capacity of the drilling fluids can be achieved by changing the frequency of the frequency converter 7 for outputting three-phase 220V currents. [0046] A test method employing a deepwater drilling condition based marine riser mechanical behavior test simulation system comprises the following steps of [0047] S 1 , regulating a top tension: a controller regulates an atmospheric pressure conveyed to a cylinder mechanism A of an air compressor 6 through a five-position three-way valve A 45 to drive a sliding block A 28 to move along a vertical sliding rail on a guide block A 29 , and the sliding block A 28 drives an upper bearing cap 18 to move upwards or downwards, the upper end of a marine riser 13 is fixedly connected to the upper bearing cap 18 , the lower end of the marine riser 13 is fixedly connected to a plate B 34 ; since the plate B 34 is fixedly connected to a lower trailer connecting plate 4 through a lower three-component dynamometer 14 , so that the lower portion of the marine riser 13 is fastened and chucked, and the upper portion of the marine riser bears a pulling force to realize application of the top tension of the marine riser 13 , and the top tension of the marine riser 13 can be regulated through the upward or downward movement of the bearing cap, the top tension is measured through a sensor and is fed back to a control cabinet 10 in real time, thus implementing pressure regulating on a five-position three-way valve A 45 through the controller so as to apply a top tension needed by the test; the top tension is increased when the sliding block A 28 vertically moves upwards and decreased when the gliding block B 40 vertically moves downwards; [0048] S 2 , regulating a drill pressure: a controller regulates an atmospheric pressure conveyed to a cylinder mechanism B of the air compressor 6 through a five-position three-way valve B 47 to drive the gliding block B 40 to move along a vertical sliding rail on a guide block B 41 , and the sliding block A 28 drives a lower fixed supporting seat 31 to move upwards or downwards, since the upper end of a drill stem 42 is connected to an upper chucking cutter bar 23 , the upper chucking cutter bar 23 is axially positioned by an upper fixed supporting seat 22 , the axial position of the upper fixed supporting seat 22 is fixed, the lower end of the drill stem 42 is connected to a lower chucking cutter bar 36 , and the lower chucking cutter bar 36 is axially positioned by the lower fixed supporting seat 31 , the upper end of the drill stem 42 is fixed, the lower end of the drill stem is supported by the lower fixed supporting seat 31 , and the drill pressure of the drill stem 42 can be regulated through the upward or downward movement of the lower fixed supporting seat 31 ; [0049] S 3 , regulating the rotational speed of the drill stem 42 : the rotational speed of a servo motor is directly inputted through the control cabinet 10 , and the control cabinet 10 transmits a control signal to a servo motor encoder 8 , so as to control a drive motor of a driving device 21 to work at a set rotational speed, thus regulating the rotational speed of the drill stem 42 ; [0050] S 4 , regulating circulation of drilling fluids: the drilling fluids outputted by a submersible pump 5 enter the interior of the marine riser 13 through a lower tee fitting, flow upwards, and finally flow out from the water outlet of an upper tee fitting, a turbine flowmeter connected to the water outlet of the upper tee fitting 17 measures and feeds back a flow to the control cabinet 10 , and the voltage output frequency of a frequency converter 7 is changed through the control cabinet 10 to control the output flow of the submersible pump 5 in real time, thus implementing the function of controlling the flow of the drilling fluids in real time; the drilling fluids pass through the submersible pump 5 , a lower tee fitting 32 , a lower bearing cap 33 , a lower barb fitting 35 , the marine riser 13 , an upper barb fitting 20 , the upper bearing cap 18 , and the upper tee fitting 17 in sequence from bottom to top, thus forming a drilling fluids circulation path; and the sealing of a drilling fluids loop is implemented through an upper dynamic seal structure 24 and a lower dynamic seal structure 24 .
The present invention discloses a deepwater drilling condition based marine riser mechanical behavior test simulation system. An upper three-component dynamometer, an tipper connecting structure, a marine riser, a lower connecting structure and a lower three-component dynamometer are connected between an upper trailer connecting plate and a lower trailer connecting plate in sequence. The invention further discloses a test method. The present invention has the advantages that the mechanical behavior of the marine riser under deepwater drilling condition and marine environment coupling effect can be simulated comprehensively and accurately, and the apparatus can simulate ocean current environment, apply top tension to the marine riser, simulate circulation of internal drilling fluids at different current rates, simulate rotation of the drill stem at different rotational speeds and apply different drill pressures.
4
TECHNICAL FIELD This disclosure relates generally to water heaters and more particularly to water heaters that are configured to provide a temporary capacity increase. BACKGROUND Water heaters are commonly used in homes, businesses and just about any establishment having the need for heated water. In many cases, a water heater is configured to heat water in a water heater tank using a gas-fired burner, an electric heater or some other heater element. When demand for hot water arises (e.g., someone turns on a faucet to run a shower), fresh, cold or ambient temperature water typically enters the water heater tank and “pushes out” or supplies the hotter water. When the temperature of the water in the water heater falls below a temperature set point, either though the mere passage of time or as a result of a hot water draw, the water heater typically activates a heater element to restore the temperature of the water in the tank back to the temperature set point. To help reduce cycling of the water heater, a temperature differential is often employed, where the water heater does not activate the heater element until the temperature of the water in the water heater falls below the temperature set point by at least a temperature differential amount. The desired temperature set point can be referred to as the first temperature set point and the temperature at which the heater element is actually activated can be referred to as the second temperature set point, where the difference between the first temperature set point and the second temperature set point corresponds to the temperature differential. A conventional water heater typically has at least one heating element or “heater,” such as a gas-fired and/or electric burner. To take advantage of the “heat-rises” principle, the heater is often located at or near the bottom of the water heater tank. Each water heater typically also has at least one thermostat or controller for controlling the heater. To facilitate the heating of water, the controller often receives signals related to the temperature of the water, oftentimes from a temperature sensor that is thermally engaged with the water within the water heater. When temperature signals from the temperature sensor indicate that the water temperature is below the second temperature set point, for example when the water temperature is below about 120° F., the controller may turn on the heater element and the water within the water heater begins to heat. After some time, the water temperature within the water heater tank may increase back to the first temperature set point, which, for example, may be about 140° F. At this point, the controller may cause the heater element to reduce its heat output or, alternatively, causes the heater element to turn off. This heating cycle may begin again when the water temperature within the water heater tank drops below the second temperature set point. Water heaters are typically available in a variety of different sizes so that a particular home or building may be equipped with a water heater having a thermal capacity, or quantity of sufficiently heated water, that is sufficient for normal conditions expected for the particular home or building. However, special circumstances, such as having overnight visitors, may mean that there may be a temporary, larger than normal demand for hot water. Typically, the increased demand is accompanied by a need to have increased hot water available within a relatively short time frame. For example, several extra house guests may wish to shower in the morning, causing a temporary increased demand for hot water in a relatively short time period. One way to accommodate this situation is to initially install an oversized water heater. However, it may not be very efficient to run an oversized water heater all the time to accommodate occasional and short-term demands for increased hot water. SUMMARY The present disclosure relates generally to water heaters and more particularly to water heaters that are configured to provide a temporary hot water capacity increase. In one illustrative embodiment, this may be accomplished by temporarily increasing the temperature of the water in the water heater tank. In some instances, the water heater may include a main controller that can accept a boost request from a remote controller or the like, and in response, may temporarily increase the temperature of the water in the water heater tank to provide additional hot water without requiring a user to, for example, go down to the basement, out to the garage, or wherever the water heater happens to be to manually and temporarily change the set point of the water heater. In an illustrative but non-limiting example, a water heater is provided that includes a water tank and a heat source that is disposed proximate the water tank. A main controller may be provided that is configured to control the heat source. The main controller may include a maximum temperature set point and an operating temperature set point, and may operate in accordance with a particular temperature differential as described above. In some cases, a remote controller may be configured to accept a request, such as from a homeowner or other user, for additional hot water capacity and may communicate a resultant boost request to the main controller. In some instances, the boost request may include instructions to increase to a boost temperature set point that is higher than the normal operating temperature set point. In some cases, the temperature differential temperature may be reduced while in the boost mode. Another illustrative but non-limiting example of the disclosure may be found in a water heater that includes a water tank and a gas burner that is disposed proximate the water tank. A communicating gas valve may be configured to control gas flow to the gas burner. The communicating gas valve may include a maximum temperature set point and an operating temperature set point and may operate in accordance with a particular temperature differential as described above. In some cases, a remote controller may be configured to accept a request for additional hot water capacity from a user, and to communicate a resultant boost request to the communicating gas valve. In some instances, the boost request may include instructions to increase to a boost temperature set point that is higher than the normal operating temperature set point. In some cases, the temperature differential temperature may be reduced while in the boost mode. Another illustrative but non-limiting example of the disclosure may be found in a method of operating a water heater that has a communicating gas valve having a main controller and a remote controller. A maximum temperature set point may be provided, as well as operating temperature set point. The main controller may operate the water heater in accordance with the operating temperature set point. If a boost request is accepted from the remote controller, the main controller may temporarily operate the water heater in accordance with a boost temperature set point. In some cases, the temperature differential temperature may be reduced while in the boost mode. The above summary is not intended to describe each and every disclosed embodiment or every implementation of the disclosure. The Description that follows more particularly exemplifies various illustrative embodiments. BRIEF DESCRIPTION OF THE FIGURES The following description should be read with reference to the drawings. The drawings, which are not necessarily to scale, depict selected embodiments and are not intended to limit the scope of the disclosure. The disclosure may be more completely understood in consideration of the following detailed description of various embodiments in connection with the accompanying drawings, in which: FIG. 1 is a schematic view of an illustrative but non-limiting water heater in accordance with the present disclosure; FIG. 2 is a schematic block view of an illustrative control system that may be used with the water heater of FIG. 1 ; FIG. 3 is a schematic view of an illustrative main controller that may be used in the control system of FIG. 2 ; FIG. 4 is a schematic view of an illustrative remote controller that may be used in the control system of FIG. 2 ; FIG. 5 is a flow diagram showing an illustrative but non-limiting example of a method that may be carried out via the control system of FIG. 2 ; and FIG. 6 is a flow diagram showing an illustrative but non-limiting example of a method that may be carried out via the control system of FIG. 2 . 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 to limit the invention to the particular illustrative embodiments described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DESCRIPTION The following description should be read with reference to the drawings, in which like elements in different drawings are numbered in like fashion. The drawings, which are not necessarily to scale, depict selected embodiments and are not intended to limit the scope of the invention. Although examples of construction, dimensions, and materials are illustrated for the various elements, those skilled in the art will recognize that many of the examples provided have suitable alternatives that may be utilized. The disclosure relates to heating water, and as such may include fossil fuel-fired water heaters, electrically heated water heaters, boilers and the like. Merely for illustrative purposes, the drawings show a fossil fuel-fired water heater. However, it is contemplated that the any type of water heater may be used. FIG. 1 shows a schematic view of an illustrative but non-limiting water heater 10 . Water heater 10 includes a water tank 12 . Cold water enters water tank 12 through a cold water line 14 and is heated by a gas burner 24 . The resulting heated water exits through a hot water line 16 . A gas control unit 18 regulates gas flow from a gas source 20 through a combustion gas line 22 and into gas burner 24 . A flue 26 permits combustion byproducts to safely exit. Water heater 10 may include a temperature sensor 28 . In some cases, temperature sensor 28 may enter water tank 12 at a location exterior to gas control unit 18 . In some instances, however, temperature sensor 28 may instead be located behind gas control unit 18 . To accommodate this, water tank 12 may include an aperture or recess (not illustrated) that is sized and configured to accept temperature sensor 28 . In some cases, gas control unit 18 may be in communication with a main controller (not seen in FIG. 1 ) that provides gas control unit 18 with appropriate command instructions. In some cases, gas control unit 18 may itself incorporate the main controller. FIG. 2 is a schematic diagram showing how a remote controller may provide instructions to gas control unit 18 . FIG. 2 shows a main controller 30 and a remote controller 32 that is in communication with main controller 30 . In some cases, remote controller 32 may communicate wirelessly with main controller 30 . In some instances, remote controller 32 may be electrically connected to main controller 30 via wires such as low voltage wiring, similar to the 24 volt wiring used to connect HVAC thermostats to furnaces and other HVAC equipment. These are only example connections that may facilitate communication between the main controller 30 and the remote controller 32 . As noted above, and in some instances, main controller 30 may be integrated into gas control unit 18 , while in other cases main controller 30 may be external to gas control unit 18 but in communication with gas control unit 18 . It is contemplated that main controller 30 may have several components. In some cases, main controller 30 may have an I/O block 34 that accepts signals from a temperature sensor 28 ( FIG. 1 ), remote controller 32 and/or any other suitable device or component. I/O block 34 may accommodate control signals from remote controller 32 . Main controller 30 may include a microprocessor 36 that may be configured to accept appropriate signals from I/O block 34 and determine appropriate output signals that can be outputted via I/O block 34 to other components within gas control unit 18 ( FIG. 1 ), remote controller 32 and/or any other suitable device or component. While not illustrated, microprocessor 36 may also include memory. In some cases, main controller 30 may also include a Gas Control block 38 . Gas Control block 38 may receive command instructions from microprocessor 36 and may in turn provide appropriate instructions to an electrically controlled gas valve disposed within or controlled by the gas control unit 18 . The illustrative remote controller 32 may also have several components. In some instances, remote controller 32 may include an I/O block 40 and a user interface 42 . I/O block 40 may, for example, receive information from the user interface 42 and provide corresponding information to main controller 30 . When provided, user interface 42 may take any desired form, and may include a display and/or one or more buttons that a user may use to enter information. In some instances, user interface 42 may be configured to permit a user to request additional hot water. For example, a homeowner may anticipate that due to a larger number of occupants, hot water may run low at a particular time of day. In some cases, the homeowner may preemptively instruct water heater 10 ( FIG. 1 ) to provide additional hot water capacity to remedy the expected shortcoming via user interface 42 . It is contemplated that remote controller 32 may be configured to permit a homeowner or other user to make a request for additional hot water capacity for a particular period of time. In other cases, it is contemplated that remote controller 32 may be programmed to provide additional hot water capacity on a regular or programmed basis, perhaps at a particular time of day and/or only on certain day(s). Turning now to FIG. 3 , an illustrative but non-limiting example of gas control unit 18 is shown. Gas control unit 18 may include a temperature set point setting device 44 . In some instances, temperature set point setting device 44 may include a rotatable knob 46 having an indicator line or arrow 48 . The rotatable knob 46 may rotate relative to a temperature scale 50 that is printed or otherwise disposed on an outer surface of gas control unit 18 . In some cases, temperature set point setting device 44 may provide gas control unit 18 with an operating temperature set point. In some instances, particularly if gas control unit 18 is in communication with a remote controller such as remote controller 32 ( FIG. 2 ), temperature set point setting device 44 may provide gas control unit 18 with a maximum temperature set point, while the remote controller may provide the operating temperature set point. In some instances, both an operating temperature set point and a maximum temperature set point may be set using one or more dials or the like at the gas control unit 18 . While a rotating knob 46 is shown, it is contemplated that any suitable user interface may be provided for setting an operating temperature set point and/or a maximum temperature set point, as desired. FIG. 4 shows an illustrative but non-limiting example of a remote controller 52 that may be considered as being an illustrative embodiment of remote controller 32 ( FIG. 2 ). Remote controller 52 may be mounted or otherwise disposed within a home or building, at a location that is remote from water heater 10 ( FIG. 1 ). In some cases, for example, remote controller 52 may be wall-mounted within a living space, proximate or incorporated into a HVAC controller such as a thermostat. In some instances, it is contemplated that remote controller 52 may be disposed in or near a bathroom, as a bath or shower is often a large consumer of hot water. Regardless of where remote controller 52 is disposed, illustrative remote controller 52 may include one or more of a display 54 , an UP arrow 56 , a DOWN arrow 58 , and/or selection buttons 60 and 62 . In some cases, it is contemplated that display 54 may be a touch screen display such as a touch screen LCD display, and as such, remote controller 52 may not include any physical buttons. In some instances, for example, display 54 may provide a graphical representation of an operating temperature set point, the current status of water heater 10 ( FIG. 1 ), i.e., whether water heater 10 is in a draw period, recovery period or standby, or any other desired information. In some cases, display 54 may provide an indication of whether or not water heater 10 is in a boost mode period. A boost mode period is a time period during which a user has requested, sometimes via remote controller 52 , an elevated water temperature within water heater 10 in order to obtain more thermal energy from water heater 10 than may otherwise be available when operating at the operating temperature set point. In some cases, UP arrow 56 and/or DOWN arrow 58 may be used by the user to raise or lower an operating temperature set point. In some instances, remote controller 52 may accept an operating temperature set point from a user and may communicate the operating temperature set point to main controller 30 ( FIG. 2 ). Main controller 30 may then operate water heater 10 in accordance with the operating temperature set point provided by the remote controller 52 , provided that certain safety parameters are met. For example, main controller 30 ( FIG. 2 ) may operate in accordance with the operating temperature set point as long as the operating temperature set point does not exceed a predetermined temperature safety limit such as 160° F., or perhaps 154° F. In some cases, main controller 30 may operate in accordance with the operating temperature set point as long as the operating temperature set point provided by remote controller 52 does not exceed the maximum temperature set point set by temperature set point setting device 44 ( FIG. 3 ). In some cases, the operating temperature set point is set at the main controller 30 , and not via the remote controller 32 . Under normal operating conditions, main controller 30 may operate water heater 10 ( FIG. 1 ) in accordance with a particular temperature differential value. The temperature differential may be a numerical difference between a temperature at which gas burner 24 is activated and a temperature at which gas burner 24 is terminated or stopped. For example, if main controller 30 is programmed with a temperature differential value of say 10° F. and a temperature set point of 120° F., gas burner 24 may be activated when a water temperature indicated by temperature sensor 28 ( FIG. 1 ) falls to 110° F., and may run until the water temperature rises to 120° F. However, in some illustrative embodiments, if a homeowner or other user requests additional hot water via remote controller 32 ( FIG. 2 ) or otherwise, main controller 30 may operate using a lower temperature differential or even a zero differential, if desired. In an illustrative embodiment, when remote controller 32 ( FIG. 2 ) instructs main controller 30 ( FIG. 2 ) that additional hot water capacity has been requested, main controller 30 may determine a boost temperature set point that may represent an increase to the operating temperature set point. For example, the boost temperature set point may be 10° F. higher than the operating temperature set point, but it will be appreciated that other temperature increases may also be employed. In some instances, the boost temperature set point may be limited by safety limits and/or by the maximum temperature set point set by, for example, the temperature set point setting device 44 ( FIG. 3 ). In some embodiments, main controller 30 ( FIG. 2 ), upon receiving a boost request from remote controller 32 ( FIG. 2 ), may operate gas burner 24 ( FIG. 1 ) until the boost temperature set point has been reached. Once the boost temperature set point has been reached, the boost period may be ended and main controller 30 may in some cases revert back to the normal operating temperature set point. In some cases, main controller 30 may operate in accordance with the boost temperature set point, turning gas burner 24 on and off as appropriate to maintain the water at the boost temperature set point for a predetermined length of time. For example, main controller 30 may maintain the boost temperature set point for a period of time up to about 2 hours, although other time periods are contemplated and permissible. In some cases, main controller 30 may maintain the boost temperature set point indefinitely, until receiving a subsequent signal from remote controller 32 ( FIG. 2 ) to return to the operating temperature set point. When operating in accordance with the boost temperature set point, the water heater 10 may operate normally but with a higher temperature set point and thus attempts to heat all of the water in the water tank, and not just water around a top portion of the tank. This can significantly increase the hot water capacity of the water heater 10 during a boost period. FIG. 5 is a flow diagram showing an illustrative but non-limiting example of a method that may be carried out in the operation of water heater 10 ( FIG. 1 ). Control begins at block 64 , where a maximum temperature set point is provided. In some cases, this may be done using temperature set point setting device 44 ( FIG. 3 ) or though some other user interface. Alternatively, or in addition, a maximum temperature set point may be hard coded. At block 66 , an operating temperature set point may be accepted, such as from the remote controller 32 ( FIG. 2 ) or through a dial or the like on the main controller 30 . Main controller 30 ( FIG. 2 ) may operate water heater 10 in accordance with the operating temperature set point, as shown at block 68 . Control passes to block 70 , where a boost request is accepted from, for example, the remote controller 32 ( FIG. 2 ). In some cases, main controller 30 ( FIG. 2 ) may calculate or otherwise determine a boost temperature set point, and may operate water heater 10 ( FIG. 1 ) in accordance with the boost temperature set point as shown at block 72 . In some instances, water heater 10 ( FIG. 1 ) may be operated in accordance with the boost temperature set point for a predetermined length of time, and sometimes set the temperature differential to zero or any other desired temperature differential. Reducing the temperature differential to zero may cause the main controller 30 to immediately activate the heater element of the water heater. In some cases, water heater 10 may be operated in accordance with a boost temperature set point only if the boost temperature set point falls below particular safety limits and/or below the maximum temperature set at block 64 . In some cases, the main controller 30 may adjust the boost temperature set point to be within particular safety limits and/or within the maximum temperature set at block 64 . FIG. 6 is a flow diagram showing another illustrative but non-limiting example of a method that may be carried out in the operation of water heater 10 ( FIG. 1 ). In FIG. 6 , it can be seen that certain steps or operations, indicated by solid lines, may be manifested within main controller 30 ( FIG. 2 ), while other steps or operations, indicated by dashed lines, may be manifested within remote controller 32 , but this is not required. At block 74 , it can be seen that a homeowner or other user has pressed a Boost button or otherwise activated a boost mode via remote controller 32 ( FIG. 2 ). A boost button may, for example, correspond to one of the selection buttons 60 or 62 shown on remote controller 52 ( FIG. 4 ), or may be a touch button on a touch screen display. At block 76 , main controller 30 receives the boost request. Control passes to block 78 , where if main controller 30 ( FIG. 2 ) is operating in accordance with an operating temperature set point, main controller 30 enters a boost mode. If main controller 30 is already in boost mode when the Boost button is pushed, the main controller may cancel the boost mode, return to operating in accordance with an operating temperature set point, and return to block 74 . At block 80 , main controller 30 enables the boost mode. In some cases, main controller 30 may also start a counter or timer that can be used to set a maximum time period for the boost mode. Control is then passed to decision block 82 . At decision block 82 , a determination is made whether the normal operating temperature set point is at or below 140° F. (where 140° F. is selected for illustrative purposes only). If the operating temperature set point is less than or equal to 140° F. at decision block 82 , control passes to block 86 where a boost temperature set point is set equal to the normal operating temperature set point plus 10° F. (where 10° F. is selected for illustrative purposes only) or the maximum temperature set point, whichever is less. Control then passes to block 88 , where the operating temperature set point is compared to the maximum temperature set point. If the operating temperature set point is already equal to the maximum temperature set point when the boost button is pressed, remote controller 32 ( FIG. 2 ) may provide a graphical or other indication of this condition (such as flash “MAX”), telling the user that no boost is available because the water heater 10 ( FIG. 1 ) is already operating at the maximum temperature set point. In some cases, this may cause the user to adjust the maximum temperature set point using, for example, temperature set point setting device 44 ( FIG. 3 ). It is contemplated that this determination, and a corresponding display such as that shown at block 88 , may also take place even if, at decision block 82 , the normal operating temperature set point was greater than 140°. Returning back to decision block 82 , if the normal operating temperature set point is greater than 140° F., control passes to block 84 where the boost temperature set point is set equal to 150° F. That is, if the normal operating temperature set point is greater than 140° F., the boost temperature set point is not increased by 10° F., but rather is only raised to 150° F. From blocks 84 and 88 , control is passed to block 90 . In block 90 , main controller 30 ( FIG. 2 ) may temporarily set the temperature differential equal to zero or some other reduced value as desired. This may trigger operation of gas burner 24 ( FIG. 1 ) sooner than it would otherwise be started, thereby initiating the heating cycle sooner. At block 92 , remote controller 32 ( FIG. 2 ) may provide a graphical or other indication that water heater 10 ( FIG. 1 ) is in a boost mode. Control is then passed to block 94 , where main controller 30 determines if the boost temperature set point has been reached, or if the timer started in block 80 has expired. In the illustrative embodiment, if either event has occurred, control passes to block 96 where the main controller 30 exits the boost mode and returns to operating at the operating temperature set point. If the boost temperature set point has not been reached and if the timer started in block 80 has not expired, control reverts to block 80 , where the timer is continued. In some cases, the main controller 30 may include an anti-stacking control algorithm to help prevent stacking in the water tank, such as described in U.S. Pat. No. 6,560,409 and 6,955,301, which are incorporated herein by reference. The disclosure should not be considered limited to the particular examples described above, but rather should be understood to cover all aspects of the invention as set out in the attached claims. Various modifications, equivalent processes, as well as numerous structures to which the invention can be applicable will be readily apparent to those of skill in the art upon review of the instant specification.
A water heater may be configured to temporarily increase its hot water capacity by heating water to a higher boost temperature. In some instances, the water heater may include a main controller that can accept a boost request from a remote controller, and thus may temporarily provide additional hot water capacity without, for example, requiring a homeowner to go down to the basement, out to the garage, or wherever the water heater happens to be to make manual adjustments to the water heater settings.
5
CROSS REFERENCE TO RELATED APPLICATION This application claims the benefit of U.S. provisional application Serial No. 60/292,214 filed May 18, 2001, the entire contents of which are incorporated herein by reference. FIELD OF THE INVENTION This invention relates generally to steering columns and more particularly to a steering column having improved locking, release and energy absorption mechanisms. BACKGROUND OF THE INVENTION Various locking mechanisms are known for use with steering columns capable of rake adjustment, such as that disclosed in co-pending U.S. patent application Ser. No. 09/664,032 dated Sep. 18, 2000, which is incorporated herein by reference. The locking mechanism in that co-pending application includes a rake bolt and associated tooth locks on both sides of the steering column. It would be desirable from the standpoint of both simplicity and cost, for the locking mechanism to have a single tooth lock on only one side of the steering column. It is also known to provide a release mechanism to allow the steering column to collapse following a frontal impact event of great magnitude, such as a head-on collision. However, such release mechanisms typically are not aligned with the rake bolt and thus lead to undesirable moments being applied to the release mechanism upon impact. Energy absorption mechanisms that allow the steering column to collapse at a controlled rate for the protection of the driver are also known. Such mechanisms, however, typically are not well integrated with the rake adjustment and release mechanisms. SUMMARY OF THE INVENTION The locking system of the present invention includes a tooth lock movable selectively into engagement with a toothed slot of a fixed bracket. The tooth lock is normally supported in meshing engagement with the toothed slot to lock the steering column in adjusted position, but is movable out of engagement with the toothed slot to enable the steering column to be adjusted. A rake bolt moves into positive engagement with the tooth lock to hold the tooth lock in meshing engagement with the toothed slot in response to an applied impact force on the steering column to prevent the steering column from accidentally moving away from adjusted position during controlled collapse of the steering column. Further in accordance with the invention, the steering column has telescoping upper and lower jackets. The rake bolt extends through a tubular capsule. The capsule is connected to a compression bracket secured to the upper jacket by one or more shear pins. The shear pin or pins are adapted to shear to enable the steering column to collapse when the driver's chest hits the steering wheel in response to a frontal vehicle impact of great magnitude. A deformable energy absorbing strap extends over the capsule which serves as an anvil to bend and then restraighten the strap to absorb energy as the steering column collapses. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing as well as other features, objects and advantages of this invention will become more apparent as the following description proceeds, especially when considered with the accompanying drawings, wherein: FIG. 1 is perspective view of a steering column and associated structure constructed in accordance with the invention; FIG. 2 is an exploded perspective view of the structure shown in FIG. 1; FIG. 3 is a side elevational view of the steering column and attached compression bracket, showing an operating handle in broken lines; FIG. 4 is an exploded view in perspective showing certain parts associated with the rake adjustment mechanism; FIG. 5 is a sectional view taken on the line 5 — 5 in FIG. 3; FIG. 5A is an exploded perspective view of a tubular capsule, a portion of the compression bracket and bushings also shown in FIG. 5; FIG. 6 is an enlargement of a portion of FIG. 5 shown within the circle 6 in FIG. 5; FIGS. 7A, 7 B and 7 C show the pre-crash adjustment position of the rake adjustment mechanism shown in FIGS. 2 and 4; FIGS. 8A, 8 B and 8 C show the same mechanism in a pre-crash locked position; FIGS. 9A, 9 B and 9 C show the same mechanism in a post-crash condition; FIG. 10 is a side elevational view of the jacket of the steering column with attached compression bracket; FIG. 11 is a view similar to FIG. 10 but is in section to better illustrate are energy absorption mechanism; FIG. 12 is a view similar to FIG. 11 but shows the parts in a different position; FIG. 13 is a side elevational view of a steering column and associated mechanism of a modified construction, also in accordance with the invention; FIG. 14 is an exploded view in perspective of the structure shown in FIG. 13; FIG. 15 is an enlarged view with parts in section of portions of FIG. 13; and FIG. 16 is essentially the same as FIG. 15, but with different directional arrows. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now more particularly to the drawings, and especially FIGS. 1-3, a steering column 20 for an automotive vehicle has a jacket assembly 22 including a lower tubular jacket 24 telescoped in an upper tubular jacket 26 . A steering shaft 28 is journaled for rotation in the jacket assembly 22 . A steering wheel (not shown) has splines which engage splines 30 on the rear end of the steering shaft 28 . The forward end of the lower jacket 24 receives a horizontal pivot pin 32 which attaches the steering column 20 to a vehicle frame for pivotal movement about a horizontal transverse rake axis of the pivot pin. The upper jacket 26 extends lengthwise within an elongated, channel-shaped compression bracket 34 and is welded or otherwise rigidly secured parallel to opposite side walls 36 and 38 of the compression bracket. Straddling the steering column 20 and the compression bracket 34 are a left side rake bracket 40 and a right side rake bracket 42 . The rake brackets 40 and 42 are parts of a rake adjustment mechanism 43 for adjusting the vertical tilt, or rake, of the steering column 20 and are rigidly secured to a vehicle frame. The left side rake bracket 40 has a vertical wall 44 formed with a generally vertically extending opening 46 . An elongated rake plate 48 is secured to the outer side of the vertical wall 44 over the opening 46 , and has a vertically elongated rake slot 50 generally in register with the opening 46 . The rake slot 50 has a series of rake teeth 52 on its front edge. A pilot projection 54 on the inner side of the plate 48 is closely received and fits snugly in the opening 46 in the wall 44 of the left side rake bracket 40 to locate the plate 48 . The right side rake bracket 42 has a vertical wall 54 formed with a generally vertically elongated rake slot 56 in a portion 57 of the wall 54 . The rake slot 56 in the wall 54 of the right side rake bracket 42 is in substantial transverse alignment with the rake slot 50 in the plate 48 on the wall 44 of the left side rake bracket 40 . An elongated, generally vertical, narrow slit 58 in the wall 54 of the right side rake bracket 42 is generally parallel to, and closely spaced forwardly from the rake slot 56 , providing a narrow, flexible, deformable strip 60 of the material of the wall 54 between the front wall 61 of the slot 56 and the slit 58 . A transverse, horizontal rake bolt 62 has ends 63 and 65 disposed in the respective rake slots 50 and 56 of the left and right side rake brackets 40 and 42 . See FIGS. 2, 4 and 5 . The rake bolt 62 also passes through the elongated, transversely aligned slots 64 and 66 which are formed in and extend lengthwise of the side walls 36 and 38 of the compression bracket 34 parallel to the steering column. A nut 68 is threaded on the threaded right end portion 70 of the bolt 62 , clamping a thrust bearing 72 between the nut 68 and the wall 54 of the right side rake bracket 42 . The rake bolt 62 is D-shaped in cross-section from a cylindrical portion 74 adjacent the polygonal head 76 of the bolt to the threaded end portion 70 . The D-shaped cross section of the rake bolt 62 includes a flat surface 75 . The rake bolt 62 extends lengthwise within a transverse tubular capsule 80 . See FIGS. 5 and 5A. The ends 81 and 83 of the capsule 80 extend through the slots 64 and 66 in the side walls 36 and 38 of the compression bracket 34 . Bushings 82 and 84 in the ends of the capsule have heads 86 and 88 which extend across the ends 81 and 83 of the capsule in confronting relation to the vertical walls 44 and 54 of the side rake brackets 40 and 42 . An annular cam 90 rotatable on the cylindrical portion 74 of the rake bolt 62 has a flange 92 engaged over an edge of the rake plate 48 to keep the cam from rotating. A cam follower 94 secured on the end of a tilt adjustment control handle 96 has a polygonal socket 98 fitted over the polygonal head 76 of the bolt 62 so that the bolt 62 is rotated when the handle 96 is turned. The cam 90 has a cam track 99 bearing against the cam follower 94 . A left annular tooth lock 100 on the rake bolt 62 has a D-shaped hole 101 with a flat surface 103 and is generally similar to but slightly larger than the D-shaped rake bolt so that the rake bolt 62 may rotate relative to the tooth lock 100 . The tooth lock 100 cannot rotate because it is generally rectangular and is confined between the walls of the rake slot 50 . The tooth lock 100 is disposed in the rake slot 50 between the bushing head 86 and the cam 90 and has teeth 102 facing the rake teeth 52 in the rake slot. The D-shaped rake bolt 62 extends through and is rotatable in the rake slot 56 in the vertical wall 44 of the right side rake bracket 40 , but there is no associated tooth lock for the right side of the rake adjustment mechanism 43 . The left and right rake brackets 40 and 42 have transversely aligned, vertically elongated slots 104 and 106 in the vertical walls 44 and 54 thereof. The slots 104 and 106 are spaced forwardly from the rake slots 50 and 56 . A bolt 108 extends through the slots 104 and 106 and also through the elongated, transversely aligned slots 110 and 112 which are formed in and extend lengthwise of the side walls 36 and 38 of the compression bracket 34 parallel to the steering column. A nut 114 is threaded on an end of the bolt 108 , with a washer 116 between the nut and the side wall 38 of the compression bracket. The bolt 108 assists in stabilizing the steering column 20 but does not interfere with the vertical adjustment or collapse of the steering column. To adjust the vertical tilt of the steering column 20 , the adjustment control handle 96 is raised from the position shown in FIGS. 1 and 3 so that the rake bolt 62 is rotated to the position shown in FIGS. 7A-7C. In this position of the rake bolt, the tooth lock 100 is withdrawn to the position of FIG. 7B to disengage its rake teeth 102 from the rake teeth 52 in the rake slot 50 , freeing the steering column 20 for vertical adjustment. After the tilt of the steering column 20 is adjusted as desired, the rake bolt 62 is reverse rotated to the position of FIGS. 8A-8C, such that the flat surface 75 of the rake bolt is opposed to the flat surface 103 of the hole 101 in the tooth lock 100 , enabling the tooth lock to be pressed forwardly by an actuator comprising a spring 118 , causing the teeth 102 of the tooth lock to engage the teeth 52 in the rake slot 50 . This engagement of the teeth 52 and 102 locks the steering column 20 in vertically adjusted position. The spring 118 is secured in the rake slot 50 opposite to rake teeth 52 . With the rake bolt 62 reverse rotated to the position of FIGS. 8A-8C, the cam track 99 on the cam 90 , in cooperation with the cam follower 94 , causes the bushing heads 86 and 88 to be compressed against the walls 44 and 54 of the rake brackets 40 and 42 to frictionally resist movement of the steering column 20 away from the adjusted position. An energy absorption mechanism 120 is best shown in FIGS. 10-12. The capsule 80 is part of this mechanism. One end 81 of the capsule 80 has dual spaced apart flanges 122 and 124 and the opposite end 83 has dual spaced apart flanges 126 and 128 (FIGS. 5, 5 A and 6 ). The flanges 122 and 124 embrace the side wall 36 of the compression bracket 34 at one end 130 of the slot 64 therein. The flange 122 has a hole 132 registering with a hole 134 in the wall 36 . The flanges 126 and 128 embrace the side wall 38 of the compression bracket 34 at one end 136 of the slot 66 therein. The flange 126 has a hole 138 registering with a hole 140 in the wall 38 . The registering holes 132 and 134 are injected with a flowable material such as a suitable plastic, for example Acetel, to produce a shear pin 142 . The registering holes 138 and 140 are also injected with the same or similar material to produce a shear pin 144 . The shear pins 142 and 144 retain the capsule 80 at the ends 130 and 136 of the slots 64 and 66 where such slots preferably have bottom wall portions 146 tapered about 15° to their lengthwise dimension. The ends 81 and 83 of the capsule 80 run on the bottoms of slots 64 and 66 and have similarly tapered bottoms 148 . A generally U-shaped energy absorption strap 150 of metal, for example, has a curved mid portion 152 extending around the capsule 80 and has one end 151 secured to a bottom wall 154 of the compression bracket 34 by a fastener 155 . There is a space or gap 156 of about 5 millimeters, more or less, between the curved mid portion 152 of the strip 150 and the capsule 80 . In the event of a high impact load, such as a head-on collision, of sufficient magnitude to shear the pins 142 and 144 and to overcome the friction hold of the capsule heads 86 and 88 on the compression bracket 34 , the steering column 20 will collapse causing the upper jacket 26 to telescope relative to the lower jacket 24 . The energy absorption strap 150 will travel a few millimeters to take up the gap 156 before contacting the capsule 80 . The gap 156 serves to eliminate the inertial effects associated with high initiation loads. It essentially separates the release loads so that they are not superimposed on one another. It also reduces the tendency of the capsule 80 to bind during the initial portion of the impact. This also prevents high initiation spike loads on impact. During continuing collapse of the steering column 20 the strap 150 will be bent in an arc around the capsule 80 and then restraightened to absorb energy. The 15° taper of the bottom wall portions 146 at the forward ends of the slots 64 and 66 together with the similar taper of the bottoms 148 of the ends of the capsule 80 eliminate any lash between the slots and the capsule and also eliminate sticking of the capsule upon initial engagement of the curved portion 152 of the strap 150 with the capsule. Also during collapse of the steering column 20 in response to a high impact load, the rake bolt 62 moves forwardly relative to the rake slot 50 (see FIGS. 9A-9C) so that that left end 63 of the rake bolt 62 positively engages and holds the tooth lock 100 in the position in which its teeth 102 engage the rake teeth 52 in the rake slot 50 , thus preventing the steering column 20 from accidentally tilting upwardly. The bolt 62 moves forward during collapse of the steering column because the bolt is inside the capsule 80 which is being pushed forward by the strap 150 . The right end 65 of the rake bolt 62 is normally prevented from moving forwardly by the front wall 61 of the rake slot 56 but on collapse of the steering column is permitted to move forwardly with the left end portion due to the deformation of the flexible strip 60 of the wall 54 between the slot 56 and the slit 58 (see FIG. 9 C), thus preventing binding of the rake bolt. Referring now to FIGS. 13-16, there is shown a modification of the invention which includes a steering column 180 having a jacket assembly 182 including a lower tubular jacket 184 telescoped within an upper tubular jacket 186 . A steering shaft 188 extends lengthwise within the jacket 182 and has a splined rear end 190 to receive the splined opening in a steering wheel (not shown). A housing 192 supports the rear end of the upper jacket 186 . A horizontal transverse pivot pin 194 pivots the front end of the steering shaft to enable up and down rake adjustment. Normally the steering column is supported at an angle A to the horizontal. A mounting bracket 198 is provided for the steering column 180 . The mounting bracket 198 is rigidly secured to the upper jacket 186 . The mounting bracket is generally channel-shaped having a bottom wall 200 beneath the upper jacket 186 of the steering column and laterally spaced upwardly extending vertical side walls or plates 202 and 204 on opposite sides of the upper jacket. The side walls each having a notch 206 in the rear edge. The notches of the two plates are transversely aligned. Each notch has a straight top edge 208 and a straight bottom edge 210 which diverge away from one another in a rearward direction at a predetermined angle and open through the rear edge of the notch. The top edge 208 is parallel to the longitudinal axis or center line 212 of the steering column and the bottom edge 210 diverges in a rearward direction away from the top edge at an arcuate angle B to the longitudinal center line. Shear capsules 214 and 216 are provided. The shear capsules 214 and 216 are identical and are rigidly supported and anchored in fixed positions on opposite sides of the steering column by a transverse bolt or bar 218 which extends horizontally across the top of the upper jacket 186 and is secured in holes 220 in the capsules. The bar 218 is secured to rigid frame structure of the vehicle. Each shear capsule has a configuration similar to the configuration of the notches 206 . Each shear capsule is in the form of a flat plate which is wider or thicker than the side walls 202 and 204 of the mounting bracket 198 . The top and bottom edges 224 and 226 of each capsule diverge at the same angle as the top and bottom edges 208 and 210 of the notches 206 . Each capsule is provided with straight open-ended grooves 228 and 230 along the top and bottom edges 224 and 226 thereof which also diverge at the same angle as the top and bottom edges 208 and 210 of the notches. The grooves 228 and 230 slideably receive the top and bottom edges 208 and 210 of the notches. Shear pins 232 and 234 are provided to hold the capsules 214 and 216 in the notches 206 of the respective side walls 202 and 204 . The shear pins 232 and 234 are preferably made of the same material as the shear pins 142 and 144 described in connection with the first embodiment. The shear pin 232 has its ends received in holes 236 and 238 in the capsule 214 and the side wall 202 of the mounting bracket, and the shear pin 234 has its ends received in holes 240 and 242 in the capsule 216 and the side wall 204 . In the normal operation of the vehicle, the capsules 214 and 216 are held in the notches 206 of the side walls 202 and 204 by the shear pins 232 and 234 , preventing collapse of the steering column 180 . However, in a frontal vehicle impact of great magnitude, when the driver is thrown forward and his chest strikes the steering wheel, the pins 232 and 234 shear and the upper jacket 186 collapses and telescopes relative to the lower jacket 184 . When entering or leaving a vehicle, the driver will often grasp the steering wheel and apply a downward force. This force is represented by the vector F 1 in FIG. 15 and is perpendicular to the central axis of the steering column. It is resisted by the capsules 214 and 216 . The force is applied by contact of the top edges 208 of the notches 206 of the side walls 202 and 204 of the mounting bracket 198 against the bottoms of the grooves 228 along the top edges 224 of the capsules. This force is perpendicular to such contact surfaces and hence does not place any stress on the shear pins 232 and 234 and thus will not accidentally shear the pins and allow the steering column to collapse. However in a sudden and violent frontal impact event, when the driver is thrown forward against the steering wheel, the force against the steering column may be great enough to shear the pins 232 and 234 and allow the steering column to collapse. During such an event, the force of the driver against the steering wheel typically applies an upward force on the steering column represented by the vector F 2 in FIG. 16 and is applied by contact of the bottom edges 210 of the notches against the bottoms of the grooves 230 along the bottom edges 226 of the capsules. This force is perpendicular to the central axis of the steering column but is not perpendicular to such contact surfaces and in fact has a component F 3 in a direction which increases the stress on the shear pins and thus assists in causing the shear pins to shear, promoting collapse of the steering column. The disclosed embodiments are representative of presently preferred forms of the invention, but are intended to be illustrative rather than definitive thereof. The invention is defined in the claims.
A vehicle steering column has a rake adjustment mechanism which includes a rake bracket having a rake slot provided with rake slot teeth. A tooth lock is supported in the rake slot with teeth opposing the rake slot teeth. A rake bolt is rotatable to a first rotative position to move the tooth lock to a retracted position with the teeth of the tooth lock out of engagement with the rake slot teeth. The bolt is axially rotatable to a second rotative position permitting the tooth lock to be moved to a locking position by a spring in which the teeth of the tooth lock engage the rake slot teeth. The bolt, when in the second rotative position, is movable, in response to an application of an impact force on the steering column to collapse the steering column, into bearing engagement with the tooth lock to positively retain the tooth lock in the locking position. The steering column is also provided with a release mechanism having shear pins and an energy absorption mechanism.
1
This application is a division of application Ser. No. 08/763,449, filed Dec. 2, 1996, now U.S. Pat. No. 5,714,603, granted Feb. 3, 1998, which is a division of Ser. No. 08/426,208, filed Apr. 21, 1995, now U.S. Pat. No. 5,621,153, granted Apr. 15, 1997. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a catalyzed process for the para-directed ring chlorination of alkylbenzenes and to novel compounds useful as catalysts. The para-alkylbenzenes, such as para-chlorotoluene, are useful as chemical intermediates for the synthesis of various chemical products, especially agricultural chemical and pharmaceutical products. 2. Prior Art The production of nuclear chlorinated alkylbenzenes, such as mono-chlorotoluene, is well-known and of considerable commercial importance. Typical commercial processes involve the chlorination of an alkylbenzene, such as toluene, in the presence of a chlorination catalyst, such as ferric chloride, antimony chloride, aluminum chloride, and the like. The usual product of such reactions is a mixture of various monochlorinated and/or polychlorinated compounds. For example, in the liquid phase substitution-chlorination chlorination of toluene by reaction of chlorine and toluene, to form monochlorotoluene, the usual product is a mixture of orthochlorotoluene and para-chlorotoluene, which may, in addition, contain varying amounts of other chlorinated products such as meta-chlorotoluene, dichlorotoluenes, various polychlorotoluenes and benzylic chlorides. In the ring chlorination of toluene, since there are two ortho sites and only one para site where substitution may occur, the production of orthochlorotoluene is favored. Because of the greater commercial value of parachlorotoluene, considerable effort has been expended in attempts to direct the chlorination reaction in such a manner as to lower the ratio of orthochlorotoluene to parachlorotoluene, that is, to discover reaction conditions under which the formation of parachlorotoluene is favored. U.S. Pat. No. 1,946,040 discloses that when alkylbenzenes are reacted with chlorine, the yield of parachlorinated product is improved with the aid of a mixed catalyst comprising sulfur and antimony trichloride and, optionally, iron or lead. In British Patent No. 1,153,746 (1969) it is disclosed that in the chlorination of toluene in the presence of a ring chlorination catalyst, such as ferric chloride, antimony chloride, and the like, the ratio of orthochloro to parachloro isomers produced may be lowered by the presence of an organic sulfur compound such as thiophene, hexadecylmercaptan, dibenzothiophene or the like. British Patent No. 1,163,927 (1969) discloses that the formation of parachlorotoluene is enhanced when toluene is reacted with chlorine in the presence of elemental sulfur, or an inorganic sulfur compound, and a ring chlorination catalyst, such as ferric chloride, aluminum chloride, antimony chloride, zinc chloride, iodine, molybdenum chloride, stannous chloride, zirconium chloride, or boron trifluoride. U.S. Pat. No. 3,226,447 (1965) teaches that in the substitution-chlorination of benzene and toluene, the ratio of ortho isomer to paraisomer in the mono-chlorinated product may be lowered when the reaction is carried out in the presence of an iron, aluminum or antimony halide catalyst and a co-catalyst which is an organic sulfur compound wherein the sulfur is divalent. Examples of such co-catalyst include various mercaptans, mercapto-aliphatic carboxylic acids, aliphatic thiocarboxylic acids, alkyl sulfides, alkyl disulfides, thiophenols, aryl sulfides, aryl disulfides and the like containing divalent sulfur. According to U.S. Pat. No. 3,317,617 (1967) the formation of parachlorotoluene is favored when toluene is reacted with chlorine in the presence of platinum dioxide. U.S. Pat. No. 4,031,144 (1977) discloses that a mono-chlorotoluene product having an unusually high para-chlorotoluene content is obtained when toluene is chlorinated in the presence of a catalyst system that contains a ferrocene compound and a co-catalyst that is sulfur or a compound that contains at least one divalent sulfur atom, such as sulfur, sulfur monochloride, sulfur dichloride carbon disulfide, thiophenes, thiophanes, alkylcycloalkyl-, aryl- and aralkyl mercaptans and dimercaptans, thioethers, and the like. U.S. Pat. No. 4,013,730 (1977) discloses a process for the preparation of monochlorotoluene having a reduced orthochloro- to parachloro isomer content which comprises reacting toluene with chlorine in the presence of a catalyst system comprising a Lewis acid catalyst and, as a co-catalyst, diphenyl selenide or aluminum selenide. Still further improvements in the preparation of monochlorotoluene having a low ortho to para isomer ratio are disclosed in U.S. Pat. Nos. 4,031,142 and 4,031,147 (1977). U.S. Pat. No. 4,031,142 discloses a process for the preparation of nuclear chlorinated alkylbenzenes, such as monochlorotoluene which comprises reacting an alkylbenzene, such as toluene, with chlorine in the presence of a Lewis acid catalyst and, as a co-catalyst, thianthrene. In accordance with U.S. Pat. No. 4,031,147, even lower ratios of ortho to para isomer are obtained in monochloroalkylbenzene products prepared by the reaction of an alkylbenzene with chlorine in the presence of a Lewis acid catalyst and a thianthrene compound having electron-withdrawing substituents, such as chlorine, present at the 2,3,7 and/or 8 position of the thianthrene nucleus. U.S. Pat. Nos. 4,069,263 and 4,069,264 disclose processes for the directed nuclear chlorination of alkylbenzenes wherein an alkylbenzene, such as toluene is reacted with chlorine in the presence of a substituted thianthrene having both electron-withdrawing substituents and electron-donating substituents on the nucleus thereof. U.S. Patent 4,250,122 (1981) to Lin discloses a process for the para-directed chlorination of toluene by reaction with chlorine in the presence of a catalyst mixture prepared by (a) reacting sulfur monochloride with toluene or chlorotoluene in the presence of a Lewis acid catalyst and (b) reacting the reaction product of (a) with chlorine. U.S. Pat. No. 4,289,916 (1981) to Nakayama et al. teaches a process for producing p-chloroalkylbenzene selectively by chlorinating an alkylbenzene in the presence of a phenoxathiin compound. U.S. Pat. No. 4,647,709 (1987) to Wolfram discloses a high proportion of p-chlorotoluene is obtained when toluene is chlorinated in the presence of a Lewis acid catalyst and a co-catalyst comprising a chlorination product of 2,8,-dimethylphenoxathiin. The primary component of the co-catalyst is 1,3,7,9-tetrachloro-2,8-dimethylphenoxathiin. U.S. Pat. No. 4,851,596 (1989) to Mais et al. discloses the ring chlorination of alkylbenzenes in the presence of Friedel-Crafts catalysts and thiazepine compounds as co-catalysts. U.S. Pat. No. 4,925,994 (1990) to Mais discloses an increase in the proportion of p-chloroalkylbenzenes when alkylbenzenes are chlorinated in the presence of a Friedel-Crafts catalyst and a 1,6-benzothiazocin co-catalyst. U.S. Pat. No. 4,990,707 (1991) to Mais et al. discloses the nuclear chlorination of alkylbenzenes in the presence of a Friedel-Crafts catalyst and, as a co-catalyst, a benzo-fused imine or benzo f!-1,4-thiazepine compound to increase the proportional yield of parachloroalkylbenzenes. U.S. Pat. No. 5,105,036 (1992) to Mais et al. discloses a process for the nuclear chlorination of alkylbenzenes in the presence of Friedel-Crafts catalysts and a co-catalyst which is a cyclic amidine that is oxy-substituted on the exocyclic N atom. The process results in a reaction product containing an increased proportion of the p-chloro isomer. SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a process for the production of nuclear chlorinated alkylbenzenes which comprise reacting an alkylbenzene of the formula: ##STR3## where Alkyl is an alkyl or cycloalkyl radical of up to 12 carbon atoms with a chlorinating agent in the presence of a Lewis acid catalyst and a cocatalyst comprising a compound or mixture of compounds characterized by the formula: ##STR4## wherein Z is: ##STR5## R is Cl, Br, F, C 1 to C 8 alkyl, or C 1 to C 8 alkoxy; x and y are each hydrogen, or taken together form a fused cyclopentyl or cyclohexyl ring; n is 0, 1, or 2, with the proviso that when Z is 3!, n is 0 or 1. The preferred co-catalysts are those wherein R is C 1 -C 4 alkyl, most preferably methyl, n is 0 or 1, and X and Y together form a fused cyclopentyl or cyclohexyl ring. In a second aspect, the present invention comprises a group of novel compounds, useful as catalysts. The novel compounds of this invention are characterized by the formula: ##STR6## wherein Z is: R is Cl, Br, F, C 1 to C 8 alkyl, or C 1 to C 8 alkoxy; X and Y are each hydrogen, or taken together form a fused cyclopentyl or cyclohexyl ring, with the proviso that when Z is 1!, X and Y represent a fused cyclopentyl or cyclohexyl ring; n is 0, 1, or 2, with the proviso that when Z is 3!, n is 0 or 1. DETAILED DESCRIPTION OF THE INVENTION A wide variety of Lewis acid catalysts may be employed in the process of the present invention. The term "Lewis acid catalyst" as employed herein includes, in addition to Lewis acids, those compounds or elements that will form Lewis acids under the conditions of the chlorination reaction. Preferred catalysts for this purpose are compounds of antimony, lead, iron, molybdenum and aluminum, including for example, the halides, oxyhalides, oxides, sulfides, sulfates, carbonyls and elemental form of these elements and mixtures of such compounds and most preferably the chlorides of aluminum, antimony, and iron. Typical of the catalysts which may be employed in the process of this invention are aluminum chloride, antimony trichloride, antimony pentachloride, antimony trioxide, antimony tetraoxide, antimony pentaoxide, antimony trifluoride, antimony oxychloride, molybdenum hexacarbonyl, lead sulfide, ferric chloride, ferrous chloride, ferrous sulfate, ferric oxide, ferrous sulfide, iron disulfide, iron pentacarbonyl, iron metal, and the like. The preferred co-catalysts which may be employed in the chlorination process of this invention include compounds of the structures: ##STR7## wherein X and Y together form a fused cyclopentyl or cyclohexyl ring, and n is 0 or 1. When n is 1, R is preferably C 1 -C 4 alkyl, and most preferably methyl. __________________________________________________________________________CO-CATALYSTS OF THIS INVENTIONCompound No. Structure and Name__________________________________________________________________________ ##STR8## (See Examples 1-6) 2,3-Dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioxepan-5-one2 ##STR9## (See Example 7) 2,3-Dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioxepan-5-thione3 ##STR10## (See Example 8) 2,3-Dihydro-2,3-trimethylene-1,5-benzo-1,4-thioxepan-5-one4 ##STR11## (See Example 9) 8-Chloro-2,3-dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioxepan-5-o ne5 ##STR12## (See Example 10) 2,3-Dihydro-1,5-benzothioxepan-5-one6 ##STR13## (See Example 11) 7-Methyl-2,3-dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioxepan-5-o ne7 ##STR14## (See Example 12) 7,8-Dimethoxy-2,3-dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioxepa n-5-one8 ##STR15## (See Example 13) 9-Methyl-2,3-dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioxepan-5-o ne9 ##STR16## (See Examples 14-17) 2,3-Dihydro-2,3-tetramethylene-1,6-benzo-1,4,6-thioxazocin-5(6H)-on e10 ##STR17## (See Example 18) 8-Methyl-2,3-dihydro-2,3-tetramethylene-1,6-benzo-1,4,6-thioxazocin -5(6H)-one11 ##STR18## (See Example 19) 10-Methyl-2,3-dihydro-2,3-tetramethylene-1,6-benzo-1,4,6-thioxazoci n-5(6H)-one12 ##STR19## (See Example 20) 8-Chloro-2,3-dihydro-2,3-tetramethylene-1,6-benzo-1,4,6-thioxazocin -5(6H)-one__________________________________________________________________________ The process of the invention is typically carried out in the liquid phase with the alkylbenzene reactant serving as solvent or primary liquid reaction medium. If desired, the reaction mixture may be diluted by addition of an inert solvent. Suitable solvents are those inert to the reactants and conditions of the process of the invention, such as methylene chloride, chloroform, and carbon tetrachloride. Preferably, the process is carried out without addition of an inert solvent. The amounts of catalyst and co-catalyst employed may vary considerably. Substantial benefits in terms of the lowering of the ratio of ortho- to para- isomer in the product may be achieved, for example, when the co-catalyst is present in an amount sufficient to provide a molar ratio of alkylbenzene:co-catalyst ranging from less than about 500:1 to 60,000:1 or higher. The preferred alkylbenzene:co-catalyst molar ratio is between about 30,000:1 and 50,000:1. The amounts of catalyst and co-catalyst are typically sufficient to provide a molar ratio of catalyst:co-catalyst of between about 0.01:1 and 20:1, preferably between about 0.0:1 and 10:1. Although it is preferred to carry out the process at atmospheric pressure, sub-atmospheric or superatmospheric pressures may be employed, if desired. Under atmospheric pressure, the chlorination of alkylbenzenes, in accordance with the present invention, may be carried out over a wide range of temperatures, ranging for example from sub-zero temperatures such as -30° C. or below to over 100° C. The upper limit of temperature is, of course, determined by the boiling point of the reaction medium, and may, depending on the boiling point limitation, range as high as 150° C. or higher. However, no practical advantage is gained through the use of higher temperatures or extremely low temperatures and it is preferred to employ temperatures in the range of about 20° to 100° C. and preferably about 40° to 60° C. The optimum temperature will vary somewhat, depending on the particular alkylbenzene and catalyst system employed. The following specific examples are provided to further illustrate this invention and the manner in which it may be practiced. Examples 1-6 In a glass reactor wrapped in aluminum foil, a mixture of 70.4 g (0.764 mole) of toluene, 0.0062 g (3.8×10 -5 mole) FeCl 3 , and 0.0045 g (1.911×10 -5 mole) of 2,3-dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioxepan-5-one (Formula 1) was heated to 50° C., in a nitrogen atmosphere, and maintained thereat, with stirring, while chlorine gas was passed through the reactor at about 70 SCCM over a period of 3.25 hours. The course of the reaction was monitored using gas chromatography to follow the disappearance of toluene. When 90% of the toluene had reacted, chlorine addition was stopped and the apparatus was swept with nitrogen and cooled to room temperature. Gas chromatographic analysis of the reaction mixture indicated a 93% yield of monochlorotoluene with an o/p of 0.85. The general procedure of Example 1 was repeated using the same reactants, catalyst and co-catalyst, varying the amounts and conditions and with the results as shown in Table 1 below. TABLE 1__________________________________________________________________________ Tol/ FeCl.sub.3T Cocat Cocat Wt of Reagents (g) Cl.sub.2EX °C. M.R..sup.a M.R..sup.a o/p PhMe FeCl.sub.3 Cocat SCCM Time__________________________________________________________________________1 50 40000 2.0 0.8500 70.4 0.0062 0.0045 70 3.252 50 2000 1.0 0.905 43.05 0.0379 0.0547 41 3.03 40 40000 2.0 0.850 56.8 0.005 0.0036 51 3.254 40 40000 1.0 0.970 50.0 0.0022 0.0032 50 3.55 50 200000 2.0 .sup. 1.400.sup.b 40.0 0.0007 0.0005 40 3.06 50 40000 2.0 0.858 42.0 0.0037 0.0027 21 5.75__________________________________________________________________________ .sup.a Mole Ratio .sup.b After about 50% reaction, chlorination was inhibited. Examples 7-13 The general procedure of Example 1 was repeated except that in place of the co-catalyst of that example, there were substituted various other co-catalysts, varying the conditions and amounts of reactants and with the results as set forth in Table II below. TABLE II__________________________________________________________________________ Tol/ FeCl.sub.3T Cocat Cocat Wt of Reagents (g) Cl.sub.2EX Cocat°C. M.R..sup.a M.R..sup.a o/p PhMe FeCl.sub.3 Cocat SCCM Time__________________________________________________________________________ 7 2 50 40000 2.0 0.970 25.0 0.0022 0.0017 25 3.25 8 3 50 40000 2.0 0.875 34.1 0.003 0.002 34 3.25 9 4 50 40000 2.0 0.968 46.6 0.0041 0.0034 48 3.010 5 50 40000 2.0 .sup. 1.135.sup.b 45.4 0.004 0.0022 44 3.011 6 50 40000 2.0 0.827 48.8 0.0043 0.0033 48 3.012 7 50 40000 2.0 1.485 31.8 0.0028 0.0025 32 3.013 8 50 40000 2.0 0.826 44.3 0.0039 0.003 43 3.0__________________________________________________________________________ .sup.a Mole Ratio Examples 14-17 The general procedure of Example 1 was repeated, substituting equal molar ratios of co-catalyst Compound 9 in place of co-catalyst 1. Temperature and amounts were varied with the results as shown in Examples 14-17 of Table III, below. TABLE III__________________________________________________________________________ Tol/ FeCl.sub.3T Cocat Cocat Wt of Reagents (g) Cl.sub.2EX Cocat°C. M.R..sup.a M.R..sup.a o/p PhMe FeCl.sub.3 Cocat SCCM Time__________________________________________________________________________14 3040000 2.0 .sup. 1.390.sup.b 32.9 0.0029 0.0022 28 3.015 4040000 2.0 .sup. 0.755.sup.c 64.8 0.0044 0.0044 65 2.516 5040000 2.0 0.813 55.7 0.0038 0.0038 54 3.017 6040000 2.0 0.906 52.3 0.0035 0.0035 50 3.0__________________________________________________________________________ .sup.a Mole Ratio .sup.b Benzyl chloride was a minor product. .sup.c o/p ratio was measured after 30% reaction. Examples 18-20 The general procedure of the preceding examples was repeated, substituting co-catalysts 10, 11, and 12 for the co-catalysts previously employed. In each example the reaction temperature was maintained at 50° C.; the toluene:co-catalyst molar ratio was 4000; and the FeCl 3 :co-catalyst molar ratio was 2.0. The amounts of reagents; reaction time; and o/p ratio obtained are set forth in Table IV below. TABLE IV______________________________________ Wt of Reagents (g) Cl.sub.2EX Cocat o/p PhMe FeCl.sub.3 Cocat SCCM Time______________________________________18 10 0.850 52.3 0.0046 0.0035 59 3.7519 11 0.932 53.4 0.0047 0.0038 58 4.0120 12 1.029 32.9 0.0029 0.0025 42 3.5______________________________________ Example 21 Preparation of 2,3-Dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioexpan-5-ones (co-catalysts 1, 3, 4, 6, 7, and 8) ______________________________________ ##STR20## ##STR21## ##STR22##Cocatalyst n R M.P. (°C.) Yield (%)______________________________________3 0 H oil 221 1 H 113.5-114.5 664 1 4-Chloro 121-122 206 1 5-Methyl 145-147 537 1 4,5-Dimethoxy Gum 128 1 3-Methyl 122-123 13______________________________________ General Procedure To a 0.8M solution of the appropriate 2-mercaptobenzoic acid derivative in reagent grade pyridine was added 1.1 mols of cyclopentene oxide or cyclohexene oxide and the mixture was heated at 80° C. for 2 hours. After cooling the reaction mixture to room temperature, pyridine and volatiles were removed using a water pump followed by vacuum pump (0.1 torr). The residual hydroxy acid derivative intermediate was found by GC to be sufficiently pure to take it to the next step. The intermediate obtained above was taken in toluene so as to obtain a 0.3M solution. To this was added a catalytic amount of p-toluenesulfonic acid (PTSA) and the mixture was refluxed for 1 hour using a Dean Stark water trap. The mixture was then cooled, and water was added. The organic layer was separated, washed twice with aq. NaHCO 3 solution, dried with MgSO 4 and concentrated to give the pure lactone product. Example 22 Preparation of 2,3-Dihydro-2,3-tetramethylene-1,5-benzo-1,4-thioexpan-5-ones (co-catalysts 2) ##STR23## Procedure A solution of 0.181 g (0.774 mmol) of 1 in 2 mL of dry toluene was treated with 0.156 g (0.387 mmol) of Lawesson's reagent and the mixture was heated under reflux for 4 days. The reaction mixture was cooled to room temperature and the toluene was evaporated. The residue was then subjected to preparative TLC using 95/5 hexanes/ether to afford 0.16 g (83%) of pure thionolactone 2 as a light orange gum. Example 23 Preparation of Cyclic Urethanes (co-catalysts 9, 10, 11, and 12) ______________________________________ ##STR24## ##STR25## ##STR26##Co-catalyst R Yield (%) M.P.______________________________________9 H 30 180-18110 8-methyl 48 212-214 (Dec)11 10-methyl 50 223-22412 8-chloro 70 223-224______________________________________ General Procedure Synthesis of compounds 9-12 were accomplished using either of the two pathways shown in the scheme above. A representative example of synthesis using each method is described below. Method A. Exemplified by synthesis of compound 9 A mixture of 5.09 g (40.6 mmol) of 2-aminothiophenol and 4.39 g (44.7 mmol) of cyclohexene oxide in 85 mL pyridine was stirred at 80° C. for 4 hours. The reaction mixture was cooled to room temperature, and pyridine and volatiles were removed under 0.1 torr. The brown residue (7.87 g, 87% yield) solidified partly upon standing. GC analysis indicated this intermediate hydroxyacid to be sufficiently pure for further transformation. A solution of 1.03 g (4.6 mmol) of the above hydroxyacid intermediate in a solvent mixture of 40 mL anhydrous diethyl ether and 20 mL dichloromethane was cooled to 0° C. and treated dropwise with a solution of 0.46 g (1.55 mmol) of triphosgene in 3 mL of anhydrous diethyl ether over 25 minutes. After addition, the ice bath was allowed to warm up to room temperature and stirred overnight. The reaction mixture was poured into 30 mL water and extracted with 60 mL ether. The water layer was extracted with 50 mL ether and combined ether extracts were washed with 3×100 mL saturated NaHCO 3 solution, then with 50 mL water, dried with MgSO 4 and concentrated to give the crude product. Purification by silica gel column chromatography (24 g silica gel, 20/80 hexanes/ether eluent) afforded 0.44 g (30%) of pure 9 as a pale yellow flaky solid; m.p. 180-181° C. The material was also characterized by its proton and carbon NMR spectra. Example 24 Method B. Exemplified By Synthesis of Compound 10 To a solution of 2.62 g (15 mmol) of 2-amino-4-methylthiophenol hydrochloride in 5 mL of ethanol, a solution of 1.47 g (15 mmol) of cyclohexene oxide and 1.98 g (30 mmol) of KOH (85% assay) in 15 mL ethanol was added and the mixture refluxed for 1 hour under nitrogen. From the mixture, 10 mL of ethanol was then evaporated and the residue was treated with water (20 mL) to precipitate a solid which was separated by filtration. After drying at room temperature, the solid was dissolved in 50 mL of ether and solution filtered through alumina (20 g, activated, acidic, Brockmann I). The eluate was then evaporated and residue crystallized from hexane to yield 2.75 g (77%) of pure hydroxamine intermediate (2-hydroxycyclohexyl-(2-amino-4-methylphenyl)sulfide); m.p. 94°-97° C. To a solution of 1.18 g (5 mmol) of the above intermediate hydroxyamine in 10 mL of dichloromethane, a solution of 1 mL (10 mmol) of triethylamine in 5 mL of dichloromethane was added. The mixture was cooled to -3° C. and 1.5 mL (20 mmol) of phosgene was sparged through the solution under slow nitrogen flow (<60 cc/min) for 0.5 hours. The dark blue mixture was allowed to warm to room temperature and left stirring overnight. The reaction mixture was treated with water, 5% NaHCO 3 aqueous solution, then water again, dried with Na 2 SO 4 , and filtered through alumina. Dichloromethane was evaporated from the eluate to give a solid residue which was crystallized from ethanol to afford 0.63 g (48%) of pure product (10) as colorless crystals; m.p. 212°-214° C. (dec). The material was also characterized from its proton and carbon NMR spectra.
Novel benzothioxepanone and benzothioxepane thione compounds are characterized by the formula ##STR1## wherein Z is: ##STR2## R is Cl, Br, F, C 1 to C 8 alkyl, or C 1 to C 8 alkoxy; X and Y are each hydrogen, or taken together form a fused cyclopentyl or cyclohexyl ring, with the proviso that when Z is 1!, X and Y represent a fused cyclopentyl or cyclohexyl ring; and n is 0, 1, or 2. The compounds are useful as co-catalysts in the para-directed nuclear chlorination of toluene.
2
CROSS-REFERENCE TO RELATED APPLICATIONS Not applicable. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT Not applicable. FIELD OF THE INVENTION The invention relates to a method and apparatus for the removal of undesirable materials on the wall of an earth formation so as to allow the measurement of formation characteristics such as pressure. More particularly, the invention relates to a device that creates a wave discharge by pulsing a volume of fluid so as to produce a resonant oscillation in the fluid. The wave discharge is directed in the form of a concentrated beam against at least partially non-permeable membranes formed on the earth wall of a borehole in order to remove these materials from the wall of the borehole. Still more particularly, the described device creates oscillations that produce the wave discharge by using a Helmholtz resonance frequency in pulsing a fluid volume. The wave discharge will disintegrate mudcake formed on the earth formation borehole wall to allow the unobstructed measurement of formation pressure within the formation. BACKGROUND OF THE INVENTION The efficient recovery of subterranean hydrocarbons such as oil and gas is assisted by obtaining reliable data about the physical conditions in a formation of interest. For example, a target formation typically includes hydrocarbon fluids that are under high pressure. Accurately measuring the formation pressure where such pressurized materials reside promotes safe and cost-effective operations in nearly all phases of hydrocarbon recovery. However, techniques for measuring formation pressure must overcome a number of technical challenges. One obstacle to pressure measurement is the mudcake that drilling mud tends to deposit on the wall of the wellbore. A wellbore is typically filled with a drilling fluid such as water or a water-based or oil-based drilling fluid. The density of the drilling fluid is usually increased by adding certain types of solids that are suspended in solution. Drilling fluids containing solids are often referred to as drilling muds. The drilling fluids cool and lubricate the drill bit and carry the cuttings uphole to the surface. The solids in drilling fluids also increase the hydrostatic pressure of the wellbore fluids. By selecting drilling fluids weighted to a particular density, the column of drilling fluids creates a pressure downhole, which is greater than the pressure of the fluids in the formation. When the drilling fluid pressure is greater than the formation fluid pressure, the well is said to be in an over balanced condition. Conversely, if the formation pressure is greater than the fluid column, then the well is said to be in an under balanced condition. Control of formation fluids flowing into the well under high pressure minimizes the risk of a well blowout. While an over balanced condition prevents well blowouts, it also has disadvantages, such as increased drilling costs due to slower penetration into the formation. Drilling fluid pressure in excess of formation pressure slows the penetration of the drill bit into the formation. In certain well environments it is preferred to maintain a neutral or slightly under balanced condition so as to achieve drilling speeds faster than those achieved while drilling in an over balanced condition. Drilling Practices Manual, Preston Moore, P. 18-22 Pennwell Publishing, 1974. Consequently, it is desirable to maintain a neutral balance or a slightly under balanced condition to maximize drilling penetration into the formation. Drilling fluids create a mudcake as they flow into a formation by depositing solids on the inner wall of the wellbore. The mudcake on the wall of the wellbore tends to act like a filter and tends to isolate the high-pressure fluids of the wellbore from the relatively lower pressures of the formation. The mudcake helps prevent excessive loss of drilling fluid into the formation. The static pressure in the wellbore and the surrounding formation is typically referred to as hydrostatic pressure. Pressure in the formation beyond the mudcake gradually tapers off with increasing radial distance outward from the wellbore. The measurement of formation pressures during drilling operations assists in locating strata most likely to produce hydrocarbons efficiently. Typically after the borehole is drilled, the well is logged by lowering a package of sensors downhole that gather data about the formation. Pressure data is useful in judging when a formation contains hydrocarbons and when such a formation may economically produce hydrocarbons. Often a wellbore may pass through more than one hydrocarbon-bearing formation, and formation pressure data assists the drilling engineer in determining whether to halt or continue drilling. Further, the ability to monitor formation pressure during drilling is important to the desired practice of continuously adjusting the drilling mud density. This facilitates drilling through the maximum amount of formation in the shortest amount of time. To maintain the proper condition during drilling, whether neutral, over balanced or under balanced, it is necessary to measure the pressure of the formation fluids at the vicinity of the drill bit. However, the dynamic environment near the drill bit makes measurement of the formation fluids particularly difficult during logging while drilling (LWD) operations. In addition, the mudcake that forms on the wall of the borehole presents a further difficulty in determining formation fluid pressure at the bit during drilling. This mudcake forms a relatively non-permeable barrier between the instrument on the one side and the formation fluids on the other. The mudcake barrier hinders accurate measurement of the pressure of the formation fluids. Prior art sensors are generally not capable of measuring formation fluid pressure during drilling. Consequently, rig personnel must closely monitor the drilling fluids flowing from the borehole for signs of increased formation fluid pressure. This often entails temporarily halting the drilling operation to allow pressure measurement of the formation. Once the drilling fluids show evidence of formation fluids flowing up the borehole, drilling is stopped and corrective measures are taken. However, this approach has particular drawbacks; and, it would be desirable to determine formation fluid pressure at the bit during drilling. One such prior art instrument is a reservoir description tool (RDT) such as that disclosed in U.S. Pat. No. 5,644,076 (the '076 patent) entitled “Wireline Formation Tester Supercharge Correction Method”, incorporated herein by reference in its entirety. The RDT of the '076 patent includes a pressure sensing element mounted within a chamber of a housing having a piston to create a vacuum within the housing chamber. Hydraulic pads force the housing against the borehole wall; and, as the piston retracts to create a pressure reduction, a drawdown pressure removes the mudcake lining from the borehole wall. Fluids in the formation then enter the housing chamber allowing the pressure-sensing element to take a pressure reading. This tool allows only stationary measurements because drawdown pressure requires a tight seal between the housing and the borehole wall. This is undesirable because, aside from being time consuming, stationary measurements provide only discrete data points, not a continuous log. The drawback to discrete data points is that the fluid pressure between the discrete data points may vary dramatically and unpredictably. Another borehole tool for removing the mudcake to measure the pressure of the formation fluids is disclosed in U.S. Pat. No. 5,969,241 (the '241 borehole tool) incorporated herein by reference. The '241 borehole tool measures pressure from within the borehole. A portion of the borehole wall is isolated from the surrounding borehole fluids by placing the chamber of the '241 borehole tool against the borehole wall. The chamber comprises a recess in an exterior surface of the '241 borehole tool. This patent describes an acoustic horn as the mechanism by which to excite fluids in a chamber. The mudcake present on the isolated portion of the borehole wall is disintegrated by an ultrasonic transducer, actuated by a piezoelectric stack, housed within the chamber. A pressure gauge then measures the pressure of the chamber to indicate the pressure of the earth formation. Such a prior art tool also has deficiencies. For example, this borehole tool is inefficient because its vibrational energy does not transfer directly to the fluid. The vibrating born is limited in the efficiency by which it transfers electrical energy to acoustical wave energy. Excitation of the piezoelectric stack creates a longitudinal wave resonance within the ultrasonic transducer. As the ultrasonic transducer resonates longitudinally, the vibrational energy is transferred to the fluid. However, the mechanical coupling of the ultrasonic transducer to the fluid is poor, thus much of the vibrational energy imparted by the piezoelectric stack remains in the ultrasonic transducer. This inefficient energy transfer is expected to reduce the vibrational energy available to break down the mudcake. Further, such tools are not compact and are not easily installed in the drill string, which must pass through the confined area of the borehole. Notwithstanding the foregoing described prior art, there remains a need for a device that possesses the features of efficiently transferring vibrational energy to create a focused wave discharge that may be used to remove mudcake from a borehole wall. Further, it is desired that such a device may be utilized so as to minimize any interruption to the drilling process. It is also desired that such a tool be capable of use on different down hole assemblies such as wire line operations and near the drill bit in drilling operations. Additionally, the tool should be able to take pressure measurements on a continuous or near-continuous basis as the drill string descends the well bore. SUMMARY OF THE INVENTION The present invention overcomes the aforementioned deficiencies of the prior art by providing a device that generates rhythmic pressure pulsations within a fluid-filled chamber, thereby producing a pressure wave discharge, which exits through an orifice of the chamber in a focused beam. The pulsations produced by the device include Helmholtz resonant frequencies for the geometry of the chamber; Helmholtz resonant frequencies efficiently transfer energy from pulse elements of the device to the fluids in the chamber. The device directs pressure waves in the fluids in the chamber through an orifice that focuses the waves against the borehole wall in the form of a concentrated beam. The wave discharge removes mudcake from the borehole wall, thereby opening a passage from the interior of the formation to the device chamber. In this manner pressure transducers associated with the device may accurately measure pressure from the formation. The device of the present invention operates with a speed that allows it to be used on a continuous to near-continuous basis. If disposed on a drill string, the drilling operation need not be slowed or halted in order for the present acoustic jet to function. Further the device may be used on both wireline operations and drilling operations. The pressure reading tool of the present invention overcomes the deficiencies of the prior art by applying a fundamentally different approach to the removal of mudcake from borehole walls. For example, the '241 borehole tool induces vibrational frequencies in an acoustic horn to transfer the vibratory energy to the fluid. The tool of the present invention induces a resonance in the fluid itself. Thus, the poor energy transfer between the acoustic horn and fluid is eliminated. Further, the tool of the present invention concentrates and focuses the wave energy so as to minimize the loss of energy while simultaneously maximizing the energy brought to bear against the borehole wall. One embodiment of the present invention includes pressure reading tool having a housing with an interior chamber and an orifice extending from the chamber to the exterior of the housing. A pulse member with a magnetostrictive ring and excitation source is disposed within the housing chamber to produce a highly agitated fluid discharge through the orifice. The magnetostrictive ring, chamber volume, and orifice may be designed to cooperate to induce Helmholtz resonance frequencies in the fluid in the chamber to thereby enhance the agitation of the fluid discharge. A sheathing may be used to encapsulate the pulse member to protect it from contact with the fluid. A dampening element may also be interposed between the pulse member and housing to isolate vibration. In operation, the tool is disposed in the wall of the drill stem having a drill bit for penetrating the formation and forming a borehole. An impermeable membrane in the form of mudcake forms on the borehole wall due to the drilling fluids. A portion of the borehole wall is isolated by placing the tool against the borehole wall. The pulse member is actuated to modulate the chamber volume to produce agitated fluids within the chamber. The fluids are agitated at a high frequency within the chamber. The tool directs a stream of pressure waves through the orifice and against the impermeable membrane to remove the impermeable membrane. A pressure transducer communicates with the chamber to read the pressure of the formation fluids. These pressure readings are communicated with the surface to direct the drilling of the bit through the formation. The readings may be continuous while drilling. Thus, the present invention comprises a combination of features and advantages that enable it to overcome various problems of prior art pressure measuring devices. The various characteristics described above, as well as other features, objects, and advantages, will be readily apparent to those skilled in the art upon reading the following detailed description of the preferred embodiments of the invention, and by referring to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS For a detailed description of a preferred embodiment of the present invention, reference will now be made to the accompanying drawings, which form a part of the specification, and wherein: FIG. 1 is a cross-sectional close-up view of a drill string and well bore; FIG. 2 is a cross-sectional view of a preferred embodiment of the present invention; FIG. 3 is a cross-sectional close-up view of the preferred embodiment of FIG. 2; and FIG. 4 is a cross-sectional view of three pressure reading tools positioned in three stabilizer blades of a down hole assembly. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT It should be appreciated that the invention may be embodied in many different forms. There are shown in the drawings, and herein will be described in detail, specific embodiments of the present invention. However, the present disclosure is an exemplification of the principles of the invention. It is not intended to limit the invention to the particular illustrated embodiments, which can be modified in the practice of the invention. For example the present invention may be used while logging on a wireline cable or in logging while drilling. The present invention is particularly advantageous in logging while drilling as further described below. The term “logging” is used herein in its broadest sense to include recording any type of data representing characteristics of the formation as a function of depth, including particularly the measurement of formation fluid pressure. Referring initially to FIG. 1, there is shown the use of an embodiment of the present invention for logging while drilling. The pressure reading tool 60 is shown disposed in a bottom hole assembly 10 for drilling a borehole 12 . The borehole 12 extends from the surface down through a plurality of different earth formations such as exemplary formation 14 . Formation 14 may include various formation fluids 16 such as water, gas and hydrocarbons. These formation fluids 16 are under pressure. The logging while drilling embodiment of the bottom hole assembly 10 includes various members including a drill collar or drill stem 18 with a drill bit 20 connected thereto. It can be seen that the drill bit 20 is penetrating the formation 14 at the bottom 22 of the borehole 12 . Drilling fluids 24 are pumped down through the drill string on which the bottom hole assembly 10 is disposed, to the bottom 22 of the borehole 12 and then return up the annulus 26 , formed by the drill string and wall 28 of borehole 12 , to the surface. The drilling fluids 24 lubricate and cool the bit 20 and remove the cuttings to the surface. As the column of drilling fluids circulates through borehole 12 , some of the drilling fluid solids 24 accumulate on wall 28 of borehole 12 forming a mudcake 30 . Mudcake 30 forms a relatively impermeable membrane between the drilling fluids and earth formation 14 . A pressure drop typically occurs across mudcake 30 . The present pressure reading tool 60 is schematically shown disposed in aperture 32 of one of the drilling string members, such as drill stem 18 . Alternatively, the tool may be disposed on various pieces of downhole machinery. For example, in the embodiment shown in FIG. 4 pressure reading tools are placed in stabilizer blades 40 . Alternatively, the pressure reading tools may be placed on the drill stem 18 or on the drill collar. Alternatively, pressure reading tools may be positioned on a dedicated piece of machinery that is itself attached to the drill string. Similarly, the tool may be employed on a wireline. While FIG. 1 portrays a single pressure reading tool disposed within the drilling apparatus, it should also be understood that more than one such tool may be included in any particular down hole assembly. For example, in one embodiment three pressure reading tools are disposed within the same drill collar or drill stem. As shown in FIG. 4, a particular drill collar has three stabilizer blades 40 . There is a tool of the present invention disposed in each of the three stabilizer blades. In that embodiment, each of the three tools is at the same horizontal position on the drill stem; however, each tool is separated radially. In this manner, the three tools record formation pressure from sections of the formation at differing azimuthal positions. In an alternative embodiment a drill collar or drill stem may be arrayed with multiple tools at differing horizontal positions. There is an advantage associated with the use of multiple pressure reading tools. As the number of such tools increases, so does the chance of successfully obtaining an accurate formation pressure reading at a particular location. Conditions inherent in drilling, such as the vibrations and mechanical shocks found in the drilling environment, raise the possibility that mechanical equipment such as the pressure reading tool may be rendered inoperable. Likewise, a poor seal between the borehole wall 28 and orifice 76 of the tool may affect the pressure reading taken by the tool. In both these instances, the placement of multiple tools on the drill string increases the chance of a successful reading. In both FIG. 1 and FIG. 4 tool 60 is directed radially outward toward mudcake 30 . In this manner, tool 60 produces and directs a wave discharge for removing the mudcake to allow the measurement of formation fluid pressure while drilling as hereinafter described in detail. Referring now to FIG. 2, there is shown a preferred embodiment of the tool 60 , which includes a pressure reader 64 , a housing 66 , and pulse device 70 for producing an agitated fluid discharge using Helmholtz resonance frequencies, thus enabling pressure readings of the earth formation. Housing 66 is generally defined by a cylindrical wall 82 , an outer cap 74 , and an inner cap 75 . The generally hollow interior of housing 66 forms a chamber 84 . Chamber 84 itself is generally cylindrical in shape, as it is defined by cylindrical wall 82 , outer cap 74 , and inner cap 75 . Outer cap 74 includes an orifice 76 . Outer cap 74 may be at least partially hardened against frictional wear caused by movement across borehole wall 28 . Hardening of outer cap 74 may be through a surface treatment or a “wear plate” mounted on outer cap 28 . Inner cap 75 is adjacent the inside diameter of drill stem 18 and includes a conduit 78 at its center, which is substantially opposite orifice 76 in outer cap 74 . Inner cap 75 also includes one or more feed-through holes 80 , 81 for receiving electrical conduits 83 , 85 . Outer cap 74 or inner cap 75 may be removable to allow access to chamber 84 . The tool has been described as having a chamber with a generally cylindrical interior geometry. While such a shape is believed to be advantageous for the transfer of energy from an electrical form to an acoustic form, the chamber may nevertheless assume other configurations. Any chamber geometry is possible, including, but not limited to, conical, spherical, cubic, rectangular, tetragonal, pyramid-shaped, elliptical, ovoid, parabolic, and polygonal. Conduit 78 is also preferably substantially opposite orifice 76 . While this is believed advantageous, alternative placements of conduit 78 are also possible. For example, conduit 78 could be placed in cylindrical wall 82 . Also, conduit 78 could be placed in an off-center position on inner cap 75 . These examples are for illustrative purposes only and are not meant to be limiting. According to the embodiment as shown in FIG. 2, outer cap 74 is curved so as to follow the shape of borehole wall 28 . Outer cap 74 would be disposed adjacent the borehole wall. In this embodiment, outer cap 74 may be hardened to withstand the contact with borehole wall 28 . In alternative embodiment, however, outer cap 74 is positioned some distance from borehole wall 28 so as to avoid direct contact with borehole wall 28 . As shown in FIG. 4, the pressure reading tool is positioned in a stabilizer blade of the downhole assembly. In this configuration, stabilizer blade 40 contacts borehole wall. Outer cap 74 is slightly recessed so that it does not directly contact borehole wall. In the configuration of FIG. 4, outer cap 74 need not assume a curved shape; nor does it need to be hardened. Preferably, housing 66 is sufficiently compact to fit into a drill collar, drill stem 18 , stabilizer blade 40 , or wireline device. The pressure reading tool may be preassembled and installed as a unit in a machined or precut aperture 32 of a selected drill piece. Some known attachment means may be used in order to affix the pressure reading tool to the drill piece. Known attachment methods include, but are not limited to, a pressure fitting, pins, threading, bolting or gluing. Preferably, a threaded lock ring 42 , shown in FIG. 4, secures the pressure reading tool to the drill piece. The body of housing 66 may also seal aperture 32 so as to prevent the interior of the drill string passing fluids to or from the exterior of the drill string. This is preferably accomplished by o-ring seals 44 . Material selection for housing 66 is largely driven by downhole environment conditions. Generally, a corrosion resistant steel will provide the necessary ruggedness for borehole applications. Acceptable materials include steels such as 17-4PH or MP-35N. Referring now to FIGS. 2 and 3, cylindrical wall 82 of chamber 84 is preferably at least partially lined with dampening element 86 . Preferably, dampening element 86 is made of a relatively soft material such as lead. Because tool 60 may be used along with an array of wireline instruments, it is preferred that the operation of tool 60 be dampened to prevent the transmission of vibrations along the drill string. This serves to minimize interference with other drill string instruments. Thus, cylindrical wall 82 of chamber 84 is lined on its interior preferably with a layer of lead to absorb much of the vibrations. In lieu of a lining, dampening element 86 may be a lead ring formed to seat at least partially along interior cylindrical wall 82 . It is emphasized that these are only two non-limiting examples of elements suitable for dampening. It is also emphasized that the dampening element is a convenient feature and may not be essential to the satisfactory operation of tool 60 . Alternatively any members that constitute housing 66 such as cylindrical wall 82 , outer cap 74 , and inner cap 75 may be selected of a material and dimension sufficient to perform any needed dampening function. Pulse device 70 is disposed within chamber 84 and comprises a member or members that can physically oscillate in response to a signal. In the preferred embodiment of FIG. 2, pulse device is a generally annular or ring-shaped member disposed within chamber 84 . Pulse device 70 seats substantially contiguously along the interior surface of cylindrical wall 82 , or, if present, along the interior surface of dampening element 86 . Preferably, pulse device 70 extends along the length of cylindrical wall 82 such that the ends of pulse device 70 rest against the interior surfaces of outer cap 74 and inner cap 75 . In the preferred embodiment, pulse device 70 seats substantially contiguously along the interior surface of cylindrical wall 82 . In this manner, the physical oscillations of pulse device 70 efficiently transfer energy to fluid in chamber 84 at all positions along the interior surface of pulse device 70 . However, it is possible to configure pulse device 70 in an alternative manner. For example, rather than being configured as a single, ring-shaped body, pulse device 70 could comprise any number of discrete units, of any geometry. These separate units could be placed at different locations within chamber 84 . A plurality of individual pulse device units could approximate the form and function of a ring-shaped pulse device when such individual units are placed in proximity to one another along the interior surface of cylindrical wall 82 . Alternatively, discrete pulse device units could be placed on the interior surfaces of outer cap 74 and inner cap 75 . Additionally, pulse device units could even be placed at some interior position of chamber 84 . If housing 66 is selected such that it defines chamber 84 to have a non-cylindrical geometry, then pulse device 70 may also have an alternative configuration and placement in the chamber. It would also be possible, and would be within the scope of this invention, to construct housing 66 with recesses or voids so as to have a honeycombed configuration. In such a configuration, pulse device units could be disposed within the recesses of housing 66 . Pulse device 70 may itself be composed of separate elements. In the ring-shaped, preferred embodiment, shown in FIG. 3, pulse device 70 has pulse elements 88 at its core. Excitation source 90 wraps around pulse elements 88 , and sheathing 72 excitation source 90 . Sheathing 72 thus forms the external surfaces of the preferred pulse device 70 . Sheathing 72 is preferably made of an elastomeric material to insulate the pulse device 70 from harmful contact with borehole fluids and particulates. Accordingly, the material for sheathing 72 should be selected to provide a impermeable barrier between the borehole environment and pulse device 70 . Another consideration in material selection is the need to efficiently couple the energy of pulse device 70 to the fluid in chamber 84 . Thus, sheathing 72 should be a resilient medium that provides efficient transfer of pulsing motion from pulse device 70 to the fluid. Generally, the modulus of elasticity of the material for sheathing 72 should be closer to that of rubber than that of steel. Materials with relatively high material stiffness will tend to limit the motion of pulse device 70 . Rubber meets the requirements of elasticity and impermeability. Other materials such as Teflon may also be designed to have the requisite material properties. Further, sheathing 72 also provides a resilient support for pulse device 70 in housing chamber 84 . Preferably, the thickness of sheathing 72 should secure pulse device 70 within housing 66 without unduly impeding the oscillating motion of pulse device 70 . Still referring to FIG. 3, pulse device 70 includes a plurality of pulse elements 88 wrapped within excitation source 90 . Pulse elements 88 physically distort in response to an excitation signal. As pulse elements 88 physically distort, the volume of chamber 84 rhythmically increases and decreases, thereby producing a pulsation of the fluid within chamber 84 . Preferably, pulse elements 88 are a ring of magnetostrictive elements capable of radial oscillatory expansion and contraction when activated. Excitation source 90 can include windings that are capable of transferring magnetic flux signals. Magnetic flux is the excitation signal that causes magnetostrictive elements to physically distort. The windings of excitation source 90 are wrapped around the magnetostrictive elements and exit housing 66 via housing feed-through holes 80 , 81 . Outside the housing, the wires may connect with an external signal source. While feed-through holes 80 , 81 allow the winding wires of excitation source 90 to exit, it is otherwise sealed to segregate fluid within chamber 84 . Pressure boots may provide one mechanism by which to make the electrical connection from wiring to the pressure reading tool. Alternatively, pulse elements 88 may be a plurality of piezoelectric elements. As with the magnetostrictive ring, the piezoelectric elements are formed into an annular or ring shape. A preferred piezoelectric material is PZT-5A Piezoelectric Material, available from EDO Corporation, Salt Lake City, Utah, 84115. Whether piezoelectric elements or magnetostrictive elements are used depends on the demands of a particular application. For example, it is generally understood that piezoelectric elements are more brittle than magnetostrictive elements and may be more easily damaged. However, a particular situation may require the higher frequency oscillations that are more efficiently provided by piezoelectric elements. In any event, magnetostrictive and piezoelectric elements are given as illustrative examples of a material that can produce harmonic pulsation of the fluids in chamber 84 . Pulse elements 88 are not intended to be limited to these two materials. Orifice 76 will focus the pressure wave discharge into a concentrated beam. However, one skilled in the art will understand that the profile of orifice 76 can be easily modified for alternate fluid discharges. Thus, nearly any profile may be utilized for chamber 84 and orifice 76 . If a Helmholtz chamber is desired, the resulting volume and geometry must satisfy the Helmholtz resonance frequency requirements. In certain downhole applications, it is foreseeable that it may not be possible to design housing 66 to create Helmholtz resonance frequencies. In such cases, it will be apparent to one skilled in the art to adjust the geometry of housing 66 and orifice 76 to produce an agitated fluid discharge. A Screen 68 is preferably positioned within chamber 84 on outer cap 74 proximate to orifice 76 . Screen 68 can prevent borehole particulates from entering chamber 84 . When the fluid in chamber 84 is vibrated, fluid in the immediate vicinity of orifice 76 develops the highest fluid velocity. It is preferable not to restrict such fluid movement. However, if screen 68 is placed too far from orifice 76 , it may allow borehole particulates to enter chamber 84 and damage pulse device 70 . Preferably, screen 68 is placed to allow the highest velocity fluid movement through orifice 76 . Further, screen 68 includes a plurality of openings designed to minimize impedance to fluid movement. Preferably, screen 68 is formed of stainless steel and secured to outer cap 74 . While particulates capable of damaging tool 60 are often present in a borehole environment, it is emphasized that satisfactory operation of tool 60 is not dependant on the presence of screen 68 . A pressure reader 64 is mounted to housing 66 . Conduit 78 provides fluid communication between pressure reader 64 and chamber 84 . Pressure reader 64 preferably includes a threaded portion that may engage mating threads within conduit 78 . Alternatively, pressure reader 64 may be secured to housing 66 by some alternative means. Because conduit 78 provides access to chamber 84 , the fluids in chamber 84 pass through conduit 78 and contact a surface of pressure reader 64 such that the pressure of the fluids can be measured. It is preferable to locate pressure reader 64 as closely as possible to chamber 84 . A remotely mounted pressure reader 64 requires a longer conduit 78 , which may be more susceptible to plugging by borehole particulates. Commercially available pressure transducers can be utilized as the pressure reader 64 in the present invention. One such pressure transducer is a strain gage based pressure transducer manufactured by Paine, Inc. Quartz gage pressure transducers are more accurate and may be used. Such devices are usually more bulky and thus of limited suitability to borehole applications. While it is not essential to the invention, in the preferred tool 60 , the geometry of housing 66 , chamber 84 , orifice 76 , and pulse device 70 are selected to produce Helmholtz resonance frequencies in the fluid expected to be encountered in the drilling environment. Helmholtz resonance is a well-known scientific principle. The shape and design of Helmholtz cavities or Helmholtz resonators is also known in the industry. One kind of Helmholtz resonator is an enclosed cavity of fluid with an open port. If the volume of fluid in the cavity is compressed, the fluid attempts to spring back to its original volume. Physical oscillations in the fluid within a ported cavity tend to resonate at specific frequencies. The natural resonant frequency for a spherical Helmholtz resonator ported with a cylindrical neck in an atmospheric environment may be represented by the following equation: f r = c 2  π  A LV where c=speed of sound in the fluid V=cavity volume A=cross sectional area of the neck, and L=length of the neck This equation necessarily changes as the fluid is changed from air to another medium. Likewise, as other factors such as the geometry of the chamber and neck become more complicated, the classical equation breaks down. Hence the selection of an optimal frequency in the pressure reading tool must also be guided by trial-and-error methods. Given the changing environment in an active wellbore arising from factors such as changing pressures and the changing densities of fluids present in the wellbore, it is sometimes necessary to design a resonating chamber that can function across a variety of frequencies. A preferred design of the present invention was tested in laboratory conditions. The fluid was a drilling mud with density of approximately 1500 kg/m 3 . The speed of sound in this material was estimated at 1500 m/s. At approximately 42 kHz the preferred embodiment of the present invention displayed a relatively low impedance while retaining good sound pressure levels. At this frequency the design was found to generate a cylindrical standing wave in laboratory testing. One preferred embodiment of pressure reading tool 60 previously described has the following dimensions. The diameter of the chamber 84 in the fully assembled tool, i.e., the chamber diameter as defined when pulse device 70 is in place, is approximately 1.10 in. The diameter of chamber 84 with pulse device 70 removed is approximately 1.75 in. No dampening element 86 was present. The annular pulse device 70 thus has a ring thickness of approximately of 0.325 in. The depth of chamber 84 is approximately 1.00 inch. Outer cap 74 has a thickness of approximately 0.250. Inner cap 75 has a thickness of approximately 0.50 in. The cylindrical interior wall is approximately 0.25 in. thick. Orifice 76 , centered in outer cap 74 , has an opening diameter, measured at the exterior wall of outer cap 74 , of approximately 0.50 in.; and orifice 76 widens toward the interior of chamber 84 at an angle of approximately 28°. In this preferred embodiment, pulse device 70 , with an annular ring thickness of approximately 0.325 in., was further designed as follows. Sheathing 72 was as long as the interior length of chamber 84 , approximately 1.00 in., and assumed the ring thickness of the pulse device 70 , approximately 0.325 in. An annular-shaped magnetostrictive assembly, composed of a magnetostrictive ring with windings, was approximately 0.75 in. long and approximately 0.10 in. in thickness. The magnetostrictive assembly formed the interior of pulse device 70 . The magnetostrictive assembly had an interior diameter of approximately 1.30 in. and an exterior diameter of approximately 1.50 in. Given the differences in diameters, the magnetostrictive assembly was thus placed in sheathing 72 in a slightly off center position. The distance from the interior surface of sheathing 72 to the interior surface of the magnetostrictive assembly was approximately 0.20 in. However, the distance from the exterior surface of sheathing 72 to the exterior surface of the magnetostrictive assembly was approximately 0.25 in. In the assembled pulse device the magnetostrictive assembly was placed equidistant from the interior surfaces of outer cap 74 and inner cap 75 , approximately 0.125 in. from each. In operation, rig personnel will install preferred tool 60 into a drilling structure such as a drill stem 18 , on a stabilizer blade 40 , or drill collar. The appropriate electrical connections are made to link pulse device 70 with a signal source. Pressure reader 64 may also be linked with an appropriate display device or recording device, usually located at a control point on the surface. Such a link is preferably done through an electronic data connection. To take pressure readings during LWD, the assembled tool is lowered into borehole 12 . When the drill string approaches a formation region of interest, several steps will take place. Of initial importance is the seal between orifice 76 of tool 60 and borehole wall 28 . The measuring of formation pressure with the pressure reading tool is best accomplished when the tool is placed firmly against the formation wall. In one embodiment, the face, or outer cap 74 , of tool 60 is curved so as to make full contact against the curved face of the borehole wall 28 . Outer cap 74 seals against borehole wall 28 and traps fluids, such as drilling fluids within chamber 84 . Alternatively, where outer cap 74 is recessed relative to stabilizer blade 40 , it is stabilizer blade 40 or alternate drill string structure that forms a seal with borehole wall 28 . A tight seal is provided between preferred tool 60 and borehole wall 28 to ensure that pressure reader 64 receives the pressure of formation 14 , and not the fluids in borehole 12 . Placement of multiple tools on a drill string, each tool placed at a differing radial position, increases the probability that the orifice of at least one such tool will be in sufficiently sealed contact with the borehole wall to assure an accurate pressure reading. The procedure for obtaining a pressure reading continues with electrical signals of a chosen frequency or frequencies delivered to tool 60 . These signals activate pulse device 70 at a corresponding mechanical frequency. Activation of pulse device 70 causes it to oscillate, thereby imparting a rhythmic expansion and contraction of the volume of chamber 84 . The rhythmic expansion and contraction of the volume in chamber 84 imparts pressure waves in the fluid. This wave energy flows through the only point of discharge, orifice 76 . Orifice 76 focuses the wave discharge into a concentrated beam. Because the pulsation frequency causes the fluid to resonate at a Helmholtz frequency, pulse device 70 efficiently transfers energy to the fluid discharge. The near instantaneous result is a flow of wave energy expelled from the tool. Orifice 76 directs the wave discharge toward borehole wall 28 layered with mudcake 30 . The fluid pulsations strike mudcake 30 , flush away the mudeake 30 , and thereby restore permeability to borehole wall 28 . At this point electrical signals to the tool can stop, and the fluid oscillation thereby ceases. The necessary period is allowed for the hydrocarbons in formation 14 to pressurize tool chamber 84 . The time period needed to pressurize chamber 84 will vary depending on factors such as the permeability of the formation and the pressure in the formation. The fluids in formation 14 seep through borehole wall 28 and into chamber 84 through orifice 76 . With hydraulic communication established via conduit 78 , chamber 84 and orifice 76 , pressure reader 64 can measure formation fluid pressure. As is known in the art, it is possible to estimate formation pressure without the need for the pressure to equalize between that of the formation and that of the chamber. Pressure reader 64 transmits the pressure data to the surface. The tool allows for continuous or near-continuous readings of formation pressure. In the logging while drilling embodiment, the movement of the drill string downward as drilling progresses also moves the tool vertically downward. However, the tool receives pressure readings from a given point on the borehole wall prior to the time that the tool descends past this point of the borehole wall. The tool clears mudcake from the borehole wall and records the formation pressure associated with the cleared area of borehole wall, prior to the orifice moving past that cleared point. Once the orifice does descend past a point on the borehole wall that has been cleared and measured for pressure, the process can begin anew. At a new, lower point on the borehole wall, the tool clears mudcake and again records formation pressure. The points of pressure measurement can be closely spaced so as to allow recording of pressure data in a continuous or near-continuous fashion. In this manner the tool will take formation pressure readings at a series of points, in an ongoing fashion, while the drill string makes its normal descent in the formation. There is no need to halt drilling in order to make these pressure readings. Preferred tool 60 provides a direct reading of formation fluid pressure that can be used to adjust the borehole pressure. That is, rig personnel can select a borehole pressure that prevents formation fluid from invading the borehole 12 without creating an excessive borehole pressure that slows drilling speed. Referring back to FIG. 1, during LWD, preferred tool 60 can be linked with a downhole telemetry system 100 to transmit formation pressure data uphole. For example, downhole telemetry system 100 could include control circuitry 102 to energize preferred tool 60 and a drive circuitry/transmitter 104 to receive pressure data from preferred tool 60 to transmit the pressure data to the surface. Drive circuitry/transmitter 104 may utilize a mud siren to transmit data in the form of pressure pulses in the drilling mud flowing uphole. Monitors 106 on the surface receive and process the pressure data transmitted by downhole telemetry system 100 . Such a system could be configured to provide continuous transmission of pressure data. Alternatively, the drive circuitry could be designed to transmit pressure data only after a threshold pressure is sensed by pressure transducer. In any event, data transmission systems for LWD in the prior art are well known, and one of ordinary skill in the art will understand how to relay pressure readings obtained from preferred tool 60 to monitoring systems on the surface. Further, one of ordinary skill in the art will know how to modify drilling mud to create a specific borehole pressure. A similar approach is followed for deploying preferred tool 60 during wireline logging operations. For wireline logging, a preferred tool 60 is usually one of several tools in a package lowered downhole. Thus, preferred tool 60 may transmit pressure data via the wireline cable to the surface. A continuous log requires that preferred tool 60 be dragged along borehole wall 28 . While it is believed that tool 60 will remove mudcake nearly instantaneously, a similarly instantaneous pressure reading may not be possible. A lag time may be involved with wireline logging. Lag time calculations are discussed in the '076 patent referenced above and incorporated by reference in its entirety. Thus, pressure reader 64 provides pressure data that allows an accurate reading of formation fluid pressure even though the fluid pressure in chamber 84 and formation 14 have not equalized. While preferred embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the scope or teaching of this invention. The embodiments described herein are exemplary only and are not limiting. Accordingly, the scope of protection is not limited to the embodiments described herein, but is only limited by the claims that follow, the scope of which shall include all equivalents of the subject matter of the claims. In the claims, the recitation of steps in a sequential order is not intended to require that the steps be performed in that order, unless explicitly so stated.
The pressure reading tool includes a housing with an interior chamber and an orifice extending from the chamber to the exterior of the housing. A pulse member with a magnetostrictive ring and an excitation source are disposed within the chamber to produce a highly agitated fluid discharge through the orifice. The magnetostrictive ring, chamber volume, and orifice cooperate to induce Helmholtz resonance frequencies in the fluid in the chamber to thereby enhance the agitation of the fluid discharge. A sheathing encapsulates the pulse member to protect it from contact with the fluid. A dampening element is also interposed between the pulse member and housing to isolate vibration.
4
TECHNICAL FIELD OF THE INVENTION [0001] This invention relates, in general, to therapy systems and, in particular, to a versatile system for providing optimal therapeutic cooling over an extensive area of a body in a convenient and highly efficient manner. BACKGROUND OF THE INVENTION [0002] There are a number of competitive, sports and athletic activities that require forceful, repetitive motion. Such activities may include, for example: pitching a baseball; throwing a football; running a race; golfing; serving a tennis ball; and swimming. As a result, participants in such activities—at all levels, from amateur to professional—can experience varying degrees of physiological stress or inflammation that may affect or inhibit their performance and participation. [0003] For example, during the course of a baseball game, a pitcher may strenuously throw a baseball 50 times or more. Such repetitive strain causes soreness and inflammation in the shoulder and arm of a player—as lactic acid builds up in the muscle tissue, and joints, tendons and muscles all become irritated and inflamed. As a result, the player may experience anything from mild discomfort that degrades on-field performance, to debilitating pain that precludes further activity. [0004] It is commonly understood that intense cooling (or “icing”) of an inflamed or sore body part can provide therapeutic benefits by reducing and relieving discomfort and inflammation. Parents, coaches, trainers and players have conventionally relied upon various icing techniques to provide such relief from sports-induced pain and discomfort, and to reduce adverse effects of sports-induced stress and strain. Typically, this took the form of placing a cold compress or an ice-bag (collectively, “compress”) on an area of the body that was sore, or prone to becoming sore. This approach was somewhat inconvenient—because someone, be it the player or another person, was usually required to hold the compress on an affected area. This approach was also limited in its scope, because the area of the body being “iced” was only as big as the compress itself. If a larger area of the body was to be treated, an individual either had to try to hold multiple compresses simultaneously, or move a single compress around periodically. [0005] Attempts were made to address these issues. Most such attempts took the general form of one of the two approaches illustrated with reference now to FIGS. 1( a ) and 1 ( b ). FIGS. 1( a ) and 1 ( b ) generally depict the torso 100 of a person having a conventional icing assembly disposed to provide relief to the shoulder/upper-arm area 102 . Referring to FIG. 1( a ), the conventional icing assembly takes the form of a bag of ice 104 disposed somewhere within area 102 and held in position by some form of wrap 106 . Ice bag 104 may be a simple as a plastic grocery or zip-seal bag, or it may actually be a conventional ice bag apparatus designed specifically to hold a limited amount of ice for medical purposes (e.g., headache relief). Some limited quantity of ice is placed into bag 104 , which is then positioned somewhere in area 102 to provide therapeutic benefit. [0006] Bag 104 may be held in place manually by an individual; or some type of wrap 106 may be utilized to position or hold bag 104 in a desired location or orientation. Wrap 106 usually takes the form of an elastic bandage, gauze, or some type of plastic wrap that is stretched repetitively around torso 100 and bag 104 . [0007] Typically, this arrangement provides a great deal of flexibility when considering the positioning of bag 104 . Bag 104 may be placed just about anywhere on the body, in a wide range of orientations, so long as wrap 106 can be positioned to hold it in place sufficiently. Furthermore, the fact that this approach utilizes actual ice provides a potentially high degree of conformity to the contours of area 102 . Depending upon the granularity of the ice used, bag 104 may be positioned and manipulated to establish direct contact with a wide variety of shapes and features of area 102 , providing a high level of therapeutic benefit. Also, ice is—generally speaking—conveniently ready in a variety of forms in many locations (e.g., snack bars, convenience stores), and can be quickly and easily replenished in a relatively short amount of time. [0008] Even so, there are a number of ways in which this approach is not optimally convenient or effective. There can be a great degree of thermal loss through the ice bag and wrap, depending upon the materials utilized—reducing the effectiveness of the icing process. Utilizing this approach to ice an extensive area can prove to be cumbersome, at best, and impossible, at worst. Concurrent icing of extensive areas of a body (e.g., the combined pectoral, shoulder and scapular areas on one side of the body) requires a large ice bag surface area. Placement of multiple standard ice bags—or even a single large ice bag (e.g., a trash bag)—and securing those bags in place with a wrap can be a laborious and time-consuming process. As such, icing by this approach may not be utilized during rest periods in the course of an event, and may be employed only after an event has concluded. Even where such awkward placement and wrapping is accomplished, full coverage of a desired area still may not be achieved. Furthermore, for the individual receiving the icing, this approach can be uncomfortable and inconvenient. Typically, once an individual has been wrapped for icing in this manner, they need to remain relatively sedentary or stationary because the ice bag and its wrapping are likely to shift or slide due to the effects of gravity, and especially if the individual moves around. Wrapping can pinch, bind and chafe the individual, and may restrict the movement of body parts not being iced. [0009] Another conventional icing assembly is described now in reference to FIG. 1( b ). This conventional assembly attempts to overcome some of the deficiencies of approach illustrated in FIG. 1( a ), but then causes other problems of its own. In this approach, the icing assembly takes the form of a compress 108 disposed somewhere within area 102 , and held in position by one or more straps 110 . Compress 108 typically comprises some sort of re-freezable medium—such as a gel pack or water bag. The re-freezable medium is separated or removed from the assembly, and kept in a freezer or refrigeration unit until needed. When icing is commenced, the medium is removed from refrigeration and reattached to straps 110 , or placed in some sort of pouch to which straps 110 are already attached. The assembly is then positioned in a desired location within area 102 , and secured in place with straps 110 . [0010] This approach usually overcomes the comfort, and certain convenience, limitations of the previously described approach. Individuals typically experience lesser, or no, restriction on their movement while icing is in progress. The straps generally keep the compress well-positioned even if the individual is active and moving. Also, in most cases, the straps tend not to bind or pinch to the same extent that a wrap 104 does. Even so, this approach does have a number of disadvantages. [0011] For example, most compresses 108 tend to be small to moderate in size, and thus effective for icing only a limited, localized area. Because the re-freezable medium has to be of a size that can easily fit within a freezer or refrigeration unit, compress 108 is typically not of a sufficient size to concurrently ice an extensive area of the body. Furthermore, once the re-freezable medium is removed from refrigeration, it is generally rigid in nature and does not readily conform to contours and shapes of icing area 102 . This results in a reduced therapeutic effect for the icing process. Thermal loss due to the materials used for the compress can further degrade the therapeutic effects of this approach. [0012] Once a compress 108 has been used for any length of time, it typically requires re-freezing before it can be reused. This renders it inconvenient for repetitive or prolonged use by multiple individuals. As a result, multiple re-freezable mediums must be on location if this icing approach is to be used on-site during an event. Further inconvenience then stems from the transport of extra material (i.e., multiple re-freezable mediums) and the need to have access to on-site refrigeration. [0013] As such, there arises a need for a versatile system that provides optimal therapeutic cooling, over an extensive area of the body, in a convenient and highly efficient manner. SUMMARY OF THE INVENTION [0014] The present invention disclosed herein provides a versatile system for providing optimal therapeutic cooling over an extensive area of the body, in a convenient and highly efficient manner. The present invention recognizes that optimal therapeutic cooling (or icing) of a part or area of a body depends on several factors, and addresses each to maximize icing effectiveness. At the same time, the present invention achieves these ends with a system that is comfortable, convenient and easy to use. [0015] The system of the present invention provides numerous structures and methods, including a therapeutic icing apparatus that may be utilized to treat an extensive area of individual's body. The present invention provides a receptacle component to hold an icing medium—whether that be ice, re-freezable mediums (e.g., gels), or removable pouch or bladder—and compress that icing medium against the desired area. A positioning component maintains the receptacle component in a desired orientation, and optimizes the individual's comfort and mobility. One or more compression components are provided to optimize compression of the receptacle component, without causing discomfort to the individual. The materials and configuration of the system are provided to optimize the adaptability, effectiveness and convenience of the system. [0016] In one aspect, the present invention provides a system for therapeutically cooling a desired area on an individual's body. The system comprises a therapeutic medium receptacle, having insulating and compression features. A positioning component is connected to the therapeutic medium receptacle, and adapted to maintain the therapeutic medium receptacle in a desired orientation with respect to the desired area. A compression component is connected to the therapeutic medium receptacle, and adapted to facilitate compression of the therapeutic medium receptacle against the desired area. [0017] In certain embodiments, a therapeutic medium may be loaded directly into therapeutic medium receptacle. In other embodiments, a container component is provided and a therapeutic medium is loaded therein. That container component is provided in a manner such that it may be easily disposed within the therapeutic medium receptacle. [0018] In another aspect, the present invention provides a method of therapeutically cooling a desired area on an individual's body. A therapeutic medium receptacle is provided with insulating and compression features. A positioning component is connected to the therapeutic medium receptacle, and adapted to maintain the therapeutic medium receptacle in a desired orientation with respect to the desired area. A compression component is connected to the therapeutic medium receptacle, and adapted to facilitate compression of the therapeutic medium receptacle against the desired area. Therapeutic medium is loaded into the therapeutic medium receptacle, either directly or within a container component, and the therapeutic medium receptacle, the positioning component, and the compression component are secured in place on the individual's body. BRIEF DESCRIPTION OF THE DRAWINGS [0019] 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 in which corresponding numerals in the different figures refer to corresponding parts and in which: [0020] FIGS. 1( a ) and 1 ( b ) are diagrams illustrating prior art materials and methods for therapeutic icing; [0021] FIG. 2 is a diagram illustrating one embodiment of a therapeutic icing system according to certain aspects of the present invention; [0022] FIG. 3 is a diagram illustrating additional aspects of the embodiment illustrated in FIG. 2 ; [0023] FIG. 4 is a diagram illustrating one embodiment of a receptacle component according to certain aspects of the present invention; [0024] FIG. 5 is a diagram illustrating a cross-sectional view of one embodiment of a receptacle panel according to certain aspects of the present invention; [0025] FIG. 6 is a diagram illustrating one embodiment of a position component according to certain aspects of the present invention; [0026] FIG. 7 is a diagram illustrating one embodiment of a therapeutic icing system according to certain aspects of the present invention; [0027] FIG. 8 is a diagram illustrating one embodiment of a container component according to certain aspects of the present invention; [0028] FIG. 9 is a diagram illustrating another view of the container component depicted in FIG. 8 ; [0029] FIGS. 10( a )- 10 ( c ) are diagrams illustrating one embodiment of a loading assembly according to certain aspects of the present invention; and [0030] FIGS. 11( a ) and 11 ( b ) are diagrams illustrating another embodiment of a therapeutic icing system according to certain aspects of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0031] 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 which can be embodied in a wide variety of specific contexts. For example, certain embodiments of the present invention are illustrated and described in relation to therapeutic cooling of the shoulder region of a human torso. The principles and practices of the present invention may also be applied to other areas or parts of the body—such as the knee region or lower back area, for example. The principles and practices of the present invention may also be applied to non-human uses, such as race horse therapy. Furthermore, certain embodiments of the present invention are described and illustrated in reference to specific materials, even though numerous other suitable materials may also be utilized in accordance with the present invention. Therefore, 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. [0032] Referring initially to FIGS. 2 and 3 , one embodiment of a therapeutic cooling apparatus 200 according to the present invention is illustrated. Apparatus 200 is illustrated in reference to therapeutic cooling (hereinafter “icing”) of the shoulder region of torso 202 , so as to provide illustrative comparison to the prior art approaches previously illustrated in FIGS. 1( a ) and 1 ( b ). It should be clearly understood, however, that other configurations in accordance with the following specification may be provided for icing of other body parts or regions. [0033] Apparatus 200 comprises: one or more positioning component(s) 204 ; one or more medium receptacle(s) 206 secured to, or integrated with, positioning component(s) 204 ; and one or more compression component(s) 208 secured to, or integrated with, medium receptacle(s) 206 and aligned with positioning component(s) 204 . [0034] Medium receptacle(s) 206 are formed and fabricated to receive and secure an icing medium (e.g., ice)—either directly, or within a container component—and to place the icing medium in close or direct contact with a desired area of the body part 202 . Medium receptacle(s) 206 are formed and fabricated to provide compressive force sufficient to maintain the icing medium in therapeutic contact with the desired area. Medium receptacle(s) 206 are configured as a pouch, sheath, pocket, shell or other suitable receptacle for receiving an icing medium. In some embodiments, an icing medium may be deposited directly into receptacle 206 . In other embodiments, receptacle 206 may be configured to receive a container component—such as a bladder, bag or other similar component—that contains the icing medium. In embodiments where an icing medium is deposited directly into receptacle 206 , the interior surfaces of the receptacle may be comprised of or covered with a suitable waterproof material, so as to prevent messes or damage from melting icing medium. For purposes of explanation and illustration, however, the description hereafter references embodiments where receptacle 206 is configured to receive a component that contains the icing medium (referred to hereinafter as “container component”). [0035] In the embodiment depicted in FIG. 2 , receptacles 206 are formed of sufficient size and shape so as to provide therapeutic icing coverage to the entire pectoral, upper shoulder and scapular area of torso 202 . Although receptacles 206 are formed to provide such extensive treatment, they may also be selectively used to treat a smaller area. In the illustrated embodiment, one large symmetrical receptacle 206 is formed in a “saddlebag” shape so as to extend from front to back evenly. This receptacle 206 , and this embodiment of apparatus 200 , is operationally symmetrical such that a single apparatus may be worn over either the left or right shoulder of an individual. Another smaller, symmetrical receptacle 206 is attached to or integrated with the larger receptacle, so as to extend coverage of the apparatus over the deltoid region of torso 202 . [0036] Apparatus 200 further comprises coverings 210 and 212 that are movably disposed over the open portions of receptacles 206 . Covering 210 comprises a large flap attached to or integrated with the large receptacles 206 in such a manner that it extends over the crest of the shoulder area of apparatus 200 . Covering 210 encloses an icing bladder within large receptacle 206 —securing the icing bladder in place, and providing thermal and compression benefits similar to those of receptacle 206 . Covering 206 is illustrated hereinafter in greater detail. Apparatus 200 may comprise some form of attachment or closure member 214 that keeps covering 210 closed securely during use of the apparatus. Covering 212 comprises a smaller flap that extends from covering 210 outwardly over smaller receptacle 206 —enclosing the icing bladder therein, and providing the same benefits as covering 210 . In alternative embodiments, covering 212 may be affixed to receptacle 206 , or removably attached to covering 210 . [0037] Apparatus 200 comprises one or more positioning components 204 that may be contiguously formed, or individually formed and integrated or attached. Positioning components 204 are integrated with, or attached to, receptacle(s) 206 . They are formed of size, shape and material to maintain or hold receptacle(s) 206 in a desired orientation with respect to torso 202 . The formation and material selection for positioning component(s) 204 may also factor in several convenience or comfort factors—such as optimizing comfort of an individual wearing apparatus 200 , or maximizing mobility the individual while wearing apparatus 200 . In the embodiment depicted, positioning component(s) 204 are formed of neoprene—or some similar substance such as Lycra™, rip-stop nylon, etc.—that provides sufficient firmness or rigidity to maintain the positioning of receptacle(s) 206 while providing some degree of comfort to the individual. In this particular embodiment, positioning component(s) 204 provide a sleeve and harness-type foundation for apparatus 200 . The closure and securing of positioning component(s) 204 around the torso is described in greater detail hereinafter. [0038] Compression components 208 are attached to, and work in conjunction with, receptacle(s) 206 to maximize contact and contouring of the icing medium along the desired area of torso 202 . Compression components 208 comprise straps that may be permanently or removably attached to receptacle(s) 206 . In the embodiment depicted, compression components 208 comprise nylon straps that are affixed to the front and back portions of large receptacle 206 , and secure together at the sides of torso 202 with friction-type buckles 216 . As such, the amount of tension provided by components 208 may be easily adjusted. Other embodiments of the present invention may comprise other connectors (e.g., snap-lock buckles, Velcro™) and other strapping materials (e.g., canvas straps, elastic straps, elastic cords). [0039] Tension provided by compression components 208 works in conjunction with certain features of receptacle(s) 206 , described hereinafter, to optimize the inward pressure applied to an icing medium disposed with the receptacle(s). This pressure provides optimal contouring of the icing medium to the body part being iced, and provides optimal icing contact across the area being treated. In some embodiments, compression components may be provided in conjunction with other receptacles—such as around the small shoulder receptacle, for example. [0040] A receptacle according to the present invention is explained with reference now to FIG. 4 , which depicts an illustrative, but generalized, embodiment of a receptacle 400 in accordance with the present invention. Receptacle 400 comprises an inward face 402 and an outward face 404 , as well as an exterior area 406 and an interior area 408 . When in use in an apparatus of the present invention, inward face 402 is the portion of the receptacle that is in direct contact with (or in closest proximity to) an area of a body under treatment. Outward face 404 is the outermost surface of the exterior portion of the receptacle. Interior area 408 is that area inside the pouch, pocket or sheath formed by receptacle 400 , within which an icing medium or icing bladder is contained. Exterior area 406 is that area around the outer perimeter of receptacle 400 , along which inward face 402 and outward face 404 are disposed. In some embodiments, inward face 402 may comprise a mesh, thin nylon, or other suitable material that is sturdy or secure enough to retain an icing medium or icing bladder, and thermally penetrable to provide optimal thermal exposure of the icing medium or icing bladder to the area of the body under treatment. [0041] Receptacle 400 further comprises an exterior panel 410 disposed along outward face 404 , between outward face 404 and interior area 408 . Panel 410 comprises a plurality of layers that provide thermal insulation, to minimize melting of an icing medium, as well as a rigid or inflexible quality to enable application of compressive force to interior area 408 . When compressive force is applied to the outward face 404 by compressive components, force is transferred via panel 410 to the icing medium within interior area 408 —resulting in optimal contouring of the icing medium to the body part being iced, and optimal icing contact with the area being treated, via inward face 402 . [0042] Referring now to FIG. 5 , an illustrative embodiment of a panel 410 is depicted in cross-sectional form. The outermost layer 500 , which forms outward face 404 , comprises a flexible fabric or material that is rugged, yet aesthetic. Layer 500 must be suitable to withstand wear and tear, repetitive cleanings, etc., while protecting the layer(s) beneath it. In the embodiments illustrated herein, layer 500 comprises a polyurethane material with a cotton fabric backing. Immediately under layer 500 is layer 502 , which is a rigidity layer. Layer 502 is of made of material of sufficient thickness, density and rigidity to provide the desired compression characteristics detailed herein. In the embodiments illustrated herein, layer 502 comprises one or more foam sub-layers. For example, layer 502 may comprise flexible foam sandwiched between expanded polystyrene and ethylene/vinyl acetate (EVA). [0043] Immediately under layer 502 is layer 504 , which is an insulation layer. Layer 504 comprises material that maintains cold within area 408 , and retards or prevents the escape of cold through panel 410 . Layer 504 may comprise any suitable insulating material—such as foam, foil, synthetic, or fiberfill materials. In the embodiments illustrated herein, layer 504 comprises an aluminum foil-based insulating material. Immediately under layer 504 is layer 506 , which is an exposure layer, forming an inner surface of area 408 . Layer 506 is directly exposed to either the icing medium or icing bladder, and comprises material suitable to withstand wear and tear, cold temperature, and potential wet conditions, while protecting the layer(s) above it. In the embodiments illustrated herein, layer 506 comprises polyester, “rip-stop” type material. [0044] Referring now to FIG. 6 , certain aspects of apparatus 200 are described now in greater detail. FIG. 6 depicts an illustrative view 600 of apparatus 200 , in which the compression component(s) 208 and outer portions of receptacle(s) 206 are not shown. Positioning component(s) 204 are shown, as are the mesh inward faces 402 of the receptacles, integrated or otherwise attached to component(s) 204 . Component(s) 204 comprise open flap portions 602 that form an opening for an individual to put the apparatus on. As depicted, flap portions 602 overlap each other, wrap securely around the torso 202 , and are fastened in place via an attachment component 604 . In other embodiments, flap portions 602 may abut one another, without overlapping, when closed and secured. As depicted, attachment component 604 comprises a Velcro™ patch that affixes to the exterior of a neoprene opposite flap portion 602 at closure area 218 . In other embodiments, attachment component 604 may comprise buckles, snaps, zippers, hooks or any other closure mechanism that provides secure and comfortable closure of the apparatus. [0045] In the embodiment depicted, component(s) 204 are formed of a nylon-covered neoprene material, of sufficient thickness and pliability to secure the orientation/position of receptacle 206 , even when the individual is moving around, and to provide support and comfort. Furthermore, faces 402 are formed and positioned to provide icing exposure and contact to an expansive area of torso 202 . [0046] For purposes of illustration and explanation, FIG. 7 presents a perspective view of the apparatus 700 of the present invention in an in-use position upon an individual 702 . The inner areas 408 are aligned along the expansive area from the pectoral region, up and over the shoulder region, to the scapular region. Mesh faces 402 are intact along the flesh or undergarment surface of individual 702 that is to be therapeutically treated. Once apparatus 700 is secured in place, an icing medium or icing bladder may be disposed within receptacles 206 , after which closures 210 and 212 may be moved into place and secured by closure member 214 . In this embodiment, closure member 214 comprises a Velcro™ type closure. Apparatus 700 is provided such that loading, and re-loading, of an icing medium may be accomplished while individual 702 is wearing the apparatus. As such, for convenience and stability, this embodiment is configured in a top-loading fashion. Other embodiments may be provided in alternative arrangements, such as front loading or side loading. [0047] Referring now to FIGS. 8 and 9 , one embodiment of a container component 800 , a removable icing bladder in this instance, is illustrated in accordance with the present invention. This embodiment of bladder 800 is shaped and formed to operate in conjunction with apparatus 700 (not shown), and is thus illustrated in relation to individual 702 . Bladder 800 comprises lateral portions 802 that symmetrically cover the pectoral and scapular areas of individual 702 , and a shoulder portion 804 that covers the deltoid area of individual 702 . A central upper portion 806 covers the trapezius area of individual 702 once a closeable loading assembly 808 is closed and secured. [0048] In this embodiment, bladder 800 is positioned within apparatus 700 such that lateral portions 802 are evenly positioned with the large receptacles 206 , and shoulder portion 804 is positioned within the small receptacle 206 . Once bladder 800 is in place within apparatus 700 , ice may be loaded into the top of bladder via assembly 808 , which is described in greater detail hereinafter. Bladder 800 is formed of material that is sufficiently rugged to withstand repetitive thermal changes and substantial wear and tear. In most embodiments, bladder 800 is formed to be substantially or completely waterproof, so as to avoid inconvenience and discomfort from leaking. Thus, in some embodiments, bladder 800 may be formed from an injection-molded rubber material. In other embodiments, it may be formed from a waterproof textile that is seam-welded together. Still other embodiments may utilize other materials and other configurations. [0049] Bladder 800 may optionally comprise one or more drain components 810 that allow melted icing medium (i.e., ice water) to be selectively drained out of the bladder without removing the bladder 800 or apparatus 700 from the individual 702 . Drain components 810 may comprise simple plastic pinch-valves or spigots, or any other suitable components that allow for selective draining of bladder 800 . Component 800 may further comprise one or more internal baffles (not shown). These internal baffles may be provided so as to control the expansion, or maintain the relative shape, of component 800 as ice is loaded therein. The baffles may also be provided in such a manner as to reduce the amount of ice necessary within component 800 to achieve optimal therapeutic effects. Component 800 may also optionally comprise other shape-retention components—such as semi-rigid ribs or panels—embedded within component 800 . [0050] Referring now to FIGS. 10( a )- 10 ( c ), one embodiment of a closable loading assembly 808 and several stages of its deployment are illustratively depicted. Assembly 808 is provided such that it may be securely closed in position as previously depicted in FIG. 9 . Assembly 808 is formed and configured such that opens outwardly from bladder 800 , preferably in a manner that provides a large, chute type, top-loading opening 1000 when fully deployed. In other embodiments, assembly 808 may be provided in a manner that provides a large, chute type opening for other loading orientations, such as front-loading or side-loading. Assembly 808 comprises a number of fan-fold features 1002 that enable a user to close the assembly in upon itself 1004 once filling is complete. Assembly 808 further comprises one or more closure components 1006 —such as snaps, Velcro™, zippers, etc.—that provide secure mechanical and thermal closure of bladder 800 . Assembly 808 may also comprise a rigid or semi-rigid upper seam 1008 to facilitate stability of the assembly when in its open deployed state. [0051] As depicted in FIG. 10( a ), assembly 808 is in an open deployed state. Ice may be loaded, through chute-type opening 1000 , into bladder 800 . Once filling is concluded, outer portions 1010 are folded in upon themselves 1004 along fold features 1002 , as depicted now in FIG. 10( b ). The top of assembly 808 , from upper seam 1008 , is then alternately folded over upon itself along fold features 1002 , and one or more closure components 1006 may be engaged. Finally, in FIG. 10( c ), the last remaining fold is completed and a closure component 1006 is engaged to keep the assembly in its closed, in-use position. [0052] Referring now to FIGS. 11( a ) and 11 ( b ), another embodiment of an icing assembly 1100 in accordance with the present invention is illustrated. In this embodiment, assembly 1100 is provided for icing the elbow region 1102 of an individual. Assembly 1100 comprises an exterior panel 410 , an inward face 402 , and an interior area 408 . An icing medium or container component is placed within area 408 , and assembly 1100 is wrapped around the elbow area 1102 and closed. Assembly 1100 comprises a closure component 1104 that to secure the assembly in a closed position. In the illustrated embodiment, component 1104 functions both as a closure component and a compression component. In other embodiments, assembly 1100 may have only a closure component, a closure component in conjunction with one or more independent compression components, or one or more compression components without a closure component. Other variations are hereby comprehended. [0053] Apparatus 1100 may be worn independently, or it may be worn in conjunction with another apparatus 200 . It may be desirable to provide one or more positioning components 1106 to operationally attach the apparatus together. In other embodiments, apparatus 1100 may be formed as an integral part of apparatus 200 . [0054] In all of the embodiments of the present invention, a variety of adaptations and configurations are comprehended and anticipated by this disclosure. For example, any component, assembly or member may be formed integrally with another, or may be formed individually and either removably or permanently attached thereto. Any number of materials or assemblies may be substituted in place of those illustrated, so long as they provide the same form, function or characteristics. Although the embodiments disclosed are illustrated in reference to treatment of a torso area, those same embodiments may be applied with equal effectiveness to treatment of other areas or regions of the body. It is further comprehended that, although the embodiments disclosed are illustrated in reference to a human body, it is within the scope of the present invention that such treatments may be applied to non-human bodies (e.g., race horses). [0055] Thus, while this invention has been described with a reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. As explained above, various modifications and combinations of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to the description. It is, therefore, intended that the appended claims encompass any such modifications or embodiments.
A system provides therapeutic reduction of, and relief from, discomfort and inflammation stemming from strenuous physical activity. The system provides a therapeutic icing apparatus that placed in position along a desired area of an individual's body. The apparatus has a receptacle component to hold an icing medium, and compress that icing medium against the desired area. A positioning component is included to maintain the receptacle component in a desired orientation, and to optimize the individual's comfort and mobility. One or more compression components are provided to optimize compression of the receptacle component, without causing discomfort to the individual. The materials and configuration of the system are provided to optimize the adaptability, effectiveness and convenience of the system.
0
BACKGROUND The present invention relates generally to apparatus for well completions, and in particular, to apparatus for isolating distinct zones from each other in a well bore. In completion of a well bore for oil, gas, or the like, it is often desired to perform certain completion operations in a particular zone of the well bore, such as gravel packing, acidizing, or the like. After completion of one of these operations, it is often necessary to protect the structure in which the operation was performed by isolating the zone in which the operation was performed from other zones of the well bore during completion operations of the other zones. However, after operations in the other isolation areas of the well bore have been completed, it is necessary to open the isolated area to complete the well bore. Therefore, there is a need for apparatus and methods for isolating a zone of the well bore that can be re-opened for final completion of the well bore. Completion of the well bore can be affected by the type of debris that is created within that well bore. Therefore, there is a need for apparatus and methods of isolating particular zones in a well bore that reduce the amount of debris that negatively influences the completion of the well bore. Before a zone is isolated in a well bore, it may be necessary to draw fluids from the zone to be isolated through any device that is later used to isolate the particular zone. Fluid flow through an isolation device, prior to use of the device to isolate a particular zone, may be at high flow rates. Therefore, there is a need for apparatus and methods which allow high fluid flow to and from the zone to be isolated, prior to isolating that particular zone. SUMMARY The present invention is directed to an apparatus that satisfies the above mentioned need. In one embodiment, the apparatus comprises a fluid loss device with a housing, a seal assembly, a running tool, and a plug. The housing has a longitudinal bore therethrough. The seal assembly includes a compression sleeve and a collet sleeve. The compression sleeve is positioned within the longitudinal bore of the housing and has an inner compression land. The collet sleeve is positioned within the compression sleeve and has a collet seal section with an outer compression land that is larger than the inner compression land of the compression sleeve. The plug is detachably attached to the running tool. This particular embodiment of the fluid loss device also includes means for sealing between the compression sleeve and the housing, and means for securing the inner compression land of the compression sleeve in engagement with the outer compression land of the collet sleeve such that the collet seal section of the collet sleeve is reduced to a predetermined size for sealing engagement with the plug. In another embodiment, the present invention comprises a fluid loss device with a housing, a seal assembly, a running tool, a plug, a housing seal, a plug seal. The housing has a longitudinal bore therethrough. The seal assembly has a plug bore therethrough. The plug is detachably attached to the running tool. The housing seal is adapted for providing a sealing engagement between the seal assembly and the longitudinal bore in the housing. This particular embodiment of the fluid loss device also includes means for releasably securing the seal assembly within the longitudinal bore of the housing such that the housing seal provides a seal between the seal assembly and the longitudinal bore of the housing. The plug seal is adapted for providing sealing engagement between the plug bore of the seal assembly and the plug. This particular embodiment of the fluid loss device also includes means for releasably securing the plug within the plug bore of the seal assembly such that the plug seal provides a seal between the plug and the plug bore of the seal assembly. In a further embodiment, the seal assembly includes a compression sleeve and a collet sleeve, the plug seal includes a collet seal section on the collet sleeve, and the means for releasably securing the plug further includes an inner compression land on the compression sleeve, an outer compression land on the collet seal section of the collet sleeve, and means for securing the inner compression land in engagement with the outer compression land. The compression sleeve is positioned within the longitudinal bore of the housing. The outer compression land is larger than the inner compression land. The means for securing the inner compression land in engagement with the outer compression land is adapted for securing the inner compression land in engagement with the outer compression land of the collet sleeve such that the collet seal section in the collet sleeve is reduced to a predetermined size for engagement with the plug. In another further embodiment, the means for releasably securing the seal assembly comprises a stop dog, a stop dog aperture in the seal assembly, a stop dog recess in the housing, and the plug has a stop dog release surface, a stop dog locking surface, and a stop dog cam surface connecting the two surfaces. The plug is disposed within the plug bore of the seal assembly such that the stop dog rests against the stop dog release surface, and movement of the plug causes the stop dog to follow the stop dog cam surface to the stop dog locking surface. The stop dog locking surface is such that the stop dog is forced to extend outwardly from the stop dog aperture in the seal assembly and into the stop dog recess in housing. In another further embodiment, includes a shear pin recess in a shear pin surface of the plug, the seal assembly includes a shear pin aperture, and the means for securing the plug includes a shear pin disposed within the shear pin aperture of the seal assembly and means for forcing the shear pin against the shear pin surface of the plug such that alignment of the shear pin recess in the plug will force the shear pin into engagement with the shear pin recess of the plug and the shear pin aperture of the seal assembly. In another further embodiment, the running tool includes a running tool mandrel having a skirt stop land and means for detachably attaching the plug, a running tool skirt having a mandrel stop land, and means for engaging the skirt stop land with the mandrel stop land. The skirt stop land of the running tool mandrel and the mandrel stop land of the running tool skirt are positioned such that when the plug detaches from the running tool mandrel the skirt stop land of the running tool mandrel contacts the mandrel stop land of the running tool skirt and the running tool skirt inhibits the running tool mandrel from contacting the plug. BRIEF DESCRIPTION OF THE DRAWINGS A more complete understanding of the apparatus and methods of the present invention may be had by reference to the following Detailed Description when taken in conjunction with the accompanying Drawings wherein: FIG. 1 is a fragmentary view in section and elevation of a well bore utilizing an embodiment of the present invention; FIG. 2 is a view as in FIG. 1, further illustrating in section the present invention from FIG. 1; FIG. 3 is an enlarged fragmentary view in section and elevation of an embodiment of the fluid loss device in FIGS. 1 and 2; FIG. 4 is a sectional view of the housing in FIG. 3; FIG. 5 is a sectional view of the seal assembly in FIG. 3; FIG. 6 is a sectional view of the wash pipe assembly, running tool assembly, and plug in FIG. 3; FIGS. 7A-7F are sectional views illustrating operation of the fluid loss device in FIGS. 3-6; FIG. 8 is an enlarged fragmentary view in section and elevation of another embodiment of the fluid loss device in FIGS. 1 and 2; FIG. 9 is a sectional view of the seal assembly in FIG. 8; FIG. 10 is a sectional view of the wash pipe assembly, running tool assembly, and plug in FIG. 8; and FIGS. 11A-11F are sectional views illustrating operation of the fluid loss device in FIGS. 8-10. DETAILED DESCRIPTION A well bore 1 is shown in FIG. 1 and generally comprises a bore hole 2 drilled through non-producing overburden layers 3a, 3b, a producing or pay zone 4, and a non-producing zone 5. A tubular casing 6 is cemented into the bore hole 2. Perforations 7 are located in the casing 6 within the producing zone 4. A production zone 23 of the well bore 1 is separated from a sump zone 22 of the well bore 1 by a sump packer 21. The production zone 23 of the well bore 1 is separated from an upper zone 25 of the well bore 1 by an upper packer 24. Between the sump packer 21 and the upper packer 24 is placed a well filtration device such as a well screen 31. The well screen 31 is connected to the sump packer 21 by a seal 32. The screen 31 is also connected by blank production tubing 33 to the fluid loss device 10, which is connected to the upper packer 24. Connection from above the upper packer 24 is accomplished by the upper production tubing 35. In one operation where gravel packing is performed, as shown in FIGS. 1 and 2, a wash pipe assembly 90, having a perforated subassembly 91 on the end of a wash pipe 92, is inserted through the fluid loss device 10 and the blank production tubing 33 before the upper production tubing 35 is connected to the upper packer 24. The wash pipe assembly 90 is positioned with the perforations of the perforated subassembly 91 located behind the screen 31. After the wash pipe assembly 90 is positioned with the perforated subassembly 91 behind the screen 31, gravel is pumped into the production zone 23 of the well bore 1 the annulus around the outside of the fluid loss device 10, the blank production tubing 33, the screen 31, and the seal 32. During the time when gravel is pumped into the production zone 23 of the well bore 1, fluids passing through the screen 31 are drawn through the perforations of the perforated subassembly 91, and exit the well bore 1 through the wash pipe 92. Other operations can also be performed with the wash pipe assembly 90, such as acidizing. After the operations requiring the wash pipe assembly 90 are performed, it is often desired to protect the formations created by these operations from other operations in the upper zone 25 of the well bore 1 by sealing off the production zone 23 from the upper zone 25 while these other operations are being performed. To seal off the production zone 23 from the upper zone 25, the fluid loss device 10 is activated and the wash pipe assembly 90 is withdrawn from the well screen 31, the blank production tubing 33, and the fluid loss device 10. Once the operations above the production zone 23 are completed, the fluid loss device 10 is deactivated or cleared to allow communication with the upper production tubing 35. One embodiment of the fluid loss device 10 of FIGS. 1 and 2 is illustrated in FIG. 3 as the fluid loss device 100. The fluid loss device 100 generally comprises a housing 200, a seal assembly 300, a running tool assembly 400, and a plug or ball 500. The housing 200, as shown in FIGS. 3 and 4, comprises a top sub 210, a middle sub 220, and a bottom sub 230. An upper portion of the top sub 210 of the fluid loss device 100 attaches to the upper packer 24 (shown in FIGS. 1 and 2), and a lower portion of the top sub 210 attaches to an upper portion of the middle sub 220. An upper portion of the bottom sub 230 attaches to a lower portion of the middle sub 220, and a lower portion of the bottom sub 230 attaches to the blank tubing 33 (shown in FIGS. 1 and 2). The top sub 210 has a first inner diameter 211 in the upper portion, and a larger second inner diameter 212 in the lower portion. A stop land 214 is created between the first inner diameter 211 and the second inner diameter 212 of the top sub 210. The middle sub 220 has a first inner diameter 221 in the upper portion, and a second inner diameter 222 in the lower portion. A stop land 223 is created between the first inner diameter 221 and the second inner diameter 222 of the middle sub 220. The bottom sub 230 has an inner diameter 231. In one embodiment, the first inner diameter 211 of the top sub 210 is approximately the same diameter as the second inner diameter 222 of the middle sub 220, and the inner diameter 231 of the bottom sub 230 is approximately the same diameter as the second inner diameter 222 of the middle sub 220. A snap ring groove 240 is defined by a snap ring recess 216 in the lower portion of the top sub 210 aligning with a snap ring recess 226 in the upper portion of the middle sub 220. A snap ring 250 resides within the snap ring groove 240. A seal 270 resides within a seal groove 224 that is recessed into the first inner diameter 221 of the middle sub 220. In one embodiment, the seal assembly 300, as shown in FIGS. 3 and 5, includes a compression sleeve assembly 310 and a collet seal assembly 360. The compression sleeve assembly 310 generally comprises a sleeve 320 and a shear ring 330. The sleeve 320 has an outer diameter 321 and an inner diameter 322. At the upper end of the sleeve 320, a sleeve stop edge 323 is created between the outer diameter 321 and the inner diameter 322. At the lower end of the sleeve 320, a compression land 324 is created by decreasing the inner diameter 322 of the sleeve 320. A snap ring groove 325 is recessed into the outer diameter 321 of the sleeve 320. The shear ring 330 has an outer diameter 331 smaller than the inner diameter 322 of the sleeve 320, and a inner diameter 332 larger than the diameter of the wash pipe assembly 90. A running tool interface edge 334 is created on a lower edge of the shear ring 330 between the outer diameter 331 and the inner diameter 332. The shear ring 330 is secured to the sleeve 320 by a plurality of shear pins 340 disposed within shear pin apertures 333 in the shear ring 330 and shear pin apertures 326 in the sleeve 320. The compression sleeve assembly 310 is secured to the housing 200 by a plurality of shear pins 350 engaging shear pin apertures 327 in the sleeve 320 and shear pin apertures 215 in the top sub 210 of the housing 200. The collet seal assembly 360 has an outer diameter 361 and an inner diameter 362. The outer diameter 361 is smaller than the second inner diameter 222 of the middle sub 220. A collet seal 365 is created in an upper portion of the collet seal assembly 360 by alternating seal fingers 366 and resilient seal material 367 longitudinally in the walls of the collet seal assembly 360. A compression land 364 is created on an upper portion of the collet seal 365 by increasing the outer diameter 361 of the collet seal 365 to a diameter larger than the compression land 324 of the sleeve 320 in the compression sleeve assembly 310, but smaller than the inner diameter 322 of the sleeve 320. The collet seal assembly 360 is secured to the housing 200 by a plurality of shear pins 370 secured within shear pin apertures 363 in the collet seal assembly 360 and shear pin apertures 225 in the middle sub 220 of the housing 200. The running tool 400, as shown in FIGS. 3 and 6, generally comprises a mounting collar 410, a running tool mandrel 420 and a running tool shear sleeve 430. The mounting collar 410 has an outer diameter 411 smaller than the inner diameter 332 of the shear ring 330 in the compression sleeve assembly 310. At an upper end of the mounting collar 410 is a threaded wash pipe mounting aperture 412 for engagement of the wash pipe assembly 90. At a lower end of the mounting collar 410 is a threaded mandrel aperture 413 for engagement of the running tool mandrel 420. The running tool mandrel 420 has a first diameter 421 on an upper portion of the running tool mandrel 420 and a second diameter 422 on a lower portion of the running tool mandrel 420. The first diameter 421 of the running tool mandrel 420 is smaller than the second diameter 422, creating a stop land 423 on the running tool mandrel 420. On the lower end of the running tool mandrel 420 is a concave ball mounting recess 424. A threaded ball mounting bolt aperture 425 extends upwardly into the running tool mandrel 420 through the concave ball mounting recess 424. The running tool shear sleeve 430 has an outer diameter 431, a first inner diameter 432, and a second inner diameter 433. The outer diameter 431 of the running tool shear sleeve 430 is greater than the inner diameter 332 of the shear ring 330, but smaller than the inner diameter 322 of the sleeve 320. The first inner diameter 432 of the running tool shear sleeve 430 is larger than the first diameter 421 of the running tool mandrel 420, but smaller than the second diameter 422 of the running tool mandrel 420. The second inner diameter 433 of the running tool shear sleeve 430 is larger than the second diameter 422 of the running tool mandrel 420. A stop land 434 is created inside the running tool shear sleeve 430 between the first inner diameter 432 and the second inner diameter 433. In this manner, the stop land 434 of the running tool shear sleeve 430 will engage the stop land 423 of the running tool mandrel 420. A shear ring interface edge 435 is located on the upper edge of the running tool shear sleeve 430 between the outer diameter 431 and the first inner diameter 432, such that vertical engagement with the running tool interface edge 334 of the shear ring 330 is possible. By-pass grooves 436 are positioned within the shear ring interface edge 435 of the running tool shear sleeve 430 such that metered fluid by-pass is possible when the shear ring interface edge 435 of the running tool shear sleeve 430 engages the running tool interface edge 334 of the shear ring 330. At the lower edge of the running tool shear sleeve 430, a ball interface surface 438 is defined between the outer diameter 431 and the second inner diameter 433. The running tool shear sleeve 430 is mounted to the running tool mandrel 420 by a plurality of shear pins 440 secured within the shear pin apertures 437 in the running tool shear sleeve 430 and shear pin apertures 426 in the running tool mandrel 420. The plug or ball 500, as shown in FIGS. 3 and 6, has an outer diameter 510 that is smaller than the inner diameter 362 of the collet seal assembly 360 in a relaxed position. A ball attachment bolt 540 is secured within a threaded bolt aperture 520 of the ball 500. A fracture clearance recess 530 provides clearance between the ball 500 and the ball attachment bolt 540 below the surface of the outer diameter 510 of the ball 500. The ball attachment bolt 540 has a prestressed area 541 which is located below the outer diameter 510 of the ball 500 and within the fracture clearance recess 530. The ball 500 is secured to the concave ball mounting recess 424 of the running tool mandrel 420 by engaging the ball attachment bolt 540 with the threaded ball mounting bolt aperture 425. In one operation to activate the fluid loss device 100, the wash pipe assembly 90 and the running tool 400 are drawn upwardly through the fluid loss device 100 until the shear ring interface edge 435 on the running tool shear sleeve 430 of the running tool 400 engages the running tool interface edge 334 on the shear ring 330 of the compression sleeve assembly 310, as shown in FIG. 7A. The wash pipe assembly 90 continues to be lifted upwardly through the fluid loss device 100 until the running tool 400 shears the shear pins 350 allowing the compression sleeve assembly 310 to progress upwardly through the fluid loss device 100 with running tool 400 and the wash pipe assembly 90. As the compression sleeve assembly 310 progresses upwardly with the running tool 400 and the wash pipe assembly 90 through the fluid loss device 100, the compression land 324 of the sleeve 320 will engage the compression land 364 of the collet seal assembly 360, thereby reducing the inner diameter 362 of the collet seal 365. At a point where the compression land 324 of the sleeve 320 reduces the inner diameter 362 of the collet seal 365 to a diameter smaller than the outer diameter 510 of the ball 500, the snap ring 250 will engage the snap ring groove 325 in the sleeve 320, thus preventing further upward movement of the compression sleeve assembly 310 in the fluid loss device 100, as shown in FIG. 7B. In the position where the snap ring 250 engages the snap ring groove 325, the seal 270 will engage the outer diameter 321 of the sleeve 320. After the snap ring 250 engages the snap ring groove 325 in the sleeve 320, movement of the wash pipe assembly 90 upwardly will sever the shear pins 440 that secure the running tool shear sleeve 430 to the running tool mandrel 420. Continued upward movement of the wash pipe assembly 90 and the running tool 400 will pull the shear ring interface edge 435 of the running tool shear sleeve 430 into engagement with the running tool interface edge 334 of the compression sleeve assembly 310, and the ball interface surface 438 of the running tool shear sleeve 430 into engagement with the ball 500, as shown in FIG. 7C. The force of the wash pipe assembly 90 and the running tool 400 being drawn upwardly through the fluid loss device 100 cause the ball attachment bolt 540 to sever at the prestressed area 541 below the outer diameter 510 of the ball 500. Once the ball attachment bolt 540 is severed, the ball 500 will drop into engagement with the collet seal 365 of the collet seal assembly 360, thereby blocking flow through the fluid loss device 100. After the ball 500 has separated from the running tool mandrel 420, the stop land 434 of the running tool shear sleeve 430 will engage the stop land 423 of the running tool mandrel 420. Continued movement of the wash pipe 90 and running tool 400 upwardly through the fluid loss device 100 will bring the shear ring interface edge 435 on the running tool shear sleeve 430 into engagement with the running tool interface edge 334 on the shear ring 330 of the compression sleeve assembly 310, as shown in FIG. 7D. During the time period in which the shear ring interface edge 435 engages the running tool interface edge 334, by-pass grooves 436 in the shear ring interface edge 435 allow a metered quantity of fluid to pass from above the shear ring 330 to below the running tool shear sleeve 430. In this manner, the pressure above and below the shear ring 330 and the running tool shear sleeve 430 are maintained at an approximately equal pressure, preventing a sudden surge of pressure on the ball 500 below when the shear ring 330 is separated from the sleeve 320. Continued upward forces of the wash pipe 90 and running tool 400 will be transmitted by the shear ring interface edge 435 to the running tool interface edge 334, severing the shear pins 340 connecting the shear ring 330 to the sleeve 320, as shown in FIG. 7E. Removal of the wash pipe assembly 90 and the running tool 400 from the fluid loss device 100 leaves the ball 500 sealed against the collet seal 365, thereby restricting flow from the above the fluid loss device 100 to below the fluid loss device 100. Once the ball 500 has separated from the running tool mandrel 420 and engaged the collet seal 365, the fluid loss device 100 is in an activated condition. In the activated position, the seal 270 provides a seal between the housing 200 and the seal assembly 300, and the collet seal 365 provides a seal between the seal assembly 300 and the ball 500. Thus, in the activated condition, the fluid loss device 100 prohibits communication from above the fluid loss device 100 to below the fluid loss device 100. At some point after the ball 500 engages the collet seal 365 preventing flow downward through the fluid loss device 100, it will be desired to deactivate or open the fluid loss device 100 to once again allow flow through the fluid loss device 100. To allow flow to resume through the fluid loss device 100, the ball 500 must be cleared from the collet seal 365, as shown in FIG. 7F. Three possible methods can be used to clear the ball 500 from the collet seal 365: mechanical, pressure, or chemical. The ball 500 can be forced clear of the collet seal 365 by applying a downward mechanical force to the ball 500. Force applied to the ball 500 is transmitted to the shear pins 370 by the collet seal assembly 360. When the force exerted on the ball 500 is great enough to sever the shear pins 370, the ball 500 and the collet seal assembly 360 will progress downward through the fluid loss device 100 until the compression land 364 of the collet seal assembly 360 clears the compression land 324 of the sleeve 320. Once the compression land 364 of the collet seal assembly 360 clears the compression land 324 of the sleeve 320, the collet seal 365 will expand until the compression land 364 of the collet seal assembly 360 resides in a relaxed position between the sleeve 320 and the stop land 223 of the housing 200. Expansion of the collet seal 365 will allow the ball 500 to pass through the collet seal 365 and exit the fluid loss device 100. After the ball 500 exits the fluid loss device 100, the ball 500 will pass through the blank production tubing 33, the well screen 31, the seal 32, and the sump packer 21 into the sump 22. The ball 500 can be forced clear of the collet seal 365 by applying pressure to the upper surface of the ball 500. Force applied to the ball 500, due to the pressure above the ball 500, is transmitted to the shear pins 370 by the collet seal assembly 360. When the force exerted on the ball 500 is great enough to sever the shear pins 370, the ball 500 and the collet seal assembly 360 will progress downward through the fluid loss device 100 until the compression land 364 of the collet seal assembly 360 clears the compression land 324 of the sleeve 320. Once the compression land 364 of the collet seal assembly 360 clears the compression land 324 of the sleeve 320, the collet seal 365 will expand until the compression land 364 of the collet seal assembly 360 resides in a relaxed position between the sleeve 320 and the stop land 223 of the housing 200. Expansion of the collet seal 365 will allow the ball 500 to pass through the collet seal 365 and exit the fluid loss device 100. After the ball 500 exits the fluid loss device 100, the ball 500 will pass through the blank production tubing 33, the well screen 31, the seal 32, and the sump packer 21 into the sump 22. The ball 500 can be cleared from the collet seal 365 by applying chemicals to the ball 500 that erode the outer diameter 510 of the ball 500. In one embodiment, the ball 500 is formed of brass and acid is used to erode the ball 500. Once the outer diameter 510 of the ball 500 has eroded to a diameter smaller than the inner diameter 362 of the collet seal 365, the ball 500 will pass through the collet seal 365 and exit the fluid loss device 100. Once the ball 500 exits the fluid loss device 100, the ball 500 will pass through the blank production tubing 33, the well screen 31, the seal 32, and the sump packer 21 in to the sump 22. After the ball 500 has exited the fluid loss device 100, the collet seal assembly 360 can be placed in a relaxed position by mechanically applying a downward force to the collet seal assembly 360 until the shear pins 370 sever and the compression land 364 of the collet seal assembly 360 clears the compression land 324 of the sleeve 320. Once the compression land 364 of the collet seal assembly 360 clears the compression land 324 of the sleeve 320, the collet seal 365 will expand until the compression land 364 of the collet seal assembly 360 resides in a relaxed position between the sleeve 320 and the stop land 223 of the housing 200. Another embodiment of the fluid loss device 10 of FIGS. 1 and 2 is illustrated in FIG. 8 as the fluid loss device 1000. The fluid loss device 1000 generally comprises a housing 2000, a seal assembly 3000, a running tool assembly 4000, and a plug 5000. An upper portion of the housing 2000 has a threaded interface aperture 2100 that attaches to the upper packer 24 (shown in FIGS. 1 and 2), and a lower portion of the housing 2000 has a threaded interface nipple 2200 that attaches to the blank tubing 33 (shown in FIGS. 1 and 2). An inner diameter 2300 of the housing 2000 is connected to an expanded lower opening 2400 by a seal interface surface 2500. The housing 2000 also has stop dog recesses 2600 in the inner diameter 2300. In one embodiment, the seal assembly 3000, as shown in FIGS. 8 and 9, has an upper or first outer diameter 3110 and a lower or second outer diameter 3120. The first outer diameter 3110 of the seal assembly 3000 is smaller than the inner diameter 2300 of the housing 2000. The second outer diameter 3120 of the seal assembly 3000 is larger than the inner diameter 2300 of the housing 2000 but smaller than the expanded lower opening 2400 of the housing 2000. A stop land 3130 is created between the first outer diameter 3110 and the second outer diameter 3120 of the seal assembly 3000. The seal assembly 3000 also has an upper or first inner diameter 3210, a middle or second inner diameter 3220, and a lower or third inner diameter 3230. The first inner diameter 3210 is larger than the second inner diameter 3220, thereby creating a first inner stop land 3240 between the two diameters. The second inner diameter 3220 is larger than the third inner diameter 3230, thereby creating a second inner stop land 3250. Seals 3320 reside within seal grooves 3310 in the first outer diameter 3110 of the seal assembly 3000. A running tool skirt interface edge 3600 is crated on an upper portion of the seal assembly 3000 between the first inner diameter 3210 and the first outer diameter 3110. A plurality of stop dogs 3410 reside within stop dog apertures 3420 between the first inner diameter 3210 and the first outer diameter 3110 of the seal assembly 3000. Shear pin apertures 3510 extend between the second inner diameter 3220 and spring recesses 3520 in the second outer diameter 3120. The running tool 4000, as shown in FIGS. 8 and 10, generally comprises a running tool mandrel 4100, a running tool skirt 4200, locking segments 4300, running tool skirt cap 4400, a locking segment spring 4500, and a running tool skirt spring 4600. The running tool mandrel 4100 has an upper or first outer diameter 4110 and a lower or second outer diameter 4120. A stop ring 4160 separates the first outer diameter 4110 from the second outer diameter 4120. The stop ring 4160 has an upper land or skirt stop land 4130. On an upper portion of the first outer diameter 4110 are running tool mandrel mounting threads 4140 for securing the running tool 4000 to the wash pipe assembly 90. On a lower portion of the first outer diameter 4110, near the stop land 4130, are a plurality of annular grooves or serrations 4150. The running tool skirt 4200 has an outer diameter 4210 that is smaller than the inner diameter 2300 of the housing 2000. In one embodiment, the outer diameter 4210 of the skirt 4200 is approximately the same diameter as the first outer diameter 3110 of the seal assembly 3000. The running tool skirt 4200 also has an upper or first inner diameter 4220, a middle or second inner diameter 4230, and a lower or third inner diameter 4240. The second inner diameter 4230 of the running tool skirt 4200 is larger than the first outer diameter 4110 of the running tool mandrel 4100 but smaller than the stop ring 4160. The first inner diameter 4220 of the skirt 4200 is greater than the second inner diameter 4230, and a segment wedging surface 4250 joins the first inner diameter 4220 to the second inner diameter 4230. The third inner diameter 4240 of the skirt 4200 is also greater than the second inner diameter 4230, thereby creating a mandrel stop land 4280 between the two diameters. The first outer diameter 4110 of the running tool mandrel 4100 is positioned within the second inner diameter 4230 of the skirt 4200, with the mandrel stop land 4280 of the skirt 4200 nearest to the stop land 4130 of the running tool mandrel 4100. A seal assembly interface edge 4260 is created between the third inner diameter 4240 and the outer diameter 4210 of the skirt 4200. The seal assembly interface edge 4260 of the running tool skirt 4200 is adapted for engagement with the running tool skirt interface edge 3600 of the seal assembly 3000. A cap mounting surface 4270 is created between the first inner diameter 4220 and the outer diameter 4210 of the skirt 4200. Each of the locking segments 4300 have an inner surface 4310 that approximates the first outer diameter 4110 of the running tool mandrel 4100, and are serrated with grooves for mating with the serrated surface 4150 of the first outer diameter 4110 on the running tool mandrel 4100. Each of the locking segments 4300 also have an outer surface 4320 that approximates a diameter smaller than the first inner diameter 4220 of the skirt 4200. On a lower portion of each of the locking segments 4300, between the inner surface 4310 and the outer surface 4320, is a skirt interface edge 4330. The locking segments 4300 are positioned with the inner surfaces 4310 adjacent to the first outer diameter 4110 of the running tool mandrel 4100, the outer surfaces 4320 adjacent to the first inner diameter 4220 of the skirt 4200, and the skirt interface edge 4330 adjacent to the segment wedging surface 4250 of the skirt 4200. In a preferred embodiment, the skirt interface edge 4330 of the segments 4300 and the segment wedging surface 4250 of the skirt 4200 are tapered surfaces that force the locking segments 4300 against the running tool mandrel 4100 as the skirt 4200 is forced upward along the running tool mandrel 4100. On an upper portion of each of the locking segments 4300, between the inner surface 4310 and the outer surface 4320, is a locking spring interface edge 4340. The running tool skirt cap 4400 has an outer diameter 4410 that is preferably the same diameter as the outer diameter 4210 of the skirt 4200. An upper or first inner diameter 4420 of the cap 4400 is greater than the first outer diameter 4110 of the running tool mandrel 4100. A skirt spring interface edge 4430 is created between the first inner diameter 4420 and the outer diameter 4410 of the skirt cap 4400. A lower or second inner diameter 4440 in the cap 4400 is preferably approximately the same diameter as the same first inner diameter 4220 in the skirt 4200. The second inner diameter 4440 of the cap 4400 is greater than the first inner diameter 4420, thereby creating a segment spring interface land 4450 in the cap 4400. A skirt interface edge 4460 is created in a lower portion of the cap 4400 between the second inner diameter 4440 and the outer diameter 4410. The cap 4400 is positioned with the first outer diameter 4110 of the running tool mandrel 4100 extending through the first inner diameter 4420 of the cap 4400, and the skirt interface edge 4460 of the cap 4400 secured against the cap mounting surface 4270 of the skirt 4200. The locking segment spring 4500 is positioned around the first outer diameter 4110 of the running tool mandrel 4100 such that force is applied between the segment spring interface land 4450 of the cap 4400 and the spring interface edges 4340 of the locking segments 4300. The running tool skirt spring 4600 is positioned around the first outer diameter 4110 of the running tool mandrel 4100 such that force is exerted between the skirt spring interface edge 4430 of the skirt cap 4400 and the wash pipe assembly 90. The inner mandrel or plug 5000, as shown in FIG. 8 and 10, has a first outer diameter 5100, a second outer diameter 5200, a third outer diameter 5300, a fourth outer diameter 5400, and a fifth outer diameter 5500, progressing from an upper portion of the plug 5000 to a lower portion of the plug 5000, respectively. The first outer diameter 5100 of the plug 5000 is smaller than the third inner diameter 4240 of the running tool skirt 4200. The second outer diameter 5200 of the plug 5000 is smaller than the first inner diameter 3210 of the seal assembly 3000, and has seal recesses 5210 circumferentially around the plug body 5000 for seals 5800. The fourth outer diameter 5400 of the plug 5000 is smaller than the first inner diameter 3210 of the seal assembly 3000. The third outer diameter 5300 of the plug 5000 is smaller than the fourth outer diameter 5400. A stop dog cam surface 5600 is created between the third diameter 5300 and the fourth diameter 5400. The fifth outer diameter 5500 of the plug 5000 is smaller than the second inner diameter 3220 of the seal assembly 3000. The fifth inner diameter 5500 of the plug 5000 is also smaller than the fourth inner diameter 5400, thereby creating a stop land 5700 between the two diameters for engagement with the first inner stop land 3240 of the seal assembly 3000. Shear pin recesses 5510 are also located in the fifth diameter of the plug 5000. A mandrel mounting aperture 5120 is disposed within an upper portion of the plug 5000. The second diameter 4120 of the running tool mandrel 4100 is secured within the mandrel mounting aperture 5120 of the plug by shear pins 5900 engaging shear pin apertures 5110 in the plug 5000 and shear pin apertures 4170 in the running tool mandrel 4100. The second outer diameter 5200, the third outer diameter 5300, the fourth outer diameter 5400, and the fifth outer diameter 5500 of the plug 5000 are secured within the first inner diameter 3210 and the second inner diameter 3220 of the seal assembly 3000 by shear pins 3700 engaging shear pin apertures 5410 in the fourth diameter 5400 of the plug 5000 and shear pin apertures 3115 in the first inner diameter 3210 of the seal assembly 3000. Springs 3800 are secured within the spring pin recesses 3520 of the seal assembly 3000 and apply a force to shear pins 3900 residing in the shear pin apertures 3510, such that the shear pins 3900 are forced against the fifth inner diameter 5500 of the plug 5000. Stop dogs 3410 reside within the stop dog apertures 3420 in the seal assembly 3000. The stop dog apertures 3420 are located such that the third outer diameter 5300 of the plug 5000 creates a stop dog release surface and the fourth outer diameter 5400 creates a stop dog lock surface. In this manner, movement of the plug 5000 relative to the seal assembly 3000 will cause the stop dogs 3410 to follow the stop dog cam surface 5600 to move between the stop dog release surface, or third outer diameter 5300, and the stop dog lock surface, or fourth outer diameter 5400. When the stop dogs 3410 rest against the stop dog release surface 5300, the stop dogs 3410 will reside within the stop dog apertures 3420 in the seal assembly 3000 and do not extend out from the first outer diameter 3110 of the plug 3000. When the stop dogs 3410 rest against the stop dog lock surface 5400, the stop dogs 3410 will extend outwardly from the plug 5000 such that the stop dogs 3410 will reside in both the stop dog apertures 3420 in the seal assembly 3000 and the stop dog recesses 2600 in the housing 2000. In one operation to activate the fluid loss device 1000, the wash pipe assembly 90 and the running tool 4000 are drawn upwardly through the fluid loss device 1000 until the stop land 3130 of the seal assembly 3000 engages the seal interface surface 2500 of the housing 2000, as shown in FIG. 11A. The wash pipe assembly 90 and running tool 4000 continue to be lifted upwardly through the fluid loss device 1000, shearing the shear pins 3700 that secure the seal assembly 3000 to the plug 5000. Continued upward movement of the wash pipe assembly 90 and the running tool 4000 will cause the stop dogs 3410 to progress along the stop dog cam surface 5600 until the stop dogs 3410 engage the stop dog locking surface or fourth outer diameter 5400 of the plug 5000, as shown in FIG. 11B, thereby kicking the stop dogs 3410 outwardly into the stop dog recesses 2600 in the housing 2000. In this manner, the seal assembly 3000 will be secured to the housing 2000 by the stop dogs 3410 located in the stop dog apertures 3420 of the seal assembly 3000 and the stop dog recesses 2600 in the housing 2000. The seals 3320 provide a seal between the seal assembly 3000 and the housing 2000. Continued upward movement of the wash pipe assembly 90 and the running tool 4000 will draw the plug 5000 upwardly through the seal assembly 3000. Once the shear pin recesses 5510 in the fifth outer diameter 5500 of the plug 5000 align with the shear pins 3900 residing in the shear pin apertures 3510 of the seal assembly 3000, the springs 3800 will force the shear pins 3900 into the shear pin recesses 5510, as shown in FIG. 11C, thereby securing the plug 5000 to the seal assembly 3000. The seals 5800 will seal between the plug 5000 and the seal assembly 3000. Continued upward movement of the wash pipe assembly 90 and the running tool 4000 through the fluid loss device 1000 will sever the shear pins 5900 securing the plug 5000 to the running tool mandrel 4100. As the wash pipe assembly 90 and the running tool mandrel 4100 continue to move upward through the fluid loss device 1000, the running tool skirt spring 4600 will force the running tool skirt cap 4400 and the running tool skirt 4200 downwardly on the running tool mandrel 4100 until the mandrel stop land 4280 of the running tool skirt 4200 engages the skirt stop land 4130 of the running tool mandrel 4100, as shown in FIG. 11D. In the position where the skirt stop land 4130 of the running tool mandrel 4100 engages the mandrel stop land 4280 of the running tool skirt 4200, the running tool mandrel 4100 is swallowed or protected by the running tool skirt 4200. In the swallowed or protected position, the skirt 4200 will engage the seal assembly 3000 due to any downward movement of the running tool 4000 before the running tool mandrel 4100 can engage the plug 5000. The protected condition of the running tool 4000 is maintained by the locking segments 4300. The locking segment spring 4500 forces the locking segments 4300 downward until the skirt interface edge 4330 of the locking segments 4300 engages the segment wedging surface 4250 of the running tool skirt 4200. The angled surface of the segment wedging surface 4250 against the skirt interface edge 4330 of the locking segments 4300, forces the serrated inter surface 4310 of the locking segments 4300 against the serrated surface 4150 on the first outer diameter 4110 of the running tool mandrel 4100. Engagement by the locking segments 4300 with the serrated surface 4150 on the running tool mandrel 4100 and the segment wedging surface 4250 of the running tool skirt 4200, will lock the running tool skirt 4200 and running tool skirt cap 4400 in the swallowed or protected position over the running tool mandrel 4100. In the locked swallowed position, should the running tool 4000 progress downwardly, the running tool skirt 4200 will always engage the seal assembly 3000 before the running tool mandrel 4100 can engage the plug 5000. Thus, the locked swallowed position of the running tool 4000 will prevent disengagement of the fluid loss device 1000 by dislodging the plug 5000 in the seal assembly 3000 should the running tool 4000 inadvertently move downwardly after the plug 5000 is secured within the seal assembly 3000. Once the running tool mandrel 4100 has separated from the plug 5000, the fluid loss device 1000 is in an activated condition and the wash pipe 90 and running tool 4000 can be removed, as shown in FIG. lE. In the activated position, the seals 3320 provide a seal between the housing 2000 and the seal assembly 3000, and the seals 5800 provide a seal between the seal assembly 3000 and the plug 5000. Thus, in the activated position, the fluid loss device 1000 prohibits communication between above and below the fluid loss device 1000. The stop dogs 3410 and the shear pins 3900 inhibit movement of the plug 5000 and seal assembly 3000 in either an upward or downward direction. Thus, the fluid loss device 1000 device prohibits communication in either an upward or downward direction. At some point after the running tool 4000 is separated from the plug 5000, it will be desired to deactivate or open the fluid loss device 1000 to once again allow flow through the fluid loss device 1000, as shown in FIG. llF. To disengage the fluid loss device 1000, a mechanical or hydraulic force is applied to the upper end of the plug 5000, until the shear pins 3900 securing the plug 5000 to the seal assembly 3000 are severed. After the shear pins 3900 are severed, continued downward force on the plug 5000 will force the plug 5000 to move downwardly through the seal assembly 3000, until the stop dogs 3410 slide back into the seal assembly 3000 along the stop dog cam surface 5600 of the plug 5000 into engagement with the stop dog release surface or third outer diameter 5300 of the plug 5000. Once the stop dogs 3410 engage the third outer diameter 5300 of the plug 5000, the stop dogs 3410 have kicked inwardly and disengaged the stop dog recesses 2600 in the housing 2000. Once the stop dogs 3410 disengage the stop dog recesses 2600 of the housing 2000, the seal assembly 3000 and plug 5000 will exit the fluid loss device 1000 and pass through the blank production tubing 33, the well screen 31, the seal 32, and the sump packer 21 into the sump 22. Use of the fluid loss device 100 or the fluid loss device 1000 as the fluid loss device 10 provides a device for isolating a zone 23 of a well bore 1 that can be reopened at a later time. The plug and related components of the present invention fall to the sump area 22 and are widely accepted in the industry as items that can be left in a well bore 1. The large size of the plug and the seal assembly allow high flow rates into and out of the zone to be isolated before that zone is isolated. Although a preferred embodiment of the apparatus and methods of the present invention has been illustrated in the accompanying Drawings and described in the foregoing Detailed Description, it will be understood that the invention is not limited to the embodiment disclosed, but is capable of numerous rearrangements, modifications and substitutions without departing from the spirit of the invention as set forth and defined by the following claims.
A fluid loss device has a housing, a seal assembly, a running tool, and a plug. The housing of the fluid loss device is placed in a production string before a well bore is completed. The plug is attached to the running tool, and the running tool is attached to a wash pipe. The fluid loss device is activated by lifting the wash pipe and the running tool, thereby engaging the plug with the seal assembly, engaging the seal assembly with the housing, and severing the plug from the running tool. Activation of the fluid loss device inhibits fluid communication through the fluid loss device and reduces damage to the well structure behind the fluid loss device while completion operations are performed in other areas of the well bore. The fluid loss device is deactivated by forcing the plug through the fluid loss device with mechanical force or pressure, or by chemically eroding the diameter of the plug until the plug passes through the fluid loss device. Once the fluid loss device is deactivated, the isolated area of the well bore is reopened for access through the production string.
4
This is a continuation of application Ser. No. 08/306,373, filed Sep. 15, 1994 now abandoned. BACKGROUND OF THE INVENTION The present invention relates generally to medical ventilators and, more specifically, to tubing for use in that portion of the ventilator commonly known as the breathing circuit, which includes the gas supply and control paths and the patient's respiratory system. The breathing circuit includes an inhalation conduit for delivering gas to the patient, an exhalation conduit for receiving gas from the patient, a patient wye at which the inhalation and exhalation conduits join, and an endotracheal tube or tracheostomy outlet for interfacing the ventilator and patient sides of the breathing circuit. Another conduit may connect the patient wye to the endotracheal tube or tracheostomy outlet. The breathing circuit may also include filters located at the junctions between the exhalation and inhalation conduits and the ventilator housing, a humidifier, and other devices. Tubular fittings on the patient wye, filters and other portions of the breathing circuit receive the conduits. The conduits include a length of flexible tubing and may also include endpieces for connecting the tubing to the fittings. One commonly used type of fitting is a barbed, cylindrical or frusto-conical projection. The end of the flexible tubing is stretched over this fitting. Alternatively, the end of the flexible tubing may be attached to an elastomeric endpiece, which is, in turn, stretched over the fitting. Another commonly used type of fitting, which is defined by the ISO 5356-1 standard, consists of a rigid frusto-conical female half, into which a male half attached to the end of the flexible tubing is inserted. The male and female halves are formed of a rigid material such as metal. Nevertheless, the friction between the mating halves maintains the connection. The conduits are an extremely critical aspect of the breathing circuit. The coupling between a conduit and the fitting to which it is connected must withstand tensile stresses to prevent disconnection. The tubing must withstand flexure resulting from normal movement of the patient or ventilator without kinking or collapsing and thus restricting gas flow. Failure of the tubing or coupling can cause damage or death to a patient. In fact, an industry standard attachment test requires that a conduit remain connected to a fitting when a 20 pound tensile force is exerted for 60 seconds. The tubing is typically ribbed, such as by providing corrugation or a continuous spiral rib, to provide sufficient lateral rigidity to prevent the tubing from kinking or collapsing while allowing it to flex laterally and longitudinally. The spiral rib may also be used to attach an endpiece to the tubing in a screw-like manner. The tubing must either be disposable or sterilizable because medical practitioners typically replace it after about 72 to 168 hours of continuous use. Re-use of tubing through sterilization is increasing in response to concerns over damage to the environment by excessive medical waste. Moreover, re-use of tubing maximizes economy. Sterilization is performed by exposing the tubing to heat ("heat-sterilization") or chemicals ("cold-sterilization"). In heat-sterilization the tubing is typically exposed to steam at 270 degrees Fahrenheit for 20 minutes. Heat-sterilization is preferred because it is easier and more economical to perform than cold-sterilization. Materials commonly used to form the flexible tubing include silicone rubber, high-density polyethylene, HYTREL®, which is a thermoplastic copolymer produced by DuPont, Inc., and KRATON®, which is a rubbery styrenic block copolymer or thermoplastic elastomer produced by Shell Chemical Company. Silicone rubber is durable and highly elastomeric. It may be reused many times over a lifetime of up to approximately fifteen years by removing it from the fittings, sterilizing it, and reattaching it to the fittings. (Hospitals, however, typically replace such tubing after three to five years because it becomes discolored and gives the appearance of uncleanliness.) In addition, the superior elastomeric and frictional properties of silicone rubber facilitate formation of a strong coupling. However, such tubing is relatively uneconomical because it is formed using a molding process. At present, a conduit between the ventilator and the patient wye made of silicone rubber tubing costs a hospital in the U.S. on the order of $150. Polyethylene is considerably more economical than silicone rubber because it can be continuously extruded and then cut into the required lengths. Unlike silicone rubber, no expensive molding process is necessary. Nevertheless, it cannot be re-used in conjunction with either heat-sterilization or cold-sterilization. Not only will it melt or deform when subjected to the high temperatures of heat-sterilization, but polyethylene tubing that has been removed from a fitting for any reason cannot be reattached to a fitting because polyethylene has little or no memory. Once stretched over a fitting, such tubing remains permanently stretched and cannot form a coupling with sufficient strength to pass the above-described attachment test. Therefore, polyethylene tubing must be discarded after a single use. HYTREL® is more economical than silicone rubber, but it is not nearly as economical as polyethylene, both because the material itself is less economical than polyethylene and because it cannot be extruded like polyethylene. Although it can withstand high temperatures without melting or otherwise deforming, the tubing will harden over time when repeatedly heat-sterilized. Moreover, like polyethylene, it is not sufficiently elastomeric to be re-used by connecting it directly to a friction fitting. Silicone rubber endpieces are therefore screwed onto the ends of a length of HYTREL® tubing having a spiral rib and sealed with liquid silicone. The silicone rubber endpieces are sufficiently elastomeric and durable to be repeatedly reconnected to a fitting without degradation in the strength of the resulting coupling. (Silicone rubber has a tensile modulus of approximately 160 psi.) KRATON® is nearly as economical as polyethylene because it can be extruded using thermoplastic processing methods. Like silicone rubber and HYTREL®, it can withstand the temperatures of heat-sterilization. However, like polyethylene and HYTREL®, it is not sufficiently elastomeric to be re-used by connecting it directly to a friction fitting. (KRATON-D® has a tensile modulus between 400 and 1,000 psi.) Moreover, silicone rubber endpieces cannot be attached to the ends of a length of KRATON® tubing because KRATON® is too soft and pliable to form a strong spiral rib onto which an endpiece could be screwed and too resistant to adhesive bonding for liquid silicone or other adhesives and sealants to be used. (It is believed that a leaching agent in KRATON® prevents adhesion.) In attempts to secure KRATON® tubing directly to a fitting, plastic cable ties and rubber O-rings have been used as crude hose clamps. However, such clamping methods are inconvenient and unreliable. Moreover, succesive couplings using the same length of KRATON® tubing become weaker as repeated uses increasingly stretch the tubing. For these reasons, medical practitioners are reluctant to rely on such methods. It would be desirable to provide a breathing circuit conduit that is not only relatively economical but can also be removed from a fitting, sterilized, and replaced in a fitting multiple times without suffering unacceptable degradation in the strength of the resulting coupling. These problems and deficiencies are clearly felt in the art and are solved by the present invention in the manner described below. SUMMARY OF THE INVENTION In one aspect, the present invention comprises a novel coupler for attaching tubing to a conventional ventilator fitting. The coupler is preferably made of a durable, rigid material, such as polycarbonate or polysulfone plastic. One end of the coupler has a releasable compression fitting for gripping the tubing. Unlike a conventional ventilator fitting, in which the tubing is secured by the friction resulting from the forces exerted by the stretched end of elastomeric tubing, the compression fitting of the present invention has two portions between which the end of the tubing is gripped or compressed. The tubing thus remains securely attached regardless of its elastic properties. The end of the tubing may have one or more features that facilitate gripping in the compression fitting. The other end of the coupler has a fitting that can be either directly or indirectly attached to the ventilator fitting. A directly attachable coupler fitting may have, for example, a rigid, conical ISO 5356-1 projection. An indirectly attached coupler fitting may have a barbed projection over which one end of an elastomeric endpiece can be stretched, with the other end stretched over the ventilator fitting. The tubing and coupling may be re-used using either heat or cold-sterilization. Similarly, the coupler may be sterilized and re-used. Medical waste and its resulting environmental damage are thus minimized. Although the tubing may be made of any suitable material, the coupler is particularly useful if the tubing is made of a material that cannot otherwise be readily attached to a ventilator fitting. The tubing may have elastic properties too poor to allow formation of a secure connection by stretching it over a ventilator fitting. The tubing may have other physical properties that prevent its attachment to an elastomeric endpiece using non-mechanical means, such as adhesive bonding, heat fusing, sonic welding, and the like, or using an integrally formed coupling member such as a spiral rib. For example, a tube made of KRATON® is heat-sterilizable, but it cannot be stretched over a ventilator fitting to form a secure connection, cannot be adhesively bonded to a silicone rubber endpiece, and cannot be provided with a strong spiral rib. The conduit defined by the combination of the releasable coupler and the tubing may be characterized as "semi-disposable" because the durable coupler may be re-used over a lifespan of many years while the tubing may be re-used for a somewhat shorter period and then discarded. For example, a tube made of KRATON® may be re-used until it becomes discolored. The combination of tubing that is both economical and semi-reusable with a highly reusable coupler both increases cost savings to health care providers and reduces the amount of medical waste that is discarded. The foregoing, together with other features and advantages of the present invention, will become more apparent when referring to the following specification, claims, and accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS For a more complete understanding of the present invention, reference is now made to the following detailed description of the embodiments illustrated the accompanying drawings, wherein: FIG. 1 is a sectional view of the present invention; and FIG. 2 is an enlarged sectional view similar to FIG. 1, showing the coupling between the two lengths of tubing; and FIG. 3 is a sectional view of an alternative inner coupling member having a conical male fitting half. DESCRIPTION OF PREFERRED EMBODIMENTS As illustrated in FIG. 1, a coupler 10 joins a length of tubing 12 to an endpiece 14. Coupler 10 comprises an inner coupling member 16 and an outer coupling member 18, both of which are preferably made of a durable, heat-sterilizable plastic, such as polycarbonate. Tubing 12 may be any suitable length. Inner coupling member 16 has a stretch fitting 20 over which the proximal end of endpiece 14, which is preferably made of silicone rubber, is stretched. Inner coupling member 16 also has an inner coupling member threaded portion 24 and a tapered or frusto-conical inner coupling member grip surface 26. Inner coupling member grip surface 26 has a plurality of male circumferential barbs 28. A bore 30 extends through inner coupling member 16. Outer coupling member 18 has an outer coupling member threaded portion 32 for mating with inner coupling member threaded portion 24. Outer coupling member 18 also has an outer coupling member grip surface 34. Outer coupling member grip surface 34 has a circumferential groove 36, a circumferential coupling lip 38, and a plurality of female circumferential barbs 40. Tubing 12 has a corrugated portion 42 and a tapered or frusto-conical non-corrugated portion 44. Non-corrugated portion 44 has a circumferential tubing lip 46. Suitable material for tubing 12 has a tensile modulus of between approximately 400 and 1,000 and can withstand the temperatures of heat-sterilization (270 degrees for 20 minutes) without deforming. It should also be economical in relation to silicone rubber, which would be the ideal material for ventilator breathing circuit tubing were cost not a factor. Tubing 12 is preferably made of KRATON® thermoplastic rubber copolymer. Not only is such material relatively economical but the tubing can be formed using relatively economical thermoplastic processes. As will be recognized by persons of skill in the art, the corrugations and other surface features of tubing 12 may be formed using a blow-molding process in conjunction with an extrusion process. In other embodiments, tubing 12 may be made of a material that has characteristics that, like those of KRATON®, prevent its direct connection to a ventilator fitting. The material may, for example, have poor elasticity, i.e., a tensile modulus over 400. The material may not, for example, be adhesively bondable to an elastomeric endpiece due to a low porosity, e.g., less than one percent, or due to the presence of a leaching agent. To connect tubing 12 to coupler 10, non-corrugated portion 44 is inserted through circumferential coupling lip 38 into outer coupling member grip portion 34 until circumferential tubing lip 46 is received in circumferential coupling groove 36. The mating of circumferential tubing lip 46 and circumferential coupling groove 36 provides a first point of engagement that aligns the resulting coupling between coupler 10 and tubing 12. Circumferential coupling lip 38 is received in the first groove 48 of corrugated portion 42. The mating of circumferential coupling lip 38 and first groove 48 provides a primary point of engagement that aligns coupling 18 to tubing 12. Inner coupling member grip portion 26 is then inserted through outer coupling member threaded portion 32 into non-corrugated portion 44 of tubing 12 until inner coupling member threaded portion 24 contacts outer coupling member threaded portion 32. Inner and outer coupling members 16 and 18 are rotated with respect to one another to engage threaded portions 24 and 32. In response to this rotation, inner coupling member grip surface 26 moves closer to outer coupling member grip surface 34 because grip surfaces 26 and 34 are tapered. As grip surfaces 26 and 34 approach one another they compress non-corrugated portion 44 of tubing 12 between them. This compression provides the most important point of engagement that strengthens the coupling between coupler 10 and tubing 12. In addition, male circumferential barbs 28 are aligned with female circumferential barbs 40 when threaded portions 24 and 32 are fully engaged. This alignment maximizes the strength of the main point of engagement. Unlike a connection between an ordinary stretch fitting and a tube, the strength of the resulting coupling of the present invention is not dependent upon the elasticity of tubing 12. The connection will remain strong despite the relatively inelastic properties of KRATON® tubing. Once assembled, the conduit comprising tubing 12, endpiece 14 and coupler 10 may be substituted for any of conventional conduit used in the breathing circuit of a ventilator (not shown). The free end of endpiece 14 may be connected to any conventional stretch fitting in the breathing circuit in the manner known in the art. The free end of tubing 12 may be connected to another coupler (not shown) that is identical to coupler 10 and its endpiece may be connected to another stretch fitting in the breathing circuit. The present invention may be removed from the ventilator breathing circuit and sterilized as often as the medical practitioner requires. Coupler 10 and endpiece 14 will not degrade for a period of many years of typical hospital use. Although tubing 12 may last nearly as long without degradation, it has been found that tubing 12, because it is made of KRATON®, may discolor and assume the appearance of uncleaniness after a period of between six months and one year of typical hospital use. Tubing 12 may then be discarded and replaced. In an alternate embodiment, illustrated in FIG. 3, an inner coupling member 16' has a conical fitting 20' in accordance with ISO standard 5356-1. Inner coupling member 16' may be used in coupler 10 in the same manner as inner coupling member 16. Inner coupling member 16' has a bore 30', an inner coupling member threaded portion 24', and an inner coupling member grip surface 26' with a plurality of male circumferential barbs 28'. Conical fitting 20' may be directly connected to a mating ventilator fitting; no intermediate elastomeric endpiece is necessary. The present invention strikes a novel balance between waste reduction and economy. The amount of waste produced using the present invention in a given period of time is substantially less than would be produced using disposable polyethylene tubing because the KRATON® tubing can be reused multiple times. The cost of ventilator breathing circuit conduits made in accordance with the present invention is substantially less than that of conduits made of silicone rubber because the KRATON® tubing is relatively economical and the coupler can be reused indefinitely. Obviously, other embodiments and modifications of the present invention will occur readily to those of ordinary skill in the art in view of these teachings. Therefore, this invention is to be limited only by the following claims, which include all such other embodiments and modifications when viewed in conjunction with the above specification and accompanying drawings.
A coupler having a releasable compression fitting connects a length of tubing to a ventilator fitting. The compression fitting allows the tubing to be made of economical and re-usable materials that would otherwise be difficult to attach to a ventilator fitting. The coupler may have a conical end that can be directly attached to a ventilator fitting, or it may have a barbed end over which an elastomeric endpiece is attached, which in turn can be attached to a ventilator fitting. The tubing and coupler may be sterilized and re-used.
5
FIELD OF INVENTION [0001] The present invention relates to interconnection structures for computing and communication systems. More specifically, the present invention relates to multiple level interconnection structures in which control and logic circuits are minimized. BACKGROUND OF THE INVENTION [0002] Many advanced computing systems, including supercomputers for example, utilize multiple computational units to improve performance in what is called a parallel system. The system of interconnections among parallel computational units is an important characteristic for determining performance. One technique for interconnecting parallel computational units involves construction of a communication network similar to a telephone network in which groups of network elements are connected to switching systems. The switching systems are interconnected in a hierarchical manner so that any switching station manages a workable number of connections. [0003] One disadvantage of a network connection is an increase in the latency of access to another computational unit since transmission of a message traverses several stages of a network. Typically, periods of peak activity occur in which the network is saturated with numerous messages so that many messages simultaneously contend for the use of a switching station. Various network types have been devised with goals of reducing congestion, improving transmission speed and achieving a reasonable cost. These goals are typically attained by rapidly communicating between nodes and minimizing the number of interconnections that a node must support. [0004] One conventional interconnection scheme is a ring of nodes with each node connected to two other nodes so that the line of interconnections forms a circle. The definition of a ring, in accordance with a standard definition of a ring network in the art of computing ( IBM Dictionary of Computing , McDaniel G. ed., McGraw-Hill, Inc., 1994, p. 584) is a network configuration in which devices are connected by unidirectional transmission links to form a closed path. Another simple conventional scheme is a mesh in which each node is connected to its four nearest neighbors. The ring and mesh techniques advantageously limit the number of interconnections supported by a node. Unfortunately, the ring and mesh networks typically are plagued by lengthy delays in message communication since the number of nodes traversed in sending a message from one node to another may be quite large. These lengthy delays commonly cause a computational unit to remain idle awaiting a message in transit to the unit. [0005] The earliest networks, generally beginning with telephone networks, utilize circuit switching in which each message is routed through the network along a dedicated path that is reserved for the duration of the communication analogous to a direct connection via a single circuit between the communicating parties. Circuit switching disadvantageously requires a lengthy setup time. Such delays are intolerable during the short and quick exchanges that take place between different computational units. Furthermore, a dedicated pathway is very wasteful of system bandwidth. One technique for solving the problems arising using circuit switching is called packet switching in which messages sent from one computational unit to another does not travel in a continuous stream to a dedicated circuit. Instead, each computational unit is connected to a node that subdivides messages into a sequence of data packets. A message contains an arbitrary sequence of binary digits that are preceded by addressing information. The length of the entire message is limited to a defined maximum length. A “header” containing at least the destination address and a sequence number is attached to each packet, and the packets are sent across the network. Addresses are read and packets are delivered within a fraction of a second. No circuit setup delay is imposed because no circuit is set up. System bandwidth is not wasted since there is no individual connection between two computational units. However, a small portion of the communication capacity is used for routing information, headers and other control information. When communication advances in isolated, short bursts, packet switching more efficiently utilizes network capacity. Because no transmission capacity is specifically reserved for an individual computational unit, time gaps between packets are filled with packets from other users. Packet switching implements a type of distributed multiplexing system by enabling all users to share lines on the, network continuously. [0006] Advances in technology result in improvement in computer system performance. However, the manner in which these technological advances are implemented will greatly determine the extent of improvement in performance. For example, performance improvements arising from completely optical computing strongly depend on an interconnection scheme that best exploits the advantages of optical technology. SUMMARY OF THE INVENTION [0007] In accordance with the present invention, a multiple level minimum logic network interconnect structure has a very high bandwidth and low latency. Control of interconnect structure switching is distributed throughout multiple nodes in the structure so that a supervisory controller providing a global control function is not necessary. A global control function is eliminated and complex logic structures are avoided by a novel data flow technique that is based on timing and positioning of messages communicating through the interconnect structure. Furthermore, the interconnect structure implements a “deflection” or “hot potato” design in which processing and storage overhead at each node is minimized by routing a message packet through an additional output port rather than holding the packet until a desired output port is available. Accordingly, the usage of buffers at the nodes is eliminated. Elimination of a global controller and buffering at the nodes greatly reduces the amount of control and logic structures in the interconnect structure, simplifying overall control components and network interconnect components, improving speed performance of message communication and potentially reducing interconnection costs substantially. Implementation of the interconnect structure is highly flexible so that fully electronic, fully optical and mixed electronic-optical embodiments are achieved. An implementation using all optical switches is facilitated by nodes exploiting uniquely simple logic and elimination of buffering at the nodes. [0008] The multiple level minimum logic network interconnect architecture is used for various purposes. For example, in some embodiments the architecture is used as an interconnect structure for a massively parallel computer such as a supercomputer. In other exemplary embodiments, the architecture forms an interconnect structure linking a group of workstations, computers, terminals, ATM machines, elements of a national flight control system and the like. Another usage is an interconnect structure in various telecommunications applications or an interconnect structure for numerous schedulers operating in a business main frame. [0009] In accordance with one aspect of the present invention, an interconnect apparatus includes a plurality of nodes and a plurality of interconnect lines selectively connecting the nodes in a multiple level structure in which the levels include a richly interconnected collection of rings. The multiple level structure includes a plurality of J+1 levels in a hierarchy of levels and a plurality of 2 J K nodes at each level. If integer K is an odd number, the nodes on a level M are situated on 2 J-M rings with each ring including 2 M K nodes. Message data leaves the interconnect structure from nodes on a level zero. Each node has multiple communication terminals. Some are message data input and output terminals. Others are control input and output terminals. For example, a node A on level 0 , the innermost level, receives message data from a node B on level 0 and also receives message data from a node C on level 1 . Node A sends message data to a node D on level 0 and also sends message data to a device E that is typically outside the interconnect structure. One example of a device E is an input buffer of a computational unit. Node A receives a control input signal from a device F which is commonly outside the interconnect structure. An example of a device F is an output buffer of a computational unit. Node A sends a control signal to a node G on level 1 . [0010] All message data enters the interconnect structure on an outermost level J. For example, a node A on level J, the outermost level, receives message data from a node B on level J and also receives message data from a device C that is outside the interconnect structure. One example of device C is an output buffer of a computational unit. Node A sends message data to a node D on level J and also sends message data to a node E on level J−1. Node A receives a control input signal from a node F on level J−1. Node A sends a control signal to a device G that is typically outside the interconnect structure. An example of a device G is an output buffer of a computational unit. [0011] Nodes between the innermost level 0 and the outermost level J communicate message data and control signals among other nodes. For example, a node A on a level T that is neither level 0 or level J receives message data from a node B on level T and also receives message data from a node C on level T+1. Node A sends message data to a node D on level T and also sends message data to a node E on level T−1. Node A receives a control input signal from a node F on level T−1. Node A sends a control signal to a node G on level T+1. [0012] Level M has 2 J-M rings, each containing 2 M K nodes for a total of 2 J K nodes on level M. Specifically: [0013] Level 0 has 2 J rings, each containing 2 0 K=K nodes for a total of 2 J K nodes on level 0 . [0014] Level 1 has 2 J− 1 rings, each containing 2 1 K=2K nodes for a total of 2 J K nodes on level 1 . [0015] Level 2 has 2 J−2 rings, each containing 2 2 K=4K nodes for a total of 2 J K nodes on level M. [0016] Level J− 2 has 2 J-(J−2) =4 rings, each containing 2 (J−2) K nodes for a total of 2 J K nodes on level J− 2 . [0017] Level J−1 has 2 (J-(J− 1)=2 rings, each containing 2 (J− 1)K nodes for a total of 2 J K nodes on level J−1. [0018] Level J has 2 J-J 32 1 ring containing 2 (J−1) K nodes for a total of 2 JK nodes on level J. [0019] For a ring R T on a level T which is not the outermost level J, then one ring R T+1 on level T+1 exists such that each node A on ring R T receives data from a node B on ring R T and a node C on ring R T+1 . For a ring R T on a level T which is not the innermost level 0 , then there exist exactly two rings R 1 T−1 and R 2 T−1 on level T−1 such that a node A on ring R T sends message data to a node D on ring R T and a node E on either ring R 1 T−1 or ring R 2 T−1 . A message on any level M of the interconnect structure can travel to two of the rings on level M−1 and is eventually able to travel to 2M of the rings on level 0 . [0020] In the following discussion a “predecessor” of a node sends message data to that node. An “ t immediate predecessor” sends message data to a node on the same ring. A “successor” of a node receives message data from that node. An “immediate successor” receives message data to a node on the same ring. [0021] For a node A RT on ring R T on level T, there are nodes B RT and D RT on ring R T of level T such that node B RT is an immediate predecessor of node A RT and node D RT is an immediate successor of node A RT . Node A RT receives message data from node B RT and sends message data to node D RT . Node A RT receives message data from a device C that is not on the ring R T and sends data to a device E that is not on ring R T . If the level is not the innermost level 0 , then device E is a node on level T−1 and there is an immediate predecessor node F on the same ring as device E. Node A RT receives control information from device F. If node A RT is on node T equal to zero, then device E is outside the interconnect structure and device E sends control information to node ART. For example, if device E is an input buffer of a computational unit, then the control information from device E to node A RT indicates to node A RT whether device E is ready to receive message data from node ART. Node D RT receives message data from a device G that is not on ring RT. Node A RT sends a control signal to device G. [0022] Control information is conveyed to resolve data transmission conflicts in the interconnect structure. Each node is a successor to a node on the adjacent outer level and an immediate successor to a node on the same level. Message data from the immediate successor has priority. Control information is send from nodes on a level to nodes on the adjacent outer level to warn of impending conflicts. [0023] When the levels are evenly spaced and the nodes on each ring and each level are evenly spaced, the interconnect structure forms a three-dimensional cylindrical structure. The interconnect structure is fully defined by designating the interconnections for each node A of each level T to devices or nodes B, C, D, E, F and G. Each node or device has a location designated in three-dimensional cylindrical coordinates (r, θ, z) where radius r is an integer which specifies the cylinder number from 0 to J, angle θ is an integer multiple of 2π/K, which specifies the spacing of nodes around the circular cross-section of a cylinder from 0 to K−1, and height z is a binary integer which specifies distance along the z-axis from 0 to 2 J −1. Height z is expressed as a binary number because the interconnection between nodes in the z-dimension is most easily described as a binary digit manipulation. On the innermost level 0 , one ring is spanned in one pass through the angles θ from 0 to K−1 and each height z designates a ring. On level 1 , one ring is spanned in two passes through the angles θ and two heights z are used to designate one ring. The ring structure proceeds in this manner through the outermost ring J in which one ring is spanned in all 2 J heights along the z-axis. [0024] Node A on a ring R receives message data from a node B, which is an immediate predecessor of node A on ring R. For a node A located at a node position N(r,θ,z), node B is positioned at N(r,(θ−1)mod K,H,(z)) on level r. (θ−1)mod K is equal K when θ is equal to 0 and equal to θ−1 otherwise. The conversion of z to H r (z) on a level r is described for z=[z J− 1, z J−2 , . . , z r , z r−1 , . . . , z 2 , z 1 , z 0 ] by reversing the order of low-order z bits from z r−1 to z 0 ] into the form z=[z J− 1, z J−2 , . . . , z 1 , z 0 , z 1 , z 2 , . . . , z r−1 ], subtracting one (modulus 2 1 ) and reversing back the modified low-order z bits. [0025] Node A also receives message data from a device C which is not on level r. If node A is positioned on the outermost level r=J, then device C is outside of the interconnect structure. If node A is not positioned on the outermost level, then device C is a node located at position N(r+1,(θ−1)mod K,z) on level r+1. [0026] Node A sends message data to a node D, which is an immediate successor to node A on ring R. Node D is located at node position N(r,(θ+1)mod K,h(z)) on level r. (θ+1)mod K is equal 0 when θ is equal to K−1 and equal to θ+1 otherwise. The conversion of z to h r (z) on a level r is described for z=[z J−1 , z J−2 , . . . , z 1 , z r−1 , . . . z 2 , z 1 , z 0 ] by reversing the order of low-order z bits from z r−1 to z 0 ] into the form z=[z J−1 , z J−2 , . . . , z r , z 0 , z 1 , z 2 , . . . , z r−1 ], adding one (modulus 2 1 ) and reversing back the low-order z bits. [0027] Node A also sends message data to a device E that is not on the same level r as node A. If node A is on the innermost level r=0, node A(r,θ,z) is interconnected with a device (e.g. a computational unit) outside of the interconnect structure. Otherwise, node A is interconnected to send message data to device E, which is a node located at node position N(r−1, (θ+1)mod K, z) on level r−1. [0028] Node A receives control information from a device F. If node A is on the innermost level r=0, the device F is the same as device E. If node A is not on the innermost level, device F is a node which is distinct from the device E. Node F is located at node position N(r−1,θ,H r−1 (z)) on level r−1. [0029] Node A sends control information to a device G. If node A is on the outermost level r=J, then device G is positioned outside of the interconnect structure. Device G is a device, for example a computational unit, that sends message data to node D. If node A is not positioned on level r=J, then device G is a node which is located at node position N(r+1,θ,h r+1 (z)) on level r+1 and device G sends message data to node D. [0030] In accordance with a second aspect of the present invention, a method is shown of transmitting a message from a node N to a target destination in a first, a second and a third dimension of three dimensions in an interconnect structure arranged as a plurality of nodes in a topology of the three dimensions. The method includes the steps of determining whether a node en route to the target destination in the first and second dimensions and advancing one level toward the destination level of the third dimension is blocked by another message, advancing the message one level toward the destination level of the third dimension when the en route node is not blocked and moving the message in the first and second dimensions along a constant level in the third dimension otherwise. This method further includes the step of specifying the third dimension to describe a plurality of levels and specifying the first and second dimensions to described a plurality of nodes on each level. A control signal is sent from the node en route to the node N on a level q in the third dimension, the control signal specifying whether the node en route is blocked. Transmission of a message is timed using a global clock specifying timing intervals to keep integral time modulus the number of nodes at a particular cylindrical height, the global clock time interval being equal to the second time interval and the first time interval being smaller than the global time interval. A first time interval a is set for moving the message in only the first and second dimensions. A second time interval α-β is set for advancing the message one level toward the destination level. A third time interval is set for sending the control signal from the node en route to the node N, the third time interval being equal to β. [0031] In accordance with a third aspect of the present invention, a method is shown of transmitting a message from an input device to an output device through an interconnect structure. The message travels through the interconnect structure connecting a plurality of nodes in a three dimensional structure. The message has a target destination corresponding to a target ring on level 0 of the interconnect structure. A message M at a node N on level T en route to a target ring on level 0 advances to a node N′ on level T−1 so long as the target ring is accessible from node N′ and no other higher priority message is progressing to node N′ to block the progress of message M. Whether the target ring is accessible from node N′ is typically efficiently determined by testing a single bit of a binary code designating the target ring. Whether a higher priority message is blocking the progress of message M is efficiently determined using timed control signals. If a message is blocked at a time t, the message is in position to progress to the next level at time t+2. If a message is blocked by a message M′ on level T−1, then a limited time duration will transpire before the message M′ is able to block message M again. [0032] A global clock controls traffic flow in the interconnect structure. Data flow follows rules that allow much of the control information to be “hidden” in system timing so that, rather than encoding all control information in a message packet header, timing considerations convey some information. For example, the target ring is encoded in the message packet header but, in some embodiments of the interconnect structure, designation of the target computational unit is determined by the timing of arrival of a message with respect to time on the global clock. [0033] The disclosed multiple level interconnect structure has many advantages. One advantage is that the structure is simple, highly ordered and achieves fast and efficient communication for systems having a wide range of sizes, from small systems to enormous systems. [0034] In addition, the interconnect structure is highly advantageous for many reasons. The interconnect structure resolves contention among messages directed toward the same node and ensures that a message that is blocked makes a complete tour of the messages at a given angle on a level before the blocking message is in position to block again. In this manner, a message inherently moves to cover all possible paths to the next level. A blocking message typically proceeds to subsequent levels so that overlying messages are not blocked for long. BRIEF DESCRIPTION OF THE DRAWINGS [0035] The features of the invention believed to be novel are specifically set forth in the appended claims. However, the invention itself, both as to its structure and method of operation, may best be understood by referring to the following description and accompanying drawings. [0036] [0036]FIGS. 1A, 1B, 1 C and 1 D are abstract three-dimensional pictorial illustrations of the structure of an embodiment of a multiple level minimum logic interconnect apparatus. [0037] [0037]FIG. 2 is a schematic diagram of a node, node terminals and interconnection lines connected to the terminals. [0038] [0038]FIGS. 3A, 3B and 3 C are schematic block diagrams that illustrate interconnections of nodes on various levels of the interconnect structure. [0039] [0039]FIG. 4 is an abstract schematic pictorial diagram showing the topology of levels of an interconnect structure. [0040] [0040]FIG. 5 is an abstract schematic pictorial diagram showing the topology of nodes of an interconnect structure. [0041] [0041]FIG. 6 is an abstract schematic pictorial diagram which illustrates the manner in which nodes of the rings on a particular cylindrical level are interconnected. [0042] [0042]FIG. 7 illustrates interconnections of a node on level zero. [0043] [0043]FIG. 8 depicts interconnections of a node on level one. [0044] [0044]FIG. 9 depicts interconnections of a node on level two. [0045] [0045]FIG. 10 depicts interconnections of a node on level three. [0046] [0046]FIG. 11 is an abstract schematic pictorial diagram which illustrates interconnections between devices and nodes of a ring on the low level cylinder. [0047] [0047]FIG. 12 is an abstract schematic pictorial diagram which illustrates interconnections among nodes of two adjacent cylindrical levels. [0048] [0048]FIG. 13 is an abstract schematic pictorial diagram showing interconnections of nodes on cylindrical level one. [0049] [0049]FIG. 14 is an abstract schematic pictorial diagram showing interconnections of nodes on cylindrical level two. [0050] [0050]FIG. 15 is an abstract schematic pictorial diagram showing interconnections of nodes on cylindrical level three. [0051] [0051]FIG. 16 is an abstract schematic pictorial diagram illustrating the interaction of messages on adjacent levels of an embodiment of the interconnection structure. [0052] [0052]FIG. 17 is a timing diagram which illustrates timing of message communication in the described interconnect structure. [0053] [0053]FIG. 18 is a pictorial representation illustrating the format of a message packet including a header and payload. [0054] [0054]FIG. 19 is a pictorial diagram which illustrates the operation of a lithium niobate node, a first exemplary node structure. [0055] [0055]FIG. 20 is a pictorial diagram which illustrates the operation of a nonlinear optical loop mirror (NOLM), a second exemplary node structure. [0056] [0056]FIG. 21 is a pictorial diagram which illustrates the operation of a terahertz optical asymmetrical demultiplexer (TOAD) switch, a third exemplary node structure. [0057] [0057]FIG. 22 is a pictorial diagram showing the operation of a regenerator utilizing a lithium niobate gate. [0058] [0058]FIG. 23 is an abstract schematic pictorial diagram illustrating an alternative embodiment of an interconnect structure in which devices issue message packets to multiple nodes. [0059] [0059]FIG. 24 is an abstract schematic pictorial diagram illustrating an alternative embodiment of an interconnect structure in which devices receive message packets from multiple nodes. [0060] [0060]FIG. 25 is an abstract schematic pictorial diagram illustrating an alternative embodiment of an interconnect structure in which devices issue message packets to nodes at various interconnect levels. DETAILED DESCRIPTION [0061] Referring to FIGS. 1A, 1B, 1 C and 1 D, an embodiment of a multiple level minimum logic interconnect apparatus 100 includes multiple nodes 102 which are connected in a multiple level interconnect structure by interconnect lines 104 . The multiple level interconnect structure is shown illustratively as a three-dimensional structure to facilitate understanding. [0062] The nodes 102 in the multiple level interconnect structure are arranged to include multiple levels 110 , each level 110 having a hierarchical significance so that, after a message is initiated in the structure, the messages generally move from an initial level 112 to a final level 114 in the direction of levels of a previous hierarchical significance 116 to levels of a subsequent hierarchical significance 118 . Illustratively, each level 110 includes multiple structures which are called rings 120 . Each ring 120 includes multiple nodes 102 . The term “rings” is used merely to facilitate understanding of the structure of a network in the abstract in which visualization of the structure as a collection of concentric cylindrical levels 110 is useful. [0063] The different FIGS. 1A, 1B, 1 C and 1 D are included to more easily visualize and understand the interconnections between nodes. FIG. 1A illustrates message data transmission interconnections between nodes 102 on the various cylindrical levels 110 . FIG. 1B adds a depiction of message data transmission interconnections between nodes 102 and devices 130 to the interconnections illustrated in FIG. 1A. FIG. 1C further shows message data interconnections between nodes 102 on different levels. FIG. 1D cumulatively shows the interconnections shown in FIGS. 1A, 1B and 1 C in addition to control interconnections between the nodes 102 . [0064] The actual physical geometry of an interconnect structure is not to be limited to a cylindrical structure. What is important is that multiple nodes are arranged in a first class of groups and the first class of groups are arranged into a second class of groups. Reference to the first class of groups as rings and the second class of groups as levels is meant to be instructive but not limiting. [0065] The illustrative interconnect apparatus 100 has a structure which includes a plurality of J+1 levels 110 . Each level 110 includes a plurality of 2 J K nodes 102 . Each level M contains 2 J-M rings 120 , each containing 2 M K nodes 102 . The total number of nodes 102 in the entire structure is (J+1)2 J K. The interconnect apparatus 100 also includes a plurality 2 J K devices 130 . In the illustrative embodiment, each device of the 2 J K devices 130 is connected to a data output port of each of the K nodes 102 in each ring of the 2 rings of the final level 114 . Typically, in an interconnect structure of a computer a device 130 is a computational unit such as a processor-memory unit or a cluster of processor-memory units and input and output buffers. [0066] Referring to FIG. 2, an interconnect structure 200 of a node 102 has three input terminals and three output terminals. The input terminals include a first data input terminal 210 , a second data input terminal 212 and a control input terminal 214 . The output terminals include a first data output terminal 220 , a second data output terminal 222 and a control output terminal 224 . The data input and output terminals of a node communicate message data with other nodes. The control terminals communicate control bits with other nodes for controlling transmission of message data. The number of control bits for controlling message transmission is efficiently reduced since much of the logic throughout the interconnect structure 200 is determined by timing of the receipt of control bits and message data in a manner to be detailed hereinafter. Only one control bit enters a node and only one control bit leaves at a given time step. Messages are communicated by generating a clock signal for timing time units. Message transmission is controlled so that, during one time unit, any node 102 receives message data from only one input terminal of the data input terminals 212 and 214 . Since, a node 202 does not have a buffer, only one of the node's output ports is active in one time unit. [0067] Referring to FIGS. 3 through 16, the topology of an interconnect structure 300 is illustrated. To facilitate understanding, the structure 300 is illustrated as a collection of concentric cylinders in three dimensions r, θ and z. Each node or device has a location designated (r, θ, z) which relates to a position (r, 2πθ/K, z) in three-dimensional cylindrical coordinates where radius r is an integer which specifies the cylinder number from 0 to J, angle θ is an integer which specifies the spacing of nodes around the circular cross-section of a cylinder from 0 to K−1, and height z is a binary integer which specifies distance along the z-axis from 0 to 2J−1. Height z is expressed as a binary number because the interconnection between nodes in the z-dimension is most easily described as a manipulation of binary digits. Accordingly, an interconnect structure 300 is defined with respect to two design parameters J and K. [0068] [0068]FIGS. 3A, 3B and 3 C are schematic block diagrams that show interconnections of nodes on various levels of the interconnect structure. FIG. 3A shows a node A RJ 320 on a ring R of outermost level J and the interconnections of node A RJ 320 to node B RJ 322 , device C 324 , node D RJ 326 , node E R(J−1) 328 , node F R(J−1) 330 and device G 332 . FIG. 3B shows a node A RT 340 on a ring R of a level T and the interconnections of node A RT 340 to node B RT 342 , node C R(T+1) 344 , node D RT 346 , node E R(T−1) 348 , node F R(T−1) 350 and node G R(T+1) 352 . FIG. 3C shows a node A R0 360 on a ring R of innermost level 0 and the interconnections of node A R0 360 to node B R0 362 , node C R1 364 , node D R0 366 , device E 368 and node G R1 372 . [0069] In FIGS. 3A, 3B and 3 C interconnections are shown with solid lines with arrows indicating the direction of message data flow and dashed lines with arrows indicating the direction of control message flow. In summary, for nodes A, B and D and nodes or devices C, E, F, G: [0070] (1) A is on level T. [0071] (2) B and C send data to A. [0072] (3) D and E receive data from A. [0073] (4) F sends a control signal to A. [0074] (5) G receives a control signal from A. [0075] (6) B and D are on level T. [0076] (7) B is the immediate predecessor of A. [0077] (8) D is the immediate successor to A. [0078] (9) C, E, F and G are not on level T. [0079] The positions in three-dimensional cylindrical notation of the various nodes and devices is as follows: [0080] (10) A is positioned at node N(r, θ, z). [0081] (11) B is positioned at node N(r, θ−1, H T (z)). [0082] (12) C is either positioned at node N(r+1, θ−1, z) or is outside the interconnect structure. [0083] (13) D is positioned at node N(r, θ+1, h T (z)). [0084] (14) E is either positioned at node N(r−1, θ+1, z) or is outside the interconnect structure and the same as device F. [0085] (15) F is either positioned at node N(r−1, θ, H T−1 (z)) or is outside the interconnect structure and the same as device E. [0086] (16) G is either positioned at node N(r+1, θ, h T (z)) or is outside the interconnect structure. [0087] In this notation, (θ−1)mod K is equal K when θ is equal to 0 and equal to θ−1 otherwise. The conversion of z to H r (z) on a level r is described for z=[z J−1 , z J−2 , . . . , z r , z r−1 , . . . , z 2 , z 1 , z 0 ] by reversing the order of low-order z bits from z r−1 to z 0 ] into the form z=[z J−1 , z J−2 , . . . , z r , z 0 , z 1 , z 2 , . . . , z r−1 ], subtracting (modulus 2 r ) and reversing back the low-order z bits. Similarly, (θ+1)mod K is equal 0 when θ is equal to K−1 and equal to θ+1 otherwise. The conversion of z to h r (z) on a level r is described for z=[z J−1 , z J−2 , . . . , z r , z r−1 , . . . , z 2 , z 1 , z 0 ] by reversing the order of low-order z bits from z r− 1 to z 0 into the form z=[z J−1 , z J−2 , . . . , z r , z 0 , z 1 , z 2 , . . . , z r−1 ], adding (modulus 2 r ) and reversing back the low-order z bits. [0088] Referring to FIG. 4, concentric cylindrical levels zero 310 , one 312 , two 314 and three 316 are shown for a J=3 interconnect structure 300 where level 0 refers to the innermost cylindrical level, progressing outward and numerically to the outermost cylindrical level 3 . A node 102 on a level T is called a level T node. [0089] An interconnect structure has J+1 levels and 2 J K nodes on each level. Referring to FIG. 5, the design parameter K is set equal to 5 so that the interconnect structure 300 has four levels (J+1=3+1=4) with 40 (2 J K=(2 3 )5=40) nodes on each level. [0090] Referring to FIG. 6, the interconnect structure is fully defined by designating the interconnections for each node A 530 of each level T to devices or nodes B 532 , C 534 , D 536 , E 538 , F 540 and G 542 . [0091] Node A(r,θ,z) 530 is interconnected with an immediate predecessor node B(r,(θ−1)mod K,H r (z)) 532 on level r. If node A(r,θ,z) 530 is on the outermost level r=J, node A(r,θ,z) 530 is interconnected with a device (e.g. a computational unit of a computer) outside of the interconnect structure. Otherwise, node A(r,θ,z) 530 is interconnected with a predecessor node C(r+1,(θ−1)mod K,z) 534 on level r+1. [0092] Node A(r,θ,z) 530 is interconnected with an immediate successor node D(r,(θ+1)mod K,h r (z)) 536 on level r. If node A(r,θ,z) 530 is on the innermost level r=0, node A(r,θ,z) 530 is interconnected with a device (e.g. a computational unit) outside of the interconnect structure. Otherwise, node A(r,θ,z) 530 is interconnected with a successor node E(r−1, (θ+1)mod K,z) 538 on level r−1 to send message data. [0093] If node A(r,θ,z) 530 is on the innermost level r=0, node A(r,θ,z) 530 is interconnected with a device (e.g. a computational unit) outside of the interconnect structure. Otherwise, node A(r,θ,z) 530 is interconnected with a node F(r−1,θ,H r−1 (z)) 540 on level r−1 which supplies a control input signal to node A(r,θ,z) 530 . [0094] If node A(r,θ,z) 530 is on the outermost level r=J, node A(r,θ,z) 530 is interconnected with a device (e.g. a computational unit) outside of the interconnect structure. Otherwise, node A(r,θ,z) 530 is interconnected with a node G(r+1, θ,h r+1 (z)) 542 on level r+1 which receives a control output signal from A(r,θ,z) 530 . [0095] Specifically, the interconnections of a node A for the example of an interconnect structure with interconnect design parameters J=3 and K=5 are defined for all nodes on a ring. Every ring is unidirectional and forms a closed curve so that the entire structure is defined by designating for each node A, a node D that receives data from node A. [0096] Referring to FIG. 7 in conjunction with FIG. 6, interconnections of a node A on level zero are shown. Node A( 0 ,θ,z)) 530 is interconnected to receive message data from immediate predecessor node B( 0 ,(θ−1)mod 5 ,z) 532 on level 0 and to send message data to immediate successor node D( 0 ,(θ+1)mod 5 ,z) 536 on level 0 . Although the interconnection term in the second dimension for nodes B and D is previously defined as H r (z) and k r (z), respectively, on level zero, H r (z) and h r (z) are equal to z. Node A( 0 ,θ,z) 530 is also interconnected to receive message data from predecessor node C( 1 ,(θ−1)mod 5 ,z) 534 on level 1 and to send message data to a device E(θ,z) 538 . Node A( 0 ,θ,z)) 530 is interconnected to receive a control input signal from a device F((θ−1)mod 5 ,z) 540 and to send a control output signal to node G( 1 ,θ,h 1 (z)) 542 on level 1 . [0097] Referring to FIG. 8 in conjunction with FIG. 6, interconnections of a node A on level one are shown. Node A( 1 ,θ,z) 530 is interconnected to receive message data from immediate predecessor node B( 1 ,(θ−1)mod 5 ,H 1 (z)) 532 on level 1 and to send message data to immediate successor node D( 1 ,(θ+1)mod 5 ,h 1 (z)) 536 on level 1 . Height z is expressed as a binary number (base 2) having the form [z 2 ,z 1 ,z 0 ]. For level one, when z is [z 2 ,z 1 , 0 ] then h 1 (z) and H 1 (z) are both [z 2 ,z 1 ,1]. When z is [z 2 ,z 1 ,1] then h 1 (z) and H 1 (z) are both [z 2 ,z 1 , 0 ]. Node A( 1 ,θ,z) 530 is also interconnected to receive message data from predecessor node C( 2 ,(θ−1)mod 5 ,z) 534 on level 2 and to send message data to successor node E( 0 ,(θ+1)mod 5 ,z) 538 on level 0 . Node A( 1 ,θ,z) 530 is interconnected to receive a control input signal from a node F( 0 ,θ,H 1 (z)) 540 on level zero and to send a control output signal to node G( 2 ,θ,h 2 (z)) 542 on level 2 . [0098] Referring to FIG. 9 in conjunction with FIG. 6, interconnections of a node A on level two are shown. Node A( 2 ,θ,z) 530 is interconnected to receive message data from immediate predecessor node B( 2 ,(θ−1)mod 5 ,H 2 (z)) 532 on level 2 and to send message data to immediate successor node D( 2 ,(θ+1)mod 5 ,h 2 (z)) 536 on level 2 . Height z is expressed as a binary number (base 2) having the form [z 2 ,z 1 ,z 0 ]. For level two, when z is [z 2 ,0,0] then h 2 (z) is [z 2 ,1,0] and H 2 (z) is [z 2 ,1,1]. When z is [z 2 ,0,1] then h 2 (z) is [z 2 ,1,1] and H 2 (z) is [z 2 ,1,0]. When z is [z 2 ,1,0] then h 2 (z) is [z 2 , 0 , 1 ] and H 2 (z) is [z 2 ,0,0.] When z is [z 2 ,1,1] then h 2 (z) is [z 2 ,0,0] and H 2 (z) is [z 2 0,1]. Node A( 2 , 0 ,z) 530 is also interconnected to receive message data from predecessor node C( 3 ,(θ−1)mod 5 ,z) 534 on level 3 and to send message data to successor node E( 1 ,(θ+1)mod 5 ,z) 538 on level 1 . Node A( 2 ,θ,z) 530 is interconnected to receive a control input signal from a node F( 1 ,θ,H 2 (z)) 540 on level 1 and to send a control output signal to node G( 3 ,θ,h 3 (z)) 542 on level 3 . [0099] Referring to FIG. 10 in conjunction with FIG. 6, interconnections of a node A on level three are shown. Node A( 3 ,θ,z) 530 is interconnected to receive message data from immediate predecessor node B( 3 ,(θ−1)mod 5 ,H 3 (z)) 532 on level 3 and to send message data to immediate successor node D( 3 ,(θ+1)mod 5 ,h 3 (z)) 536 on level 3 . For level three, when z is [0,0,0] then h 3 (z) is [1,0,0] and H 3 (z) is [1,1,1]. When z is [0,0,1] then h 3 (z) is [1,0,1] and H 3 (z) is [1,1,0]. When z is [0,1,0] then h 3 (z) is [1,1,0] and H 3 (z) is [1,0,0]. When z is [0,1,1] then h 3 (z) is [1,1,1] and H 3 (z) is [1,0,1]. When z is [1,0,0] then h 3 (z) is [0,1,0] and H 3 (z) is [0,0,0]. When z is [1,0,1] then h 3 (z) is [0,1,1] and H 3 (z) is [0,0,1]. When z is [1,1,0] then h 3 (z) is [0,0,1] and H 3 (z) is [0,1,0]. When z is [1,1,1] then h 3 (z) is [0,0,0] and H 3 (z) is [0,1,1]. Node A( 3 ,θ,z) 530 is also interconnected to receive message data from predecessor node C( 4 ,(θ−1)mod 5 ,z) 534 on level 4 and to send message data to successor node E( 2 ,(θ+1)mod 5 ,z) 538 on level 2 . Node A( 3 ,θ,z) 530 is interconnected to receive a control input signal from a node F( 2 ,θ,H 3 (z)) 540 on level 2 and to send a control output signal to node G( 4 ,θ,h 4 (z)) 542 on level 4 . [0100] [0100]FIG. 11 illustrates interconnections between devices 130 and nodes 102 of a ring 120 on the cylindrical level zero 110 . In accordance with the description of the interconnect structure 200 of a node 102 discussed with respect to FIG. 2, a node 102 has three input terminals and three output terminals, including two data input terminals and one control input terminal and two data output terminals and one control output terminal. In a simple embodiment, a device 130 has one data input terminal 402 , one control bit input terminal 404 , one data output terminal 406 and one control bit output terminal 408 . [0101] Referring to FIG. 11, nodes 102 at the lowest cylindrical level 110 , specifically nodes N( 0 ,θ,z), are connected to devices CU(θ,z). In particular, the data input terminal 402 of devices CU(θ,z) are connected to the second data output terminal 222 of nodes N( 0 ,θ,z). The control bit output terminal 408 of devices CU(θ,z) are connected to the control input terminal 214 of nodes N( 0 ,θ,z). [0102] The devices CU( 0 ,z) are also connected to nodes N(J,θ,z) at the outermost cylinder level. In particular, the data output terminal 406 of devices CU(θ,z) are connected to the second data input terminal 212 of nodes N(J,θ,z). The control bit input terminal 404 of devices CU(θ,z) are connected to the control output terminal 224 of nodes N( 0 ,θ,z)). Messages are communicated from devices CU(θ,z) to nodes N(J,θ,z) at the outermost cylindrical level J. Then messages move sequentially inward from the outermost cylindrical level J to level J−1, level J−2 and so forth unit the messages reach level 0 and then enter a device. Messages on the outermost cylinder J can reach any of the 2 J rings at level zero. Generally, messages on any cylindrical level T can reach a node on 2 T rings on level zero. [0103] [0103]FIG. 12 illustrates interconnections among nodes 102 of two adjacent cylindrical levels 110 . Referring to FIG. 12 in conjunction with FIG. 2, nodes 102 at the T cylindrical level 110 , specifically nodes N(T,θ,z) 450 , have terminals connected to nodes on the T level, the T+1 level and the T−1 level. These connections are such that the nodes N(T,θ,z) 450 have one data input terminal connected to a node on the same level T and one data input terminal connected to another source, usually a node on the next outer level T+1 but for nodes on the outermost level J, a device is a source. In particular, nodes N(T,θ,z) 450 have a first data input terminal 210 which is connected to a first data output terminal 220 of nodes N(T+1,θ−1,z) 452 . Also, nodes N(T,θ,z) 450 have a first data output terminal 220 which is connected to a first data input terminal 210 of nodes N(T−1,θ+1,z) 454 . [0104] The nodes N(T,θ,z) 450 also have a second data input terminal 212 and a second data output terminal 222 which are connected to nodes 102 on the same level T. The second data input terminal 212 of nodes N(T,θ,z) 450 are connected to the second data output terminal 222 of nodes N(T,θ−1,h T (z)) 456 . The second data output terminal 222 of nodes N(T,θ,z) 450 are connected to the second data input terminal 212 of nodes N(T,θ+1,H T (z)) 458 . The cylinder height designation H T (z) is determined using an inverse operation of the technique for determining height designation h T (z). The interconnection of nodes from cylindrical height to height (height z to height H T (z) and height h T (z) to height z) on the same level T is precisely defined according to a height transformation technique and depends on the particular level T within which messages are communicated. Specifically in accordance with the height transformation technique, the height position z is put into binary form where z=z J−1 2 J−1 +z J−1 2 J−2 + . . . +z T 2 T +z T−1 2 T−1 + . . . +z 1 2 1 +z 0 2 0 . A next height position h T (z) is determined using a process including three steps. First, binary coefficients starting with coefficient z, up to and but not including coefficient z T are reversed in order while coefficients z T and above are kept the same. Thus, after the first step the height position becomes z JH−1 2 J−1 +z J−2 2 J−2 + . . . +z T 2 T +z 0 2 0 +z 1 2 1 + . . . +z T−2 2 T−2 +z T−1 2 T−1 . Second, an odd number modulus 2 T, for example one, is added to the height position after inversion. Third, circularity of the height position is enforced by limiting the inverted and incremented height position by modulus 2 T . Fourth, the first step is repeated, again inverting the binary coefficients below the z J coefficient of the previously inverted, incremented and limited height position. The inverse operation for deriving height descriptor H T (z) is determined in the same manner except that, rather than adding the odd number modulus 2 T to the order-inverted bit string, the same odd number modulus 2 T is added to the order-inverted bit string. [0105] The interconnection between nodes 102 on the same level is notable and highly advantageous for many reasons. For example, the interconnection structure resolves contention among messages directed toward the same node. Also, the interconnection structure ensures that a message on a particular level that is blocked by messages on the next level makes a complete tour of the messages on that level before any message is in position to block again. Thus a message inherently moves to cover all possible paths to the next level. Furthermore, a blocking message must cycle through all rings of a level to block a message twice. Consequently, every message is diverted to avoid continuously blocking other messages. In addition, blocking messages typically proceed to subsequent levels so that overlying messages are not blocked for long. [0106] When messages are sent from second data output terminal 222 of a node N(T,θ,z) 450 to a second data input terminal 212 of a node N(T,θ+1,h T (z)), a control code is also sent from a control output terminal 224 of the node N(,θ,z) 450 to a control input terminal 214 of a node N(T+1,θ,h T+1 (z)), the node on level T+1 that has a data output terminal connected to a data input terminal of node N(T,θ+1,h T (z)). This control code prohibits node N(T+1,θ,h T+1 (z)) from sending a message to node N(T,θ+1,h T+1 (z)) at the time node N(T,θ,z) 450 is sending a message to node N(T,θ+1,h T+1 (z)). When node N(T+1,θ,h T+1 (z)) is blocked from sending a message to node N(T,θ+1,h T+1 (z)), the message is deflected to a node on level T+1. Thus, messages communicated on the same level have priority over messages communicated from another level. [0107] The second data output terminal 222 of nodes N(T,θ−1,H T z)) are connected to a second data input terminal 212 of nodes N(T,θ,z) 450 so that nodes N(T,θ,z) 450 receive messages from nodes N(T,θ−1,H T (z)) that are blocked from transmission to nodes N(T−1,θ,H T (z)). Also, the control output terminal 224 of nodes N(T−1,θ,H T (z)) to the control input terminal 214 of nodes N(T,θ,z) 450 to warn of a blocked node and to inform nodes N(T,θ,z) 450 not to send data at this time since no node receives data from two sources at the same time. [0108] Referring to FIG. 13, interconnections of nodes 102 on cylindrical level one exemplify the described interconnections and demonstrate characteristics and advantages that arise from the general interconnection technique. In this example, the number of nodes K at a cylindrical height is five and the number of heights 2 J is 2 2 , or 4, for a three level (J+1) interconnect structure 500 . Nodes N( 1 ,θ,z) 510 have: (1) a first data input terminal 210 connected to a first data output terminal 220 of nodes N( 2 ,θ−1,z) 512 , (2) a control output terminal 224 connected to control input terminal 214 of nodes N( 2 ,θ,h 2 (z)) 512 , (3) a first data output terminal 220 connected to a first data input terminal 210 of nodes N(( 0 ,θ+1,z) 516 , (4) a control input terminal 214 connected to a control output terminal 224 of nodes N( 0 ,θ,H,(z)) 516 , (5) a second data input terminal 212 connected to the second data output terminal 222 of nodes N( 1 ,θ−1,H 1 (z)) 520 , and (6) a second data output terminal 222 connected to the second data input terminal 212 of nodes N( 1 ,θ+1,h 1 (z)) 522 . For nodes N( 1 ,θ,z) 510 on level one, height z differs from height h 1 (z) and height H 1 (z) only in the final bit position. [0109] Messages are communicated through the interconnect structure 500 in discrete time steps. A global clock (not shown) generates timing signals in discrete time steps modulus the number of nodes K at a cylindrical height z of a cylindrical level r. When messages traverse the interconnect structure 500 on the same level (for example, level one) because nodes on an inner level are blocked, messages are communicated from node to node in the discrete time steps. For the interconnect structure 500 with an odd number (K=5) of nodes at a cylindrical level, if data traverses level one for 2K time steps, then the message packet visits 2K different nodes. On time step 2K +1, message packets will begin repeating nodes following the sequential order of the first node traversal. Because the global clock generates the discrete time steps integral time modulus K, if a message packet on level one is over the target ring of that packet at a time T=0 (modulus K) and is deflected by a message on level zero, the message will be over the target ring also at a time T=0 (modulus K) to make another attempt to enter the target ring. In various embodiments, this timing characteristic is consistent throughout the interconnect structure so that, if a message packet is in a position to descend to the next level at a time T=0 (modulus K), the packet will once again be in a position to descend at a subsequent time T=0 (modulus K). [0110] Referring to FIG. 14 in conjunction with FIG. 13, interconnections of nodes 102 on cylindrical level two further exemplify described interconnections. In FIG. 14, a level two message path 620 is shown overlying the paths 610 and 612 of messages moving on level one. The number of nodes K at a cylindrical level is five and the number of levels 2 J is 2 2 , or 4, for a three level (J+1) interconnect structure 500 . Same-level interconnections of nodes N( 2 ,θ,z) include: (1) a second data input terminal 212 connected to the second data output terminal 222 of nodes N( 2 ,θ−1,h 2 (z)) and (2) a second data output terminal 222 connected to the second data input terminal 212 of nodes N( 2 ,θ+1,H 2 (z)). For nodes N( 2 ,θ,z) on level two, height z differs from height h 2 (z) and height H 2 (z) only in the final two bit positions. Generally stated in binary form for any suitable number of nodes K at a height and number of heights 2 J in a level, bits z and h 2 (z) on cylindrical level two are related as follows: [0111] [z J−1 , z J−2 , . . . , z 2 , 0 , 0 ]′=[z J−1 , z J−2 , . . . , z 2 , 1 , 0 ]; [0112] [z J−1 , z J−2 , . . . , z 2 , 1 , 0 ]′=[z J−1 , z J−2 , . . . , z 2 , 0 , 1 ]; [0113] [z J−1 , z J−2 , . . . , z 2 , 0 , 1 ]′=[z J−1 , z J−2 , . . . , z 2 , 1 , 1 ] and [0114] [z J−1 , z J−2 , . . . , z 2 , 1 , 1 ]′=[z J−1 , z J−2 , . . . , z 2 , 0 , 0 ]. PCT [0115] A second advantage of this interconnection technique for nodes on the same level is that blocked messages are directed to avoid subsequent blocking. FIG. 14 illustrates a message blocking condition and its resolution. On level one, a message m 0 610 is shown at node N 001 and a message m 1 612 at node N 011 . A message M 620 on level two at node N 002 is targeted for ring zero. At a time zero, message M 620 is blocked and deflected by message m 1 612 to node N 122 at time one. Assuming that messages m 0 and m 1 are also deflected and traversing level one, at a time one message m 0 610 is at node N 111 and message m 1 612 at node N 101 . At a time two, message M 620 moves to node N 212 , message m 0 610 to node N 201 and message m 1 612 to node N 211 . Thus, at time two, message M 620 is deflected by message m 0 610 . At time four, message M 620 is again blocked by message m 1 612 . This alternating blocking of message M 620 by messages m 0 610 and m 1 612 continues indefinitely as long as messages m 0 610 and m 1 612 are also blocked. This characteristic is pervasive throughout the interconnect structure so that a single message on an inner level cannot continue to block a message on an outer level. Because a single message packet cannot block another packet and blocking packets continually proceed through the levels, blocking does not persist. [0116] Referring to FIG. 15, interconnections of nodes 102 on cylindrical level three show additional examples of previously described interconnections. A level three message path 720 is shown overlying the paths 710 , 712 and 714 of messages moving on level two. The number of nodes K at a cylindrical height is seven and the number of heights 2 J is 2 3 (8), for a four level (J+1) interconnect structure. Same-level interconnections of nodes N( 3 ,θ,z) include: (1) a second data input terminal 212 connected to the second data output terminal 222 of nodes N( 3 ,θ−1,h 3 (z)) and (2) a second data output terminal 222 connected to the second data input terminal 212 of nodes N( 3 ,θ+1,H 3 (z)). For nodes N( 3 ,θ,z) on level three, height z differs from height h 3 (z) and height H 3 (z) only in the final three bit positions. Generally stated in binary form for any suitable number of nodes K at a cylindrical height and number of heights 2 J in a level, bits z and h 3 (z) on cylindrical level three are related as follows: [0117] [z J−1 , z J−2 , . . . z 3 , 0 , 0 , 0 ]′=[z J−1 , z J−2 , . . . , z 3 , 1 , 0 , 0 ]; [0118] [z J−1 , z J−2 , . . . z 3 , 1 , 0 , 0 ]′=[z J−1 , z J−2 , . . . , z 3 , 0 , 1 , 0 ]; [0119] [z J−1 , z J−2 , . . . z 3 , 0 , 1 , 0 ]′=[z J−1 , z J−2 , . . . , z 3 , 1 , 1 , 0 ]; [0120] [z J−1 , z J−2 , . . . z 3 , 1 , 1 , 0 ]′=[z J−1 , z J−2 , . . . , z 3 , 0 , 0 , 1 ]; [0121] [z J−1 , z J−2 , . . . z 3 , 0 , 0 , 1 ]′=[z J−1 , z J−2 , . . . , z 3 , 1 , 0 , 1 ]; [0122] [z J−1 , z J−2 , . . . z 3 , 1 , 0 , 1 ]′=[z J−1 , z J−2 , . . . , z 3 , 0 , 1 , 1 ]; [0123] [z J−1 , z J−2 , . . . z 3 , 0 , 1 , 1 ]′=[z J−1 , z J−2 , . . . , z 3 , 1 , 1 , 1 ]; [0124] [z J−1 , z J−2 , . . . z 3 , 1 , 1 , 1 ]′=[z J−1 , z J−2 , . . . , z 3 , 0 , 0 , 0 ]; [0125] [0125]FIG. 15 illustrates another example of a message blocking condition and its resolution. On level two, a message m 0 710 is shown at node N 002 , a message m 1 712 at node N 012 , a message m 2 714 at node N 022 and a message m 3 716 at node N 032 . A message M 720 on level three at node N 303 is targeted for ring zero. At a time zero, message M 720 is blocked and deflected by message m 3 716 to node N 173 at time one. Assuming that messages m 0 , m 1 , m 2 and m 3 are also deflected and traversing level two, at a time one message m 0 710 is at node N 132 , message m 1 712 at node N 122 , message m 2 714 at node N 102 and message m 3 716 at node N 112 . At a time two, message M 720 moves to node N 233 , message m 0 710 to node N 212 , message m 1 712 to node N 202 , message m 2 714 to node N 232 and message m 3 716 to node N 222 . Thus, at time two, message M 720 is deflected by message m 1 712 . At time four, message M 720 is blocked by message m 2 714 . At time six, message M 720 is blocked by message m 0 710 . At time eight, message M 720 is again blocked by message m 3 716 . This alternating blocking of message M 720 by messages m 0 710 , m 1 712 , m 2 714 and m 3 716 continues indefinitely as long as messages m 0 710 , m 1 712 , m 2 714 and m 3 716 are also blocked. [0126] This analysis illustrates the facility by which the described interconnect structure avoids blocking at any level. Thus, “hot spots” of congestion in the structure are minimized. This characteristic is maintained at all levels in the structure. [0127] The described interconnect structure provides that every node N( 0 ,θ,z) on level zero is accessible by any node N(J,θ,z) on outermost level J. However, only half of the nodes N( 0 ,θ,z) on level zero are accessible by a node N(J−1 ,θ,z) on the level once removed from the outermost level. Data at a node N( 1 ,θ,z) on level one can access any node N( 0 ,θ,z) on level zero so long as the binary representation of height z of level one and the binary representation of ring r of level zero differ only in the last bit. Similarly, data at a node N( 2 ,θ,z) on level two can access any node N( 0 ,θ,z) on level zero so long as the binary representation of height z of level two and the binary representation of ring r of level zero differ only in the last two bits. A general rule is that, data at a node N(T,θ,z) on level T can access any node N( 0 ,θ,z) on level zero so long as the binary representation of height z of level T and the binary representation of ring r of level zero differ only in the last T bits. Accordingly, moving from the outermost level J to level J−1 fixes the most significant bit of the address of the target ring. Moving from level J−1 to level J−2 fixes the next most significant bit of the address of the target ring and so forth. At level zero, no bits are left to be fixed so that no header bit is tested and a message is always passed to a device. In some embodiments, an additional header bit is included and tested at a level zero node. This final bit may be used for various purposes, such as for directing message data to a particular buffer of a device when the device accepts the message data. An advantage of including an additional bit in the header and performing a bit test at the final node is that all the nodes at all levels of the interconnect structure operate consistently. [0128] In some embodiments of an interconnect structure, an additional header bit is included in a message packet. This bit indicates that a message packet is being transmitted. Another purpose for such an additional bit in the header is to identify which bit in the header is the control bit. [0129] A message packet moves from a level T to the next inner level T−1 so long as two conditions are met, as follows: (1) the target ring of the message packet is accessible from level T−1, and (2) the message packet is not blocked by a message on the level T−1. [0130] One significant aspect of this structure is that any message packet at a node N(T,θ,z) on a level T that can access its target ring can also access the target ring from a node N(T−1,θ+1,z) only if the bit T−1 of the address ring is the same as bit T−1 of the target ring. Therefore, analysis of only a single bit yields all information for determining a correct routing decision. [0131] Referring to FIG. 16, a general relationship between message packets on two adjacent levels T and T+1 is described. In this example, a message packet M at a node N 450 on level four, which is targeted for ring zero, is potentially blocked by eight message packets m 0 810 , m 1 811 , m 2 812 , m 3 813 , m 4 814 , m 5 815 , m 6 816 and m 7 817 at nodes N 3i0 residing on each of the heights 0 to 7 on level three. Although the behavior of the interconnect structure is analyzed with respect to levels three and four for purposes of illustration, the analysis is applicable to any arbitrary adjacent levels. At an arbitrary time step, illustratively called time step zero, the message M moves from node N 450 on level four to node N 351 on level three unless a control code is send to node N 450 from a level three node having a data output terminal connected to node N 351 . In this example, node N 310 has a data output terminal connected to node N 351 and, at time step zero, message m 7 817 resides at node N 310 . Accordingly, node N 310 sends a control code, in this example a single bit code, to node N 450 , causing deflection of message M to node N 4D1 (where D is a hexadecimal designation of 13 ) on an interconnection line. A bit line illustratively shows the control connection from node N 310 to node N 450 . At a time step one, message M moves from node N 4D1 to node N 432 on interconnection line regardless of whether a node N 328 is blocked because ring zero is not accessible from node N 328 . At a time step two, message M moves from node N 432 to node N 334 unless a control blocking code is sent from node N 352 to node N 432 where node N 352 is the node on level three that has a data output terminal connected to a data input terminal of node N 334 . However, the message M is blocked from accessing node N 334 because message m 6 currently resides at node N 352 at time step two. A deflection control code is sent from node N 352 to node N 432 on control bit line 822 . Furthermore, assuming that none of the message packets t progresses to level two and beyond, at time step four, message M is blocked by message m 2 via a control code sent on control bit line. At time six, message M is blocked by message m 4 though a blocking control code on control bit line. [0132] This example illustrates various advantages of the disclosed interconnection structure. First, deflections of the message M completely tour all of the heights on a level T if messages m j on level T−1 continue to block progression to the level T−1 for all levels T. Accordingly, a message M on a level T is blocked for a complete tour of the heights only if 2 T−1 messages are in position on level T−1 to 15 block message M. In general, a message m j on a level T−1 must remain on the level T−1 for 2 T+1 time steps to block the same message M on level T twice. [0133] The description exemplifies an interconnect structure in which messages descend from an outer level to devices at a core inner layer by advancing one level when the height dimension matches the destination ring location and traversing the rings when the ring location does not match the height designation. In other embodiments, the messages may move from an inner level to an outer level. In some embodiments, the heights may be traversed as the level changes and the height held constant as the level remains stationary. In these embodiments, the progression of messages through nodes is substantially equivalent to the disclosed interconnect structure. However, the advantage of the disclosed network that avoids blocking of messages is negated. [0134] Referring to FIG. 17, a timing diagram illustrates timing of message communication in the described interconnect structure. In various embodiments of the interconnect structure, control of message communication is determined by timing of message arrival at a node. A message packet, such as a packet 900 shown in FIG. 18, includes a header 910 and a payload 920 . The header 910 includes a series of bits 912 designating the target ring in a binary form. When a source device CU(θ 1 ,z 1 ) at an angle θ 1 and height z, sends a message packet M to a destination device CU(θ 2 ,z 2 ) at an angle θ 2 and height z 2 , the bits 912 of header 910 are set to the binary representation of height z 2 . [0135] A global clock servicing an entire interconnect structure keeps integral time modulus K where, again, K designates the number of nodes n at a cylinder height z. There are two constants α and β such that the duration of α exceeds the duration of β and the following five conditions are met. First, the amount of time for a message M to exit a node N(T,θ+1,h T (z)) on level T after exiting a node N(T,θ,z) also on level T is α. Second, the amount of time for a message M to exit a node N(T−1,θ+1,z) on level T−1 after exiting a node N(T,θ,z) on level T is α−β. Third, the amount of time for a message to travel from a device CU to a node N(r,θ,z) is α−β. Fourth, when a message M moves from a node N(r,θ,z) to a node N(r,θ+1, h r (z)) in time duration (a, the message M also causes a control code to be sent from node N(r,θ,z) to a node N(r+1,θ+1,h r (z)) to deflect messages on the outer level r+1. The time that elapses from the time that message M enters node N(r,θ,z) until the control bit arrives at node N(r+1,θ+1,h r+1 (z)) is time duration β. The aforementioned fourth condition also is applicable when a message M moves from a node N(J,θ,z) to a node N(J,θ+1,h J (z)) at the outermost level J so that the message M also causes a control code to be sent from node N(J,θ,z) to a device CU(θ,z). The time that elapses from the time that message M enters node N(r,θ,z) until the control bit arrives at device CU(θ,z) is time duration β. Fifth, the global clock generates timing pulses at a rate of α. [0136] When the source device CU(θ 1 ,z 1 ) sends a message packet M to the destination device CU(θ 2 ,z 2 ), the message packet M is sent from a data output terminal of device CU(θ 1 ,z 1 ) to a data input terminal of node N(J,θ 1 ,z 1 ) at the outermost level J. Message packets and control bits enter nodes N(T,θ,z) on a level T at times having the form nα+Lβ where n is a positive integer. The message M from device CU(θ 1 ,z 1 ) is sent to the data input terminal of node N(J,θ 1 ,z 1 ) at a time t 0 −β and is inserted into the data input terminal of node N(J,θ 1 ,z 1 ) at time t 0 so long as the node N(J,θ 1 ,z 1 ) is not blocked by a control bit resulting from a message traversing on the level J. Time to has the form (θ 2 −θ 1 )α+Jβ. Similarly, there is a time of the form (θ 2 −θ 1 )α+Jβ at which a data input terminal of node N(J,θ 1 ,z 1 ) is receptive to a message packet from device CU(θ 1 ,z 1 ). [0137] Nodes N(r,θ,z) include logic that controls routing of messages based on the target address of a message packet M and timing signals from other nodes. A first logic switch (not shown) of node N(r,θ,z) determines whether the message packet M is to proceed to a node N(T−1,θ+1,z) on the next level T−1 or whether the node N(T−1,θ+1,z) is blocked. The first logic switch of node N(r,θ,z) is set according to whether a single-bit blocking control code sent from node N(T−1,θ,H T (z)) arrives at node N(r,θ,z) at a time to. For example, in some embodiments the first logic switch takes a logic 1 value when a node N(T−1,θ+1,z) is blocked and a logic 0 value otherwise. A second logic switch (not shown) of node N(r,θ,z) determines whether the message packet M is to proceed to a node N(T−1,θ+1,z) on the next level T−1 or whether the node N(T−1,θ+1,z) is not in a suitable path for accessing the destination device CU(θ 2 ,z 2 ) of the message packet M. The message packet M includes the binary representation of destination height z 2 (z 2(J) , z 2(J−1) , . . . , z 2(T) , . . . , z 2(1) , z 2(0) . The node N(T,θ,z) on level T includes a single-bit designation z T of the height designation z (z J , z J−1 , . . . , z T , . . . , z 1 , z 0 ). In this embodiment, when the first logic switch has a logic 0 value and the bit designation z 2(T) of the destination height is equal to the height designation z T , then the message packet M proceeds to the next level at node N(T−1,θ+1,z) and the destination height bit z 2(T) is stripped from the header of message packet M. Otherwise, the message packet M traverses on the same level T to node N(T,θ+1,h T (z)). If message packet M proceeds to node N(T−1,θ+1,z), then message packet M arrives at a time t 0 +(α−β) which is equal to a time (z 2 −z 1 +1)α+(J−1)β. If message packet M traverses to node N(T,θ+1,h T (z)), then message packet M arrives at a time t 0 +α, which is equal to a time (z 2 −z 1 +1)α+Jβ. As message packet M is sent from node N(r,θ,z) to node N(T,θ+1,h T (z)), a single-bit control code is sent to node N(T+1,θ+1,H T+1 (z)) (or device CU(θ,z) which arrives at time t 0 +β. This timing scheme is continued throughout the interconnect structure, maintaining synchrony as message packets are advanced and deflected. [0138] The message packet M reaches level zero at the designated destination height z 2 . Furthermore, the message packet M reaches the targeted destination device CU(θ 2 ,z 2 ) at a time zero modulus K (the number of nodes at a height z). If the targeted destination device CU(θ 2 ,z 2 ) is ready to accept the message packet M, an input port is activated at time zero modulus K to accept the packet. Advantageously, all routing control operations are achieved by comparing two bits, without ever comparing two multiple-bit values. Further advantageously, at the exit point of the interconnect structure as message packets proceed from the nodes to the devices, there is no comparison logic. If a device is prepared to accept a message, the message enters the device via a clock-controlled gate. [0139] Many advantages arise as a consequence of the disclosed timing and interconnect scheme. In an optical implementation, rather than an electronic implementation, of the interconnect structure, signals that encode bits of the header typical have a longer duration than bits that encode the payload. Header bits are extended in duration because, as messages communicate through the interconnect structure, timing becomes slightly skewed. Longer duration header bits allow for accurate reading of the bits even when the message is skewed. In contrast, payload bits encode data that is not read during communication through the interconnect structure. The disclosed timing scheme is advantageous because the number of header bits in a message is greatly reduced. Furthermore, in some embodiments the number of header bits is decremented as bits are used for control purposes at each level then discarded while messages pass from level to level in the interconnect structure. In embodiments that discard a control bit for each level of the interconnect structure, logic at each node is simplified since the control bit at each level is located at the same position throughout the interconnect structure. [0140] That messages communicated on the same level have priority over messages communicated from another level is similarly advantageous because message contention is resolved without carrying priority information in the message header. Message contention is otherwise typically resolved by giving priority to messages that have been in an interconnect structure the longest or to predetermined prioritization. These techniques use information stored in the header to resolve contention. [0141] Although it is advantageous that the interconnect structure and message communication method determines message transmission routing using self-routing decision-making which is local to the nodes and depends on message timing, in some embodiments of the control structure, both local and global communication control is employed. For example, one embodiment of an interconnect structure uses local control which is based on timing to control transmission of message packets in a first transmission mode and alternatively uses global control via a scheduler to administer communication of lengthy strings of message data in a second mode. In the global mode, the usage of a scheduler makes the usage of control bit input and output terminals unnecessary. [0142] One consequence of self-routing of message packets is that the ordering of message packet receipt at a target device may be variable. In some embodiments, the correct order of message segments is ordered by sending ordering information in the message header. Other embodiments employ an optical sorter to order message packets. [0143] Although many advantages are realized through a control structure and communication method which utilizes timing characteristics, rather than control bits in the header, to control message routing, some interconnect node technologies more suitably operate in a routing system utilizing no timing component. Thus in these technologies, instead of introducing a message at predetermined time so that the message arrives at a preset destination at a designated, routing information is contained in additional header bits. Accordingly, a designated target device position is included in header bits, for example bits following the designated target ring position. [0144] In one embodiment, the label of a target device is represented as a single logic one in a string of logic zeros. Thus, when a message arrives at a device N, the device samples the Nth bit of the device element of the header (as distinguished from the ring element) and accepts the message if the Nth bit is a logic one. This technique is highly suitable for optical node implementations. [0145] Nodes [0146] The nodes N(r,θ,z) have been described in generic terms to refer to various data communication switches for directing data to alternative data paths. Node structures which are presently available include electronic nodes, optical nodes and mixed optical/electronic nodes. What is claimed include, for example, interconnect and timing methods, an interconnect apparatus and an interconnect topology. These methods and apparati involve nodes in a generic sense. Thus, the scope of the claims is not limited by the particular type of node described herein and is to extend to any node known now or in the future, which performs the function of the nodes described herein. [0147] One example of a node 1300 is shown, referring to FIG. 19, which includes a lithium niobate (LiNbO3) gate 1302 . The lithium niobate gate 1302 has two data input terminals 1310 and 1312 , two data output terminals 1320 and 1322 and one control input terminal 1330 . Various control circuitry 1340 is added to the lithium niobate gate 1302 to form a control output terminal 1332 of the node 1300 . Node 1300 also includes optical to electronic converters 1354 , 1356 and 1358 . The lithium niobate gate 1302 is forms a 2×2 crossbar. Data paths 1342 and 1344 are optical and the control of the node 1300 is electronic. The lithium niobate gate 1302 is combined with a photodetectors 1350 and 1352 and a few electronic logic components to form a node 1300 for various embodiments of an interconnect structure. [0148] In operation, as a message packet 1360 approaches the node 1300 , part of the message packet signal 1360 is split off and an appropriate bit of the message packet header (not shown) designating a bit of the binary representation of destination ring in accordance with the discussion hereinbefore, is read by the photodetector 1350 . This bit is converted from optical form to an electronic signal. This bit, a bit designating the cylinder height upon which the node 1300 lies and a bit designating whether a destination node on the next level is blocked are processed electronically and a result of the logical tests of these bits is directed to the control input terminal 1330 of the lithium niobate gate 1302 . In a first type of lithium niobate gate technology, if the result signal is a logic zero, the gate switches in the cross state. In a second type of lithium niobate gate technology, a logic zero result signal switches the gate in a bar (straight through) state. [0149] Referring to FIG. 20, an additional example of a node 1400 is shown. Node 1400 uses a nonlinear optical loop mirror (NOLM) 1410 to perform a switching function. A nonlinear optical loop mirror is a device that makes use of the refractive index of a material to form a completely optical switch that is extremely fast. One example of a NOLM switch includes a data input terminal 1412 and a control input terminal 1414 . Depending upon the signal at the control input terminal 1414 , data either leaves the NOLM 1410 through the same data input terminal 1412 from which the data entered (hence the term mirror) or the data exits through a data output terminal 1416 . Data is polarized and split into two signal “halves” of equal intensity. In the absence of a control pulse, the two halves of the signal recombine and leave the NOLM 1410 through the data input terminal 1414 . When a control pulse is applied to the control input terminal 1414 , the control pulse is polarized at right angles to the data pulse and inserted into the NOLM 1410 so that the control pulse travels with one half of the data pulse. The control pulse is more intense than the data pulse and the combined first half of the data pulse and the control pulse quickly pass the second half of the data pulse so that the second half of the data pulse is only minimally accelerated. Thus, the two halves of the data pulse travel with slightly different velocities and are 180° out of phase when the two halves are recombined. This phase difference causes the combined data pulse signal to pass through the data output terminal 1416 . One disadvantage of the NOLM 1410 is that switching is operational only when a long optical transmission loop is employed, thus latency is a problem. [0150] Referring to FIG. 21, another example of a node 1500 is shown which uses a terahertz optical asymmetrical demultiplexer (TOAD) switch 1510 . The TOAD switch 1510 is a variation of the NOLM switch 1410 . The TOAD 1510 includes an optical fiber loop 1512 and a semiconductor element 1514 , a nonlinear element (NLE) or a semiconductor optical amplifier for example. The TOAD switch 1510 has an input data terminal 1520 which also serves as an output data port under some conditions. The TOAD switch 1510 also has a separate second output data terminal 1522 . The semiconductor element 1514 is placed asymmetrically with respect to the center 1516 of the fiber optic loop 1512 . A distance 1518 from the semiconductor element 1514 to the center 1516 of the fiber optic loop 1512 is the distance to transmit one bit of data. The TOAD 1510 functions by removing a single bit from a signal having a high data rate. The TOAD 1510 is switched by passing a constant electrical current through the semiconductor element 1514 . An optical signal entering the semiconductor material causes the index of refraction of the material to immediately change. After the optical signal terminates, the index of refraction slowly (a time span of several bits) drifts back to the level previous to application of the optical signal. A control pulse is an optical signal having an intensity higher than that of an optical data signal and polarization at right angles to the optical data signal. An optical data input signal is polarized and split into two signal “halves” of equal intensity. The control pulse is injected in a manner to move through the fiber optic loop 1512 directly over the bit that is to be removed. Because the distance 1518 is exactly one bit long, one half of the split optical data signal corresponding to a bit leaves the semiconductor element 1514 just as the other half of the bit enters the semiconductor element 1514 . The control pulse only combines with one half of the optical data signal bit so that the velocity of the two halves differs. The combined data and control signal bit exits the TOAD 1510 at the input data terminal 1520 . Thus, this first bit is removed from the data path. A next optical signal bit is split and a first half and second half, moving in opposite directions, are delayed approximately the same amount as the index of refraction of the semiconductor element 1514 gradually changes so that this bit is not removed. After a few bits have passes through the semiconductor element 1514 , the semiconductor material relaxes and another bit is ready to be multiplexed from the optical data signal. Advantageously, the TOAD 1510 has a very short optical transmission loop 1512 . [0151] Regenerators [0152] It is a characteristic of certain nodes that messages lose strength and pick up noise as they propagate through the nodes. Using various other nodes, message signals do not lose strength but noise accumulates during message transmission. Accordingly, in various embodiments of the interconnect structure, signal regenerators or amplifiers are used to improve message signal fidelity after messages have passed through a number of nodes. [0153] Referring to FIG. 22, one embodiment of a regenerator 1600 is shown which is constructed using a lithium niobate gate 1602 . A lithium niobate gate 1602 regenerates message data having a transmission speed of the order of 2.5 gigabits. The lithium niobate gate 1602 detects and converts an optical message signal to an electronic signal which drives an electronic input port 1604 of the lithium niobate gate 1602 . The lithium niobate gate 1602 is clocked using a clock signal which is applied to one of two optical data ports 1606 and 1608 of the gate 1602 . The clock signal is switched by the electronic control pulses and a high fidelity regenerated signal is emitted from the lithium niobate gate 1602 . [0154] Typically, an interconnect structure utilizing a lithium niobate gate 1602 in a regenerator 1600 also uses lithium niobate gates to construct nodes. One large power laser (not shown) supplies high fidelity timing pulses to all of the regenerators in an interconnect structure. The illustrative regenerator 1600 and node 1650 combination includes an optical coupler 1620 which has a first data input connection to a node on the same level C as the node 1650 and a second data input connection to a node on the overlying level C+1. The illustrative regenerator 1600 also includes a photodetector 1622 connected to an output terminal of the optical coupler 1620 , optical to electronic converter 1624 which has an input terminal connected to the optical coupler 1620 through the photodetector 1622 and an output terminal which is connected to the lithium niobate gate 1602 . An output terminal of the lithium niobate gate 1602 is connected to a second lithium niobate gate (not shown) of a node (not shown). Two signal lines of the lithium niobate gate (not shown) are combined, regenerated and switched. [0155] When regenerators or amplifiers are incorporated to improve signal fidelity and if the time expended by a regenerator or amplifier to recondition a message signal exceeds the time α−β, then the regenerator or amplifier is placed prior to the input terminal of the node and timing is modified to accommodate the delay. [0156] Other Embodiments [0157] The interconnect structure shown in FIGS. 1 through 16 is a simplified structure, meant to easily convey understanding of the principles of the invention. Numerous variations to the basic structure are possible. Various examples of alternative interconnect structures are discussed hereinafter, along with advantages achieved by these alternative structures. [0158] Referring to FIG. 23, an alternative embodiment of an interconnect structure 1000 includes devices 1030 which issue message packets to multiple nodes 1002 of the outermost level J. In the interconnect apparatus 100 shown in FIGS. 1 through 16, a device CU(θ,z) initiates a message transmission operation by sending a message packet to a node N(J,θ,z). In the alternative interconnect structure 1000 , the device CU(θ,z) initiates a message transmission operation by sending a message packet to node N(J,θ,z) but, in addition, also includes interconnections to additional multiple nodes N(J,θ,z) where z designates cylinder heights selected from heights 0 to 2 J of the outermost level J and θ designates node angles selected from angles 0 to K of the heights z. In the case that a device sends messages to more than one node in the outermost level, the disclosed timing scheme maintains the characteristic that messages arrive at the target node at time zero modulus K. [0159] Devices are connected to many nodes in the outermost level J to avoid congestion upon entry into the interconnect structure caused by multiple devices sending a series of messages at a high rate to nodes having converging data paths. In some embodiments, the nodes to which a device is connected are selected at random. In other embodiments, the multiple interconnection of a device to several nodes is selected in a predetermined manner. An additional advantage arising from the connection of a device to several nodes increases the input bandwidth of a communication network. [0160] Referring to FIG. 24, an alternative embodiment of an interconnect structure 1100 includes devices 1130 which receive message packets from multiple nodes 1102 of the innermost level 0 . In this example, the number of nodes K at a particular height z is nine and each device 1130 is connected to receive message from three nodes on level zero. The interconnect structure 1100 is advantageous for improving network exit bandwidth when the number of nodes K on at a particular height is large. [0161] In the example in which the number of nodes K on a height z is nine and each device receives messages from three nodes on level zero, each node on ring zero is connected to a buffer that has three levels. At time 0 , message data is injected into the level zero buffer. At time three, data is injected into the level one buffer. At time 6 , data is injected into the level two buffer. A device CU(θ, 0 ) reads from the level zero buffer at node N( 0 ,θ, 0 ), from the level one buffer at node N( 0 ,(θ+3)mod 9 , 0 ), and from the level two buffer at node N( 0 ,(θ+6)mod 9 , 0 ). This reading of message data is accomplished in a synchronous or nonsynchronous manner. If in the synchronous mode, a time t is expended to transfer data from the buffer to the device. In this case, the device CU(θ, 0 ) reads from the level zero buffer at time t, reads from the level three buffer at time 3+t, and reads from the level six buffer at time 6+t. In an asynchronous mode, device CU(θ,O) interconnects to the three buffers as described hereinbefore and reads message data whenever a buffer signals that data is available. [0162] Referring to FIG. 25, an alternative embodiment of an interconnect structure 1200 includes devices 1230 which issue message packets to multiple nodes 1202 , not only in the outermost level J but also in other levels. In the alternative interconnect structure 1200 , the device CU(θ,z) initiates a message transmission operation by sending a message packet to node N(J,θ,z) but, in addition, also includes interconnections to additional multiple nodes N(T,θ,z) where T designates levels of the interconnect structure 1200 , z designates cylinder heights selected from heights 0 to 2 J of the outermost level J and θ designates node angles selected from angles θ to K of the heights z. In the case that a device sends messages to nodes in more than level, message communication is controlled according to a priority, as follows. First, messages entering a node N(r,θ,z) from the same level T have a first priority. Second, messages entering a node N(r,θ,z) from a higher level T+1 have a second priority. Messages entering a node N(r,θ,z) from a device CU(θ,z) have last priority. The alternative embodiment of interconnect structure 1200 allows a device to send messages to neighboring devices more rapidly. The disclosed timing scheme maintains the characteristic that messages arrive at the node designated in the message header at time zero modulus K. [0163] In these various embodiments, devices accept data from level zero nodes using one of various predetermined techniques. Some embodiments rely exclusively on timing to determine when the devices accept data so that devices accept data at time zero modulus K. Some embodiments include devices that accept message data at various predetermined times with respect to modulus K timing. Still other embodiments have devices that accept data whenever a buffer is ready to accept data. [0164] Wave Division Multiplexing Embodiment [0165] In another embodiment of an interconnect structure, message signal bandwidth is increased using wave division multiplexing. A plurality of K colors are defined and generated in a message signal that is transmitted using an interconnect structure having K devices at a cylinder height. Accordingly, each device is assigned a particular color. Message packets travel to a preselected target ring in the manner described hereinbefore for a single wavelength interconnect system. Message packets pass from level zero to the appropriate device depending on the color assigned to the message packet. [0166] A message includes a header and a payload. The header and payload are distinguished by having different colors. Similarly, the payload is multiplexed using different colors, which are also different from the color of the header. Message bandwidth is also increased by combining different messages of different colors for simultaneous transmission of the messages. Furthermore, different messages of different colors are bound on a same target ring, combined an transmitted simultaneously. All messages are not demultiplexed at all of the nodes but, rather, are demultiplexed at input buffers to the devices. [0167] Variable Base i j Height Structure Embodiment [0168] In a farther additional embodiment, an interconnect structure has i J cylindrical heights on a level for each of J+1 levels, where i is a suitable integer number such as 2 (the previously described embodiment), 3, 4 or more. As was described previously, each height contains K nodes, and each node has two data input terminals, two data output terminals, one control input terminal and one control output terminal. [0169] For example, an interconnect structure may have 3 J heights per level. On level one, message data is communicated to one of three level zero heights. On level two, message data is communicated to one of nine level zero heights and so forth. This result is achieved as follows. First, the two output data terminals of a node N(r,θ,z) are connected to input data terminals of a node N(T−1,θ+1,z) and a node N(T,θ+1,h T (z)), in the manner previously discussed. However in this further embodiment, a third height transformation h T h T (h T (z))) rather than a second height transformation h T (h T (z)) is equal to the original height designation z. With the nodes interconnected in this manner, the target ring is accessible to message data on every third step on level one. In an interconnect structure having this form, although nodes having two output data terminals are suitable, advantages are gained by increasing the number of output data terminals to three. Thus, one data output terminal of a node on a given level is connected to two nodes on that level and to one node on a successive level. Accordingly, each level has 3 J heights and a message packet and a message can descend to a lower level every other step. [0170] In this manner, many different interconnect structures are formed by utilizing i J heights per level for various numbers i. Where i is equal to 4, the fourth height transformation h T (h T (h T (h T (z)))) is equal to the original height designation z. If i is 5, the fifth height transformation h T (h T (h T (h T (h T (z))))) is the same as the original height z, and so forth. [0171] In the variable base i J height structure embodiment, whether the target ring is accessible from a particular node is determined by testing a more than one bit 10 of a code designating the target ring. [0172] Variable Base Transformation Technique Embodiment [0173] In a still further embodiment of an interconnect structure, the height transformation technique outlined hereinbefore is modified as follows. In this embodiment, a base three notation height transform technique is utilized rather than the binary height transformation technique discussed previously. In the base three transformation technique, a target ring is designated by a sequence of base three numbers. Thus, one a level n, the n low-order base three numbers of the height designation are reversed in order, the low-order-bit-reversed height designation is incremented by one, and the n low-order base three numbers are reversed back again. An exemplary interconnect structure has four levels (J=3 plus one), nine heights (3 J =3 3 ) per level and five nodes (K=5) per height. In accordance with the base three height transformation technique, node N 2(201)3 on level 2 has a first data input terminal connected to a data output terminal of node N 3(220)2 on level 3 , a second data input terminal connected to a data output terminal of node N 2(220)2 on level two. Node N 2(201)3 also has a first data output terminal connected to a data input terminal of node N 1(201)4 on level one and a second data output terminal connected to a data input terminal of node N 2(211)4 . Node N 2(201)3 also has a control input bit connected to a control output bit of node N 1(200)3 and a control output bit connected to a control input bit of node N 3(211)3 . In this embodiment, the header includes a synch bit followed by the address of a target ring in base three. For example, the base three numbers are symbolized in binary form as 00, 01 and 10 or using three bits in the form 001, 010 and 100. [0174] Further additional height transformation techniques are possible using various numeric bases, such as base 5 or base 7 arithmetic, and employing the number reversal, increment and reversal back method discussed previously. [0175] Multiple Level Step Embodiment [0176] In another embodiment, an interconnect structure of the nodes have ten terminals, including five input terminals and five output terminals. The input terminals include three data input terminals and two control input terminals. The output terminals include three data output terminals and two control output terminals. In this interconnect structure, nodes are generally connected among five adjacent cylindrical levels. Specifically, nodes N(T,θ,z) at the T cylindrical level have terminals connected to nodes on the T, T+1, T+2, T−1 and T−2 levels. These connections are such that the nodes N(T,θ,z) have data input terminals connected to nodes on the same level T, the next outer level T+1 and the previous outer level T+2. In particular, nodes N(T,θ,z) have data input terminals connected to data output terminals of nodes N(T,θ−1,h T (z)), N(T+1,θ−1,z) and N(T+2,θ−1,z). Nodes N(T,θ,z) also have control output terminals, which correspond to data input terminals, connected to nodes on the next outer level T+1 and the previous outer level T+2. Nodes N(T,θ,z) have control output terminals connected to control input terminals of nodes N(T+1,θ−1,z) and N(T+2,θ−1,z). Nodes N(T,θ,z) also have data output terminals connected to nodes on the same level T, the next inner level T−1 and the subsequent inner level T−2. In particular, nodes N(T,θ,z) have data output terminals connected to data output terminals of nodes N(T,θ+1,H T (z)), N(T−1,θ+1,z) and N(T−2,θ+1,z). Nodes N(T,θ,z) also have control input terminals, which correspond to data output terminals, connected to nodes on the next inner level T−1 and the subsequent inner level T−2. Nodes N(T,θ,z) have control input terminals connected to control output terminals of nodes N(T−1,θ+1,z) and N(T−2,θ+1,z). [0177] This ten-terminal structure applies only to nodes at the intermediate levels to J−2 since nodes at the outer levels J and J−1 and at the inner levels 1 and 0 have the same connections as the standard six-terminal nodes. [0178] This ten-terminal structure allows messages to skip past levels when possible and thereby pass through fewer nodes at the cost of increasing logic at the nodes. Only one message is allowed to enter a node at one time. The priority of message access to a node is that a message on the same level has top priority, a message from a node one level removed has second priority and a message from a node two levels away has last priority. Messages descend two levels whenever possible. The timing rules for an interconnect structure using the six-terminal nodes. Advantages of the ten-terminal node interconnect structure are that messages pass more quickly through the levels. [0179] Other interconnect structure embodiments include nodes having more than ten terminals so that data and control terminals are connected to additional nodes on additional levels. For example, various nodes N(T,θ,z) also have associated control input terminals and data output terminals, which are connected to nodes on inner levels T−3, T−4 and so on. In other examples, various nodes N(T,θ,z) also have associated control output terminals and data input terminals, which are connected to nodes on outer levels T+3, T+4 and so on. In various interconnect structure embodiments, nodes may be connected among all levels or selected levels. [0180] Multiple Interconnections to the Same Level Embodiment [0181] Additional interconnect structure embodiments utilize additional interconnections among nodes on the same level. Specifically, nodes N(T,θ,z) on the level T have interconnections in addition to the connections of (1) an output data terminal connected to an input data terminal of nodes N(T,θ+1,h T (z)) and (2) an input data terminal connected to an output data terminal of nodes N(T,θ−1,H T (z)). Thus nodes N(T,θ,z) on the level T have interconnections including a connection of (1) an output data terminal connected to an input data terminal of nodes N(T,θ+1,g T (z)) and (2) an input data terminal connected to an output data terminal of nodes N(T,θ−1,hr(z)). Like cylinder height h T (z), height g T (z) is on the half of the interconnect structure of level T that is opposite to the position of height z (meaning bit T of the binary code describing height h T (z) and g T (z) is complementary to bit T of height z). [0182] Multiple Interconnections to a Next Level Embodiment [0183] A multiple interconnections to a next level embodiment is similar to the multiple interconnections to the same level embodiment except that node N(T,θ,z) has one output data terminal connected to one node N(T,θ+1,h T (z)) on level T and two output data terminals connected to two nodes N(T−1,θ+1,z) and N(T−1,θ+1,g T−1 (z)) on level T−1. Thus one data output interconnection traverses the same level, a second interconnection progresses one level and a third interconnection both progresses one level and traverses. Like height h T (z), height g T (z) is on the half of the interconnect structure of level T that is opposite to the position of height z. Conflicts between node access are resolved by applying a first priority to messages moving on the same level, a second priority to messages progressing one level and a third priority to messages both progressing one level and traversing. [0184] The description of certain embodiments of this invention is intended to be illustrative and not limiting. Numerous other embodiments will be apparent to those skilled in the art, all of which are included within the broad scope of this invention. For example, many different types of devices may be connected using the interconnect structure including, but not limited to, workstations, computers, terminals, ATM machines, elements of a national flight control system and the like. Also, other interconnection transformations other than h T and H T may be implemented to describe the interconnections between nodes. [0185] The description and claims occasionally make reference to an interconnect structure which is arranged in multiple dimensions. This reference to dimensions is useful for understanding the interconnect structure topology. However, these dimensions are not limited to spatial dimensions but generally refer to groups of nodes which are interconnected in a particular manner.
A network or interconnect structure utilizes a data flow technique that is based on timing and positioning of messages communicating through the interconnect structure. Switching control is distributed throughout multiple nodes in the structure so that a supervisory controller providing a global control function and complex logic structures are avoided. The interconnect structure operates as a “deflection” or “hot potato” system in which processing and storage overhead at each node is minimized. Elimination of a global controller and buffering at the nodes greatly reduces the amount of control and logic structures in the interconnect structure, simplifying overall control components and network interconnect components and improving speed performance of message communication.
6
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] Not applicable. BACKGROUND OF THE INVENTION [0002] 1. The Field of the Invention [0003] The present invention relates to methods and corresponding instruments for gaining surgical access to the knee cavity by performing a tibial tubercle osteotomy as part of a minimally invasive total or partial knee arthroplasty or other knee related surgery. [0004] 2. Related Technology [0005] As a result of accident, deterioration, or other causes, it is often necessary to surgically replace all or portions of a knee joint. Joint replacement is referred to as arthroplasty. Conventional total knee arthroplasty requires a relatively long incision that typically extends longitudinally along the lateral side of the leg spanning across the knee joint. To allow the use of conventional techniques, instruments, and implants, the incision typically extends proximal of the knee and into the muscular tissue. In general, the longer the incision and the more muscular tissue that is cut, the longer it takes for the patient to recover and the greater the potential for infection. [0006] Accordingly, what is needed are minimally invasive procedures and corresponding apparatus for accessing the knee joint to perform total or partial knee arthroplasty. BRIEF DESCRIPTION OF THE DRAWINGS [0007] Various embodiments of the present invention will now be discussed with reference to the appended drawings. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. [0008] [0008]FIG. 1 is an elevated front view of a leg in a bent position; [0009] [0009]FIG. 2 is a elevated front view of a tibia of the leg shown in FIG. 1 with a portion of the tibial tuberosity removed; [0010] [0010]FIG. 3 is an elevated side view of the tibia shown in FIG. 2; [0011] [0011]FIG. 4 is a perspective view of a die cutter; [0012] [0012]FIG. 5 is a perspective view of the arm assembly of the die cutter shown in FIG. 4; [0013] [0013]FIG. 6 is an elevated front view of a guide; [0014] [0014]FIG. 7 is a perspective view of the guide shown in FIG. 6; and [0015] [0015]FIG. 8 is a top plan view of the guide shown in FIG. 6. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0016] The present invention relates to methods and corresponding instruments for performing a tibial tubercle osteotomy to gain access to the knee cavity as part of a minimally invasive total or partial knee arthroplasty or other knee related surgery. By way of example and not by limitation, depicted in FIG. 1 is a knee 10 having an anterior side 12 . Knee 10 is flexed to about 90 degrees. A transverse incision 14 , approximately 10 cm long, is made mediolaterally through the skin layer across the midline of knee 10 proximal of the tibial tuberosity. As depicted in FIG. 2, the tissue is retracted exposing in part a patellar ligament 18 and a tibial tuberosity 20 of a tibia 22 . A portion of tibial tuberosity 20 connected to patellar ligament 18 is now elevated such that patellar ligament 18 remains connected thereto. [0017] Specifically, FIG. 2 shows a lateral view of the proximal end of tibia 22 . A distal portion 30 of tibial tuberosity 20 has been elevated while a proximal portion 32 of tibial tuberosity 20 remains integral with tibia 22 . Patellar ligament 18 is excised from proximal portion 30 of tibial tuberosity 20 so that the distal end of patellar ligament 18 can be freely elevated in connection with distal portion 30 of tibial tuberosity 20 . In one embodiment, distal portion 30 of tibial tuberosity 20 is sized such that between about ⅓ to about ½ of the central mediolateral width of patella ligament 18 and tibial tuberosity 20 is osteotimized from the proximal end of tibia 22 . Thus about ⅓ to about ½ of the distal contact surface of patellar ligament 18 remains connected to distal portion 30 of tibial tuberosity 20 . [0018] Tibia 22 has an anterior cut surface 34 . With reference to the lateral side view of tibia 22 depicted in FIG. 2, cut surface 34 includes a proximally arched undercut portion 36 formed on the distal end of proximal portion 32 of tibial tuberosity 20 . As a result of cut surface 34 , proximal portion 32 of tibial tuberosity 20 terminates at a distally projecting anterior ridge 42 . [0019] Cut surface 34 also includes a distally sloping portion 38 extending from undercut portion 36 to an anterior border 40 of tibia 22 . Cut surface 34 partially bounds a pocket 35 and has a transverse configuration taken along a plane extending proximal to distal that is similar to a vertically bisected heart design as depicted on conventional playing cards. In contrast to forming a smooth bisected heart shape design, cut surface 34 can also form a sharp or slightly rounded inside angle that is typically 90° or less. [0020] As depicted in FIG. 3, cut surface 34 also has a substantially wedged shaped transverse configuration taken along a plane extending anterior to posterior. Specifically, cut surface 34 comprises a lateral side 24 and an opposing medial side 26 that each slope inwardly so as to intersect at a vertical midline 28 . In one embodiment, the inside angle θ between lateral side 24 and medial side 26 is in a range between about 60° to about 120° with about 80° to about 100° being more preferred. In alternative embodiments, cut surface 34 can be substantially flat extending mediolaterally or can form a rounded groove. [0021] Elevated distal portion 30 of tibial tuberosity 20 has a cut surface 46 that is complementary to cut surface 34 . As will be discussed below in greater detail, one of the benefits of the configuration of cut surfaces 34 and 46 is that once the procedure is complete, distal portion 30 of tibial tuberosity 20 is easily reinserted within pocket 35 . The complementary mating with undercut surface 36 helps lock distal portion 30 within pocket 35 as distal potion 30 is pulled proximal by patellar ligament 18 . [0022] Distal portion 30 of tibial tuberosity 20 can be elevated using a number of different techniques. By way of example and not by limitation, depicted in FIG. 4 is one embodiment of a die cutter 50 incorporating features of the present invention. Die cutter 50 comprises a housing 52 having a substantially box shaped configuration. Housing 52 has a front face 56 and an opposing back face 57 with side faces 58 and 60 extending therebetween. A top face 54 and an opposing bottom face 55 also extend between faces 56 and 57 . Housing 52 bounds a chamber 62 . Chamber 62 communicates with the exterior through an elongated slot 64 formed on front face 52 and an opening 66 formed on each side face 58 and 60 . [0023] A handle 68 outwardly projects from top face 54 of housing 52 . A threaded alignment bolt 69 passes through handle 68 and a portion of housing 52 so as to centrally project beyond front face 56 of housing 52 . Alignment bolt 69 threadedly engages with handle 68 and/or housing 52 such that selective rotation of alignment bolt 69 facilitates selective positioning of alignment bolt 69 beyond front face 56 of housing 52 . [0024] Partially disposed within chamber 62 of housing 52 are a pair of translating arms 70 and 72 . As depicted in FIG. 5, each translating arm 70 and 72 has a distal end 74 and an opposing proximal end 76 . In one embodiment of the present invention, means are provided for selectively advancing at least one of the first and second translating arms 70 , 72 toward the other. By way of example and not by limitation, a shaft 78 has threads formed along each end thereof with the threads being oriented in opposing directions. Each translating arm 70 and 72 is threaded onto a corresponding end of shaft 78 . Accordingly, selective rotation of shaft 78 causes translating arms 70 , 72 to either move together or move apart. A socket 83 is formed on each end face of shaft 78 . Shaft 78 is selectively rotated by inselting a tool, such as a drill bit, through one of openings 66 (FIG. 4) of housing 52 and into socket 83 of shaft 78 . Rotation of the tool thus facilitates rotation of shaft 78 . [0025] In alternative embodiments for the means for selectively advancing, it is appreciated that shaft 78 can be replaced with a variety of other conventional threaded shaft or bolt mechanisms. Furthermore, shaft 78 can be replaced with elongated levered handles or other conventional apparatus that facilitate manual movement of translating arms 70 and 72 . In yet other embodiments, it is appreciated that hydraulic, pneumatic, or electrical mechanisms can be used for movement of translating arms 70 and 72 . [0026] A plurality of spaced apart rails 79 outwardly project from each side of each translating arm 70 , 72 . Rails 79 mesh with complementary rails 92 formed on the interior of housing 52 . The meshing of rails 79 and 92 helps to ensure that translating arms 70 , 72 are maintained in alignment during movement. Proper alignment of translating arms 70 , 72 is further maintained by a pin 75 slidably extending through each of translating arms 70 , 72 . [0027] Returning to FIG. 4, distal end 74 of each translating arm 70 , 72 extends outside of chamber 62 through slot 64 . Mounted at distal end 74 of each translating arm 70 and 72 is an outwardly sloping head plate 80 . Each head plate 80 has an interior face 81 with an undercut engagement slot 82 formed thereon. Each interior face 81 is disposed in a corresponding plane. The planes intersect so as to form an inside angle that is substantially equal to the angle θ formed on cut surface 34 . Slidably disposed within each slot 82 is a die 84 . Each die 84 has a base 86 that is connected with a corresponding head plate 80 by being slidably engaged within slot 82 . As a result, dies 84 can be easily replaced with new dies or with dies having an alternative configuration. [0028] A blade 88 outwardly projects from each base 86 so as to extend orthogonally from interior face 81 of the corresponding head plate 80 . Each blade 88 terminates at a free sharpened edge 90 . Each blade 88 and corresponding sharpened edge 90 has a profile that is the same configuration as the profile of cut surface 34 of tibial tuberosity 20 previously discussed. Blades 88 are disposed so as to opposingly face at an intersecting angle. Accordingly, as shaft 78 is selectively rotated, translating arms 70 , 72 move together causing sharpened edges 90 to mate together. [0029] During use, once tibial tuberosity 20 is exposed as discussed above, die cutter 50 is positioned such that dies 84 are positioned on the lateral and medial side of tibial tuberosity 20 . The free end of bolt 69 rests against the anterior surface of tibial tuberosity 20 and helps to facilitate proper positioning of dies 84 . In this regard, bolt 69 functions as a spacer. In alternative embodiments, bolt 69 can be replace with a variety of other mechanism that permit selective spacing adjustment. For example, a rod and clamp configuration can be used. [0030] Once die cutter 50 is appropriately positioned, shaft 78 is selectively rotated, such as by the use of a drill, so that translating arm 70 and 72 are advanced together. In so doing, the dies 84 penetrate laterally and medially into tibial tuberosity 20 . Dies 84 continue to advanced until distal portion 30 of tibial tuberosity 20 is separated from proximal portion 32 thereof. [0031] One of the benefits of using this process is that dies 84 produce very clean cut surfaces 34 and 46 with minimal bone loss. As a result, once the subsequent surgical procedure is completed, distal portion 30 can be fit back into pocket 35 with a close tolerance fit. It is appreciated that a variety of alternative configurations of die cutters can be used for selective die cutting of tibial tuberosity 20 . [0032] In contrast to die cutting tibial tuberosity 20 , distal portion 30 of tibial tuberosity 20 can also be elevated using a saw blade. For example, depicted in FIGS. 6 - 8 is a guide 100 . Guide 100 comprises a central plate 102 having a front face 104 and an opposing back face 106 . Each of faces 104 and 106 extend between opposing sides 108 and 110 . Extending between front face 104 and back face 106 are a plurality of passageways 112 . [0033] Formed on sides 108 and 110 of central plate 102 is a first side housing 114 and a second side housing 116 , respectively. Each side housing 114 and 116 is formed so as to project beyond front face 104 of central plate 102 . Each of side housings 114 and 116 has an inside face 118 and an opposing outside face 120 . A cavity 122 extends through each of side housings 114 and 116 between faces 118 and 120 . Removably disposed within cavity 122 of side housing 114 is a first template 124 . A second template 126 is disposed within cavity 122 of side housing 116 . Each template 124 and 126 has a substantially box-shaped configuration which includes an inside face 128 and an opposing outside face 130 . Inside face 128 of templates 124 and 126 are each disposed in a corresponding plane. The planes intersect so as to form an inside angle that is substantially equal to the angle θ formed on cut surface 34 . [0034] A guide slot 132 extends through each of templates 124 and 126 between inside face 128 and outside face 130 . Each guide slot 132 has a configuration complementary to the profile of cut surface 34 and extends through templates 124 and 126 at an orientation perpendicular to inside face 128 . [0035] During use, once tibial tuberosity 20 is exposed, front face 104 of central plate 102 is biased against the anterior side of tibial tuberosity 20 such that templates 124 and 126 are disposed on the lateral and medial side thereof. Guide slots 132 are aligned with distal portion 30 of tibial tuberosity 20 to be elevated. Once guide 100 is appropriately positioned, fasteners, such as screws, nails, or the like, are passed through passageways 112 and into tibia 22 so as to securely retain guide 100 to tibia 22 . It is noted that passageways 112 are sloped such that the fasteners extending therethrough extend into portions of tibia 22 outside of distal portion 30 which is to be elevated. [0036] Once guide 100 is positioned in place, a saw blade 140 is passed through guide slot 132 of template 124 from outside face 130 to inside face 128 . Saw blade 140 is moved in a reciprocating manner so as to penetrate half way into tibial tuberosity 20 . Once the reciprocating saw blade 140 has completed passage along guide slot 132 , saw blade 140 is moved over to template 126 and passed through the guide slot 132 thereof. The process is then repeated. Once both cuttings are performed, distal portion 30 of tibial tuberosity 20 is freely removable from the remainder of tibia 22 . The fasteners are then removed along with guide 100 . As with die cutters 50 , it is appreciated that guide 100 can come in a variety of alternative configurations. [0037] As previously mentioned, once distal portion 30 of tibial tuberosity 20 is elevated, patellar ligament 18 is retracted proximally, thereby exposing the knee joint. Once the knee joint is exposed, any number of knee related surgical procedures, such as total or partial knee arthroplasty, can be performed. Referring back to FIG. 2, upon completion of the surgical procedure, patellar ligament 18 is secured back in place by inserting distal portion 30 of tibial tuberosity 20 back into pocket 35 . As a result of undercut portion 36 , distal portion 30 of tibial tuberosity 20 is self-locking within pocket 35 . If desired, however, various types of conventional bone anchors can be used to further secure distal portion 30 of tibial tuberosity 20 within pocket 35 . [0038] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
A method of performing a tibial tubercle osteotomy includes cutting a bone portion of a tibial tubercle from a remaining portion of the tibial tubercle, at least a portion of a patella ligament being attached to the bone portion. The bone portion of the tibial tubercle is separated from the remaining portion of the tibial tubercle such that the patella ligament remains attached to the bone portion. After completing a surgical procedure, the separated bone portion of the tibial tubercle is reattached to the remaining portion of the tibial tubercle.
0
FIELD OF THE INVENTION This invention relates to a rack system for vehicles, and, more particularly, to a rack system for pickup trucks and similar vehicles including improved structure for clamping to the side walls of the vehicle, novel tie-downs and an enhanced aesthetic appearance. BACKGROUND OF THE INVENTION Rack systems for mounting ladders and other equipment to the bed of pickup trucks and similar vehicles are well known in the prior art. Most systems of this type generally comprise a framework of four or more upright side rails, two of which are mounted atop or alongside one of the side walls of the truck with the other two located on the opposite sidewall. Cross bars are connected between aligning side rails on opposite side walls so that they span the bed of the truck in position to support equipment or materials in an elevated position above the truck bed. Many owners of pickup trucks are reluctant to permanently mount a rack system or any other device to the vehicle, or to attach such items in a way that would leave mounting holes or the like in the side walls or bed of the truck in the event the rack system or other device is ever removed. This issue has been addressed in the prior art by rack systems which provide one or more base supports adapted to clamp onto the side walls of the truck. Typically, these base support(s) rest atop one of the side walls of the truck in position to support one or both of the upright side rails of the rack system noted above. The joint connection between the base support(s) and upright side rails is typically cumbersome, or, at best, of limited aesthetic appeal. Further, the clamping devices employed to secure the base support(s) to the side walls of the truck are in many cases overly complicated and expensive. Tie-down devices are also commonly used in rack systems for vehicles in order to secure ladders of other items atop the cross bars described above. Most prior art tie-downs suffer from one or more limitations, e.g. it is difficult to adjust their position along the cross bars, or they are not easily mounted to and removed from the cross bars and/or they lack versatility in how rope, cords or other securing means may be mounted to the tie-down and to the items to be secured on the rack system. SUMMARY OF THE INVENTION This invention is directed to a rack system for vehicles such as pickup trucks comprising a number of base supports each clamped atop one of the opposed vehicle side walls by effective but economical clamping devices, a side rail mounted to each base support in an aesthetically pleasing fashion, and, tie-down devices releasably secured to cross bars extending between side rails located on opposite side walls of the vehicle. In one aspect of this invention, clamping devices are provided having three legs that are spaced from one another. Two of the legs capture a base support between them, and a third leg receives a bolt in position to engage the vehicle side wall thus clamping the base support in place. The base supports may be easily removed from the vehicle by loosening the bolts, and no holes or the like are left in the side walls or bed of the vehicle. A side rail is mounted to each base support via threaded fasteners extending from underneath such base supports into an internally threaded bore formed in a base plate located in the lower end of each side rail. In order to improve the aesthetics of the rack system, an adaptor is position over the point of connection between each side rail and base support. Each adaptor has an outer wall which encircles the bottom end of each side rail and rests atop the base support. Each adaptor is held in place by an internal plate through which the threaded fasteners extend so that when the side rails are tightened down on the base supports, the internal plate of each adaptor is captured between one of the side rails and base supports. In another aspect of this invention, a number of tie-down devices are provided which may be easily and rapidly mounted in any location along the length of the cross bars of the rack system. Each tie-down device has a number of convenient locations to which a rope, cord or other securing means may be attached in order to mount equipment or materials atop the rack assembly. DESCRIPTION OF THE DRAWINGS The structure, operation and advantages of the presently preferred embodiment of this invention will become further apparent upon consideration of the following description, taken in conjunction with the accompanying drawings, wherein: FIG. 1 is a perspective view of the rack system of this invention mounted to the bed of a pickup truck; FIG. 2 is a cross sectional view of a clamping device for mounting a base support to a side wall of the pickup truck shown in FIG. 1 ; FIG. 3 is an exploded, perspective view of a side rail, adaptor and base support; FIG. 4 is a top perspective view of the adaptor depicted in FIG. 3 ; FIG. 5 is a partially disassembled front view of the tie-down device of this invention; FIG. 6 is an assembled view of the tie-down device illustrated in FIG. 5 ; and FIG. 7 is an exploded, perspective view of the self-ratcheting handle employed to attach a tie-down device to a cross bar of the rack system. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to the Figs., a pickup truck 10 is schematically depicted having a side wall 12 , an opposed side wall 14 and a floor 16 between them which collectively define a bed 18 located behind the cab 19 . The terms “front” and “forward” when used herein refer to a location proximate the cab 19 of the truck 10 , whereas the terms “rear” and “rearward” denote the opposite end of the bed 18 . The rack system 20 of this invention generally comprises a forward rack structure 22 and a rear rack structure 24 which are essentially identical to one another. Each rack structure 22 , 24 includes a base support 26 located on the side wall 12 of the truck 10 , and a second base support 26 located on the opposite side wall 14 in substantial alignment with the first base support 26 . Each base support 26 mounts an upright side rail 28 , and a cross bar 30 is connected at opposite ends to each side rail 28 so that it extends between the side walls 12 , 14 of the truck 10 in position above the bed 18 . One or more tie-downs 32 , described below, may be mounted to each of the cross bars 30 for securing equipment, materials and other items to the rack system 20 . As best seen in FIGS. 1 , 2 and 3 , each base support 26 is formed in and L-shape including a top plate 32 having a recess 33 extending along its length, and a side plate 34 substantially perpendicular to the top plate 32 . The side plate 34 is preferably formed with a downwardly extending lip 35 . The upper portion of each side wall 12 , 14 of the truck 10 has a channel 36 that extends along the length of the bed 18 in the forward to rearward direction. The channel 36 has and upper wall 37 , an inner wall 38 and a lower wall 39 . The base support 26 is positioned with respect to the truck bed 18 so that its top plate 32 overlies the upper wall 37 of the channel 36 and its side plate 34 abuts the inner wall 38 of channel 36 . At least one, and preferably two, clamping devices 40 are provided to mount each base support 26 to one of the side walls 12 or 14 . Each clamping device 40 includes a clamp body 42 comprising an upper leg 44 , a lower leg 46 and an intermediate leg 48 located between the upper and lower legs 44 , 46 . As shown in FIG. 2 , the upper leg 44 has a downwardly extending leading edge 50 that fits into the recess 33 formed in the top plate 32 of base support 26 . The intermediate leg 48 of clamping device 40 forms a seat 52 that receives the lip 35 of the side plate 34 of base support 26 , such that the base support 26 is essentially captured between the upper and intermediate legs 44 , 48 . The lower leg 46 of the clamping device 40 extends generally parallel to and spaced from the lower wall 39 of the channel 36 . A bolt 54 or other fastener is threaded through a bore formed in the lower leg 46 of clamping device 40 and into engagement with the lower wall 39 of channel 36 to secure the base support 26 to the side wall 12 or 14 of the truck bed 18 . Referring now to FIGS. 3 and 4 , in order to improve the aesthetics of the rack system 20 of this invention, an adaptor 56 is placed over the joint connection between each side rail 28 and base support 26 . Each adaptor 56 has an outer wall 58 defining a hollow interior within which an internal plate 62 is mounted. The internal plate 62 is formed with two through bores 64 , 66 . One adaptor 56 fits over the lower end of each side rail 28 such that the bottom edge 68 of the side rail engages the internal plate 62 of the adaptor 56 . A base plate 70 , shown in phantom in FIG. 3 , is mounted within the hollow, lower end of each side rail 28 so that internally threaded bores (not shown) in the base plate 70 align with the bores 64 , 66 in the internal plate 62 of the adaptor 56 . One side rail 28 and one adaptor 56 are placed atop a base support 26 so that holes 72 , 74 formed in the base support 26 align with the bores 64 , 66 in the internal plate 62 of adaptor 56 and with the internally threaded bores in the base plate 70 of side rail 28 . A fastener 76 is extended through each of the holes 72 , 74 in base support 26 , and through the bores 64 , 66 in internal plate 62 , into the internally threaded bores in the base plate 70 of side rail 28 to secure both the side rail 28 and adaptor 56 to the base support 26 . Preferably, the adaptors 56 are formed of plastic or other resilient material, and are intended for aesthetic purposes rather than as a means of securing the side rails 28 to the base supports 26 . As noted above, one or more tie-down devices 32 may be mounted to each of the cross bars 30 for securing equipment, materials and other items to the rack system 20 . Referring to FIGS. 5 and 6 , each tie-down device 32 includes a tie-down body 80 and a clamping member 82 . The tie-down body 80 comprises a middle plate 84 , a foot section 86 and a curved center section 88 located between the middle plate and foot section 84 , 86 . An extension 89 is preferably connected at the base of the curved center section 88 of tie-down body 80 . A pair of outer ribs 90 and 92 are connected to or integrally formed at opposite ends of the middle plate 84 , and an inner rib 94 is joined to the middle plate 84 in between the outer ribs 90 , 92 . The outer ribs 90 , 92 extend outwardly from the middle plate 84 at an angle to one another, and connect together at an upper end thereof to form a generally triangular shape. The inner rib 94 connects to the outer ribs 90 , 92 at their upper end. One opening 96 is formed between the outer rib 90 and inner rib 94 , and a second opening 98 is formed between the outer rib 92 and inner rib 94 . The clamping member 82 includes a head section 100 , a foot section 102 and a curved, center section 104 located in between the head and foot sections 100 , 102 . One end of the middle plate 84 is formed with a channel 106 which receives the head section 100 of the clamping member 82 , i.e. the head section 100 may be slid into the channel 106 and retained therein. With the head section 100 in place within channel 106 , the foot section 102 of clamping member 82 abuts the foot section 86 of tie-down body 80 so that internally threaded bores (not shown) in each foot section 86 , 102 align with one another. A fastener 108 is then tightened down in the threaded bores to urge the clamping member 82 and tie-down body 80 together so that a cross bar 30 is captured between them and the tie-down device 32 is securely mounted thereto. See also FIG. 1 . It can be appreciated that the tie-down devices 32 each provide a number of locations within which rope, cords or other securing means may be attached in order to retain equipment or materials on the cross bars 30 of the rack system 10 . Such securing means may be inserted through the openings 96 or 98 in the tie-down body 80 and connected to any one of the ribs 90 , 92 or 94 , as well as the middle plate 84 . Additionally, the extension 89 , which is located below the cross bars 30 when the tie-downs 32 are mounted in place, is capable of connecting rope, cord or other securing means. With reference to FIG. 7 , a ratchet device 110 is illustrated which is employed to connect and disconnect the fastener 108 to the tie-down 32 . The ratchet device 110 comprises a handle 112 connected to a socket potion 114 portion formed with a stepped cavity having an upper cavity portion 116 and a larger diameter lower cavity portion 117 . An annular plate 118 is mounted at the juncture of the upper and lower cavity portions 116 , 117 immediately above an internal coupling element, which, in the illustrated embodiment, may take the faun of internal teeth 120 arranged in a ring. A bore is formed in annular plate 118 which receives a spacer 124 having a head 126 and a threaded shaft 128 , e.g. the head 126 of the spacer 124 rests atop the annular plate 118 and its threaded shaft 128 extends through its bore into the lower cavity portion 117 . The fastener 108 has threaded shank 129 , and, a head section 130 formed with an internally threaded, blind bore (not shown) and external teeth 134 which mate with the internal teeth 120 in the stepped cavity of the socket portion 114 . The threaded shaft 128 of spacer 124 extends into the blind bore 132 of the fastener 108 to connect the spacer 124 and fastener 108 together. Preferably, a spring 136 extends around the spacer 124 in between the annular plate 118 and the head section 130 of the fastener 108 . The ratchet device 110 is movable between an extended position and a retracted position. In the extended position, the head 126 of the spacer 124 rests on the annular plate 118 such that the external teeth 134 on the fastener 108 are spaced from the internal teeth 120 in the stepped cavity of the socket portion 114 . The spring 136 biases the fastener 108 to this extended position, acting between the annular plate 118 and the head section 130 of the fastener 108 . When in the extended position, the handle 112 and socket 114 of the ratchet device 110 freely rotate with respect to the fastener 108 . In order to secure the fastener 108 to the foot sections 86 and 102 of the tie-down body 80 and clamping member 82 , respectively, the socket 114 is urged toward the fastener 108 , overcoming the force exerted by spring 136 , to the retracted position in which the internal teeth 120 within the socket 114 engage the external teeth 134 on the head section 130 of the fastener 108 . With the internal and external teeth 120 , 134 engaged, the fastener 108 may be tightened down within the aligning threaded bores in the foot sections 86 and 102 . If the socket 114 is released, the spring 136 returns the ratchet device 110 to the extended position wherein the internal and external teeth 120 , 134 are disengaged. While the invention has been described with reference to a preferred embodiment, it should be understood by those skilled in the art that various changes may be made and equivalents substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
A rack system for vehicles such as pickup trucks comprises a number of base supports each clamped atop one of the opposed vehicle side walls by effective but economical clamping devices, a side rail mounted to each base support in an aesthetically pleasing fashion, and, tie-down devices releasably secured to cross bars extending between side rails located on opposite side walls of the vehicle.
1
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to locks and more particularly, to a lock assembly, which is the combination of a combination lock and a pin tumbler lock. [0003] 2. Description of the Related Art [0004] Conventional locks mainly include two types, namely, the combination lock operatable by a plurality of numbered wheels and the pin tumbler lock operatable by a key. If a suitcase uses a combination lock, the user must rotate the numbered wheels of the combination lock to show the correct combination when wishing to open the suitcase. If a suitcase uses a pin tumbler lock, the user must insert the correct key into the keyway of the pin tumbler lock and then rotate the plug of the pin tumbler lock with the key to the unlocking position when wishing to open the suitcase. [0005] If a suitcase uses a combination lock and the user forgets the correct combination of the combination lock, the user must deliver the suitcase to the distributor or a locksmith to open the combination lock. If a suitcase uses a pin tumbler lock and the user does not have the key in hand, the user still cannot open the suitcase. [0006] Further, in order to prevent a terrorist attach, customs clerks may have to check suitcases and luggage. When checking a suitcase that uses a combination lock, the customs clerk must destroy the suitcase so that the content of the suitcase can be seen. In this case, a dispute may arise between the customs clerk and the passenger. SUMMARY OF THE INVENTION [0007] The present invention has been accomplished under the circumstances in view. It is the main object of the present invention to provide a lock assembly, which is the combination of a combination lock and a pin tumbler lock and can be conveniently opened by selectively using the numbered wheels of the combination lock or the key of the pin tumbler lock. [0008] To achieve this object of the present invention, the lock assembly comprises a casing, a combination lock and a pin tumbler lock mounted respectively in the casing. The combination lock has a plurality of numbered wheels and a lifting plate movable relative to the numbered wheels. The pin tumbler lock has a plug rotatable between a locked position and an unlocked position. The plug has an actuating block which stops at the lifting plate when the plug is in the locked position and moves the lifting plate away from the numbered wheels when the plug is moved from the locked position to the unlocked position. BRIEF DESCRIPTION OF THE DRAWINGS [0009] FIG. 1 is an exploded view of a lock assembly according to a preferred embodiment of the present invention. [0010] FIG. 2 is a schematic top view of the lock assembly according to the preferred embodiment of the present invention. [0011] FIG. 3 is a sectional view of the preferred embodiment of the present invention, showing positions of the lifting plate and the sliding plate after unlocking of the combination lock. [0012] FIG. 4 is a sectional view of the preferred embodiment of the present invention, showing positions of the lifting plate and the sliding plate after locking of the combination lock. [0013] FIG. 5 is similar to FIG. 2 but showing the status of the lock assembly after unlocking of the pin tumbler lock. [0014] FIG. 6 is similar to FIG. 4 but showing the status of the lock assembly after unlocking of the pin tumbler lock. DETAILED DESCRIPTION OF THE INVENTION [0015] As shown in FIGS. 1 and 2 , a lock assembly 10 in accordance with the preferred embodiment of the present invention comprises a casing 20 , a combination lock 30 , a sliding plate 40 , and a pin tumbler lock 50 . [0016] The casing 20 , which can be firmly fastened to a half shell (not shown) of a suitcase or a luggage, comprises a flat rectangular bottom wall 202 , two first sidewalls 204 respectively perpendicularly extending from the two opposite long sides of the flat rectangular bottom wall 202 , two second sidewalls 206 respectively perpendicularly extending from the two opposite short sides of the flat rectangular bottom wall 202 and respectively fixedly connected between the first sidewalls 204 . The flat rectangular bottom wall 202 , the first sidewalls 204 and the second sidewalls 206 define a rectangular receiving open chamber 22 . Two locating plates 24 are fixedly mounted inside the rectangular receiving open chamber 22 in vertical posture and arranged in parallel. Each of the locating plates 24 has a through hole 242 and a locating notch 244 . The casing 20 further has two openings 208 formed in one first sidewall 204 for insertion of two hooks of a locking bar 26 that can be firmly fastened to another half shell (not shown) of a suitcase or a luggage. [0017] The combination lock 30 comprises a shaft 31 , three numbered wheels 32 mounted on the shaft 31 , three actuating wheels 33 respectively mounted in the numbered wheels 32 and supported on the shaft 31 , a lever 34 supported on the shaft 31 and coupled to one of the actuating wheels 33 , and a lifting plate 35 for supporting the numbered wheels 32 and the actuating wheels 33 . The lifting plate 35 is engagable with the hooks of the locking bar 26 when the locking bar 26 is inserted into the casing 20 through the openings 208 . The combination lock 30 is installed in the receiving open chamber 22 of the casing 20 by means of inserting two distal ends of the lifting plate 35 into the through holes 242 of the locating plates 24 . Further, the lifting plate 35 has a butt 352 at the bottom side and a stop rod 354 at one end. Rotating the numbered wheels 32 can cause a vertical movement of the lifting plate 35 relative to the numbered wheels 32 . When the numbered wheels 32 are aligned to show the correct combination, the combination lock 30 is opened, i.e. the locking bar 26 can be moved away from the lifting plate 35 . [0018] The sliding plate 40 is moveably mounted in the receiving open chamber 22 of the casing 20 and coupled to the locating notches 244 of the locating plates 24 . The sliding plate 40 has an oval insertion slot 42 cut through the top and bottom walls thereof at one end, and a rectangular through hole 44 cut through the top and bottom walls on the middle thereof. [0019] The pin tumbler lock 50 comprises a plug holder 52 fixedly mounted in the receiving open chamber 22 of the casing 20 , and a plug 54 inserted through the plug holder 52 and secured thereto by a C-shaped retainer 56 . The plug 54 can be rotated with the key (not shown) relative to the plug holder 52 between a locking position and an unlocking position. The plug 54 has a keyway 542 in the top side for the insertion of the key, a bottom pin 544 inserted through the insertion slot 42 of the sliding plate 40 , and a bottom actuating block 546 , which has a beveled actuating face 548 stopped against the stop rod 354 of the lifting plate 35 of the combination lock 30 . When the user inserting the key into the keyway 542 to rotate the plug 54 to the unlocking position, the sliding plate 40 will be moved toward the combination lock 30 by the bottom pin 544 , and at the same time the stop rod 354 of the lifting plate 35 of the combination lock 30 will be forced by the actuating block 546 to lower the lifting plate 35 relative to the numbered wheels 32 , thereby forcing the butt 352 into the rectangular through hole 44 of the sliding plate 40 . When the pin tumbler lock 50 is in the locking position, the actuating block 546 is stopped against the stop rod 354 of the lifting plate 35 of the combination lock 30 , and the butt 352 is disengaged from the rectangular through hole 44 of the sliding plate 40 . [0020] Referring to FIG. 3 , when the lock assembly 10 is used in a suitcase (not shown) and the user wishes to open the suitcase by means of the combination lock 30 , the user must rotate the numbered wheels 32 to show the correct combination so as to further unlock the combination lock 30 . When the combination lock 30 is unlocked, the butt 352 is kept away from the rectangular through hole 44 of the sliding plate 40 , the lifting plate 40 and the locking bar 26 are in a staggered manner, and the lifting plate 35 is suspending above the locking bar 26 . [0021] Referring to FIG. 4 , when the user rotating the numbered wheels 32 to lock the combination lock 30 , the lifting plate 35 will be lowered relative to the numbered wheels 32 to the same elevation of the locking bar 26 so that the locking bar 26 can not be moved out of the casing 20 due to the interference of the lifting plate 35 . [0022] Referring to FIGS. 5 and 6 , if the user cannot remember the correct combination of the combination lock 30 or if the customs clerk wishes to check the content of the suitcase but doesn't know the correct combination of the combination lock 30 , the key can be inserted into the keyway 542 of the pin tumbler lock 50 and rotated to move the sliding plate 40 toward the combination lock 30 and to simultaneously force the actuating block 546 against the stop rod 354 of the lifting plate 35 of the combination lock 30 , thereby lowering the lifting plate 35 to force the butt 352 of the lifting plate 35 into the rectangular through hole 44 of the sliding plate 40 . At this time, the lifting plate 35 and the locking bar 26 are again in a staggered manner, i.e. the lifting plate 35 is kept below the elevation of the locking bar 26 ; therefore, the hooks of the locking bar 26 can be freely moved away from the openings 208 of the casing 20 . This means that the suitcase can be opened. [0023] By means of the linking design of the combination lock 30 and the pin tumbler lock 50 , the user can selectively use the combination lock 30 or the pin tumbler lock 50 to open the suitcase. When the customs clerk wishes to check the content of the suitcase, the pin tumbler lock 50 can be operated to open the suitcase even if the combination lock is in the locked manner. [0024] Although a particular embodiment of the invention has been described in detail for purposes of illustration, various modifications and enhancements may be made without departing from the spirit and scope of the invention. Accordingly, the invention is not to be limited except as by the appended claims.
A lock assembly includes a casing accommodating therein a combination lock and a pin tumbler lock. The combination lock has a set of numbered wheels and a lifting plate vertically movable relative to the numbered wheels. The pin tumbler lock has a plug rotatable between a locked position and an unlocked position. The plug has an actuating block which stops at the lifting plate when the plug is in the locked position and moves the lifting plate away from the numbered wheels when the plug is moved from the locked position to the unlocked position.
4
BACKGROUND TO THE INVENTION This invention relates to apparatus for smoothing and/or polishing part-spherical surfaces. Such surfaces may be concave or convex. The invention has been developed primary for smoothing and polishing lenses. Machines which are in use at the present time for smoothing and polishing part-spherical surfaces on lenses each comprise two carriers, one of which is freely rotatable about a first axis and the other of which is rotatable by a motor about a second axis. The lens to be smoothed or polished is mounted on a first of the carriers and the smoothing or polishing tool is mounted on the second of the carriers. The second axis is usually fixed with respect to a base on which the machine stands and the first axis is moved to cause a traversing movement of the tool across the lens and also to maintain proper contact between the working surface of the tool and the surface of the lens which is being smoothed or polished. Traversing of the tool across the lens is necessary to avoid the formation of circular marks on the lens. It is usually desirable to adjust the stroke of the traversing movement when there is a change in the size and/or radius of curvature of the lens surfaces being smoothed or polished. Adjustments of the relative positions of the axes are also necessary so that a considerable proportion of a period which is required to smooth or polish a series of different lenses on a single machine is occupied by adjustment of the machine. It is necessary for the lens and tool to be urged together resiliently, since some movement of the respective carriers or associated supporting parts towards and away from each other is necessary as the tool traverses across the lens face. Since the lens is not positively held in the machine, there is a possibility of a lens moving completely off the tool during operation. The risk of this occurring increases with increasing speed of operation. For this reason, rotation about the second axis is normally limited to a value in the region of 550 rpm. SUMMARY OF THE INVENTION According to the present invention there is provided apparatus for smoothing and/or polishing a part-spherical surface and comprising a first carrier which is rotatable about a first axis, a support which is movable relative to the first axis, a second carrier which is mounted on the support and is rotatable relative to the support about a second axis, the arrangement being such that by moving the support, the second carrier can be moved relative to the first carrier along a curved path which lies in a plane, and the carriers being spaced apart in a direction contained in said plane, the apparatus further comprising biasing means for urging the carriers towards each other and drive means for rotating one of the carriers about its axis and for moving the support. BRIEF DESCRIPTION OF THE DRAWING The invention will now be described by way of example with reference to the accompanying drawing which shows a cross section of a machine in accordance with the invention. DESCRIPTION OF THE PREFERRED EMBODIMENT The machine comprises a body 10 having feet 11 on which the machine stands. A support 12 of plate-like form is supported within the body 10 for rocking movement about a horizontal axis 13. The support is carried by a bearing 14 secured to an internal wall 15 of the body. A lower carrier 16 is mounted on the support 12 for rotation relative thereto about an axis 17 which intersects the rocking axis 13 at right angles. Also mounted on the support is a motor 18 for driving the lower carrier, the motor being secured to the support at a position below the carrier 16 and having an upwardly extending output shaft 19, on an upper end portion of which the lower carrier 16 is releasably secured. In an upwardly presented face of the lower carrier there is formed a circular socket 20, from the bottom of which a pair of tapered pins 21 project upwardly. The pins are situated at diametrically opposite positions with respect to the axis 17 and are fixed with respect to the carrier. An upper carrier 22 is mounted at a position above the carrier 16 for free rotation about an axis 23. The axis 23 is inclined at an acute angle to the axis 17 and diverges upwardly therefrom. The axis 23 may lie in a vertical plane containing the rocking axis 13. Biasing means is provided for urging the upper carrier 22 resiliently along the axis 23 towards the lower carrier 16. This biasing means comprises a pneumatic piston and cylinder unit 24, the cylinder of which is rigidly mounted on the internal wall 15 of the body with its axis coinciding with the rotary axis 23 of the upper carrier. The piston rod extends downwardly from the cylinder and the upper carrier 22 is mounted on a lower end portion of the piston rod. An adjustable screw stop 25 is provided for limiting downward movement of the upper carrier 22. A further drive motor 26 is provided for rocking the support 12 and lower carrier 16 about the rocking axis 13. This motor is rigidly mounted on the internal wall 15 of the body and applies rotary drive through a gear box 27 to an eccentric 28 which is mounted in a bearing 29 supported in the wall 15 for rotation about an axis 30 parallel to the rocking axis 13. A portion of the eccentric 28 which is eccentric with respect to the axis 30 co-operates with a circular aperture in the support 12 through a bearing 31. Rotation of the eccentric 28 rocks the support about the axis 13, the limits of the stroke of the support being at positions in which the lower carrier axis 17 is inclined at equal angles to the vertical. Such rocking of the support causes the lower carrier 16 to move relative to the upper carrier 22 along an arcuate path which lies in a vertical plane containing the axis 17. As shown, for smoothing or polishing a convex part-spherical surface on a lens 1, the lens is mounted on the lower carrier 16. To enable rotary drive to be transmitted to the lens, the lens is adhered in a known manner to a metal pallet 2 having a spigot portion which is complementary to the socket 20, this spigot portion being formed with recesses to receive the drive pins 21. A tool 3 having a complementary concave face is mounted on the upper carrier 22. Since rotary drive is not required to be transmitted from the upper carrier to the tool, and the tool is required to be free to rock in different directions relative to the upper carrier, the upper carrier is provided at its lower end with a part-spherical head 32 which engages in a hemi-spherical recess formed in the tool. The tool is held in contact with the lens under a predetermined pressure which can be controlled by controlling the pressure of air supplied to the piston and cylinder unit 24. Typically, a force of 5 lbs would be applied to the tool. The motor 18 is energized to rotate the lower carrier 16 and the lens at a speed which is typically in the region of 2,700 rpm. The motor 26 is energised to rock the lens at a relatively low speed to and fro under the tool. A slurry containing suitable abrasive particles is fed to the interface between the tool and the lens by means of one or more nozzles (not shown). To contain the slurry in the region of the tool and lens, this region is enclosed by a housing 33 having at one side a hinged door 34 through which the lens and tool can be loaded into the machine and removed from the machine. A floor 35 of the housing slopes downwardly towards the lower carrier 16 and between the floor and the lower carrier there is an annular opening 36 through which the slurry can drain into a pump chamber 37. In this chamber, there is an impellor 38 which is secured on the shaft 19 with the lower carrier. The impellor causes the slurry to flow from the chamber 37 to the nozzles from which it is directed to the interface between the tool and the lens. As can be seen from the drawing, the upper carrier axis 23 diverges upwardly from the lower carrier axis 17 in a rearward direction, that is away from the door 34. The axis 23 intersects the lower carrier 16 at a position to the rear of the axis 17 and therefore intersects the interface between the tool and the lens also at a position to the rear of the axis 17. Movement of the head 32 of the upper carrier is confined to reciprocation along a rectilinear path coinciding with the axis 23. The centre of curvature of the arcuate path along which the lower carrier 16 and the lens are moved by rocking of the support 12 lies on the rocking axis 13. If the distance from the interface between the lens and the tool to this axis is approximately equal to the radius of curvature of the surface being polished or smoothed, there will be no significiant reciprocation of the upper carrier 12 and tool during operation. Typically, the rocking axis 13 is spaced from the interface between the lens and the tool by a distance of 70 mm. In cases where the radius of curvature of the surface being smoothed or polished differs substantially from this FIGURE, the acceleration of the upper carrier 22 is not so great as to permit the tool to escape from the upper carrier. It will be noted that no provision is made for adjusting the length of the arcuate path along which the lower carrier 16 is moved during use of the machine. Typically, a point at the centre of the upper side of the lower carrier moves along an arc having a length of 12 mm. The length of such arc is preferably within the range 6 mm to 20 mm. In the particular example shown, this arc lies in a vertical plane. The angle of inclination of the upper carrier axis 22 to this vertical plane is preferably within the range 5°-15° a preferred value being 8°. In a case where a concave part-spherical surface of a lens is to be smoothed or polished, a tool having a complementary convex surface is mounted on the lower carrier 16 and the lens is mounted by means of a metal pallet on the upper carrier 22. Rotary drive is then transmitted to the tool from the motor 26 and the tool is moved along an arcuate path about the rocking axis 13. The machine is particularly simple to operate, since no adjustments of the machine are required to be carried out by the operator when smoothing or polishing lenses having differently curved surfaces. The upper carrier 22 is automatically moved by the piston and cylinder unit 24 to accommodate the thickness of the lens. No other changes in the geometry of the machine are necessary. The length of the path along which the lower carrier moves is fixed. The inclination of the axis 22 to the plane in which the lower carrier moves is fixed. When the driven carrier of the machine illustrated in the accompanying drawing is rotated at a speed in excess of 550 rpm, the risk of a lens moving completely off the tool is less than is the case with the known machine hereinbefore described. This presents the possibility of using a lower pressure between the lens and the tool and/or driving one of the lens and the tool at a higher speed than is usual at the present time. Such higher speed enables a lens surface to be smoothed or polished relatively quickly.
In a machine for smoothing and polishing part-spherical surfaces on lenses, a tool and a lens are supported in contact with each other for rotation about respective axes and one of the tool and lens is driven. One of the tool and the lens is rocked about an axis which is perpendicular to its axis of rotation while the axis of the other of the tool and lens is maintained at a fixed acute angle to the plane in which the rocking occurs.
1
CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 60/696,774 filed Jul. 5, 2005, the contents of which are incorporated herein by reference. FIELD OF INVENTION This invention relates generally to devices and methods for removing a stop from a bottle. BACKGROUND OF THE INVENTION Some bottles, such as wine bottles, have a stop or cork like structure to retain the bottle's contents inside the bottle. In bottles with a stop, the stop is generally positioned with a friction or interference fit between the inner walls of the bottle opening to block the opening and prevent the contents from spilling, evaporating, spoiling or becoming contaminated. Often a stop, particularly a cork, cannot be easily removed from the bottle without a tool. One tool used to remove stops from bottles is a corkscrew with a handle or lever. To remove the stop, the corkscrew is rotated into the stop and the handle is pulled or the lever is used to draw the corkscrew out of the bottle along with the stop. Using a corkscrew on older stops and corks, however, may result in the stop or cork being severed, damaged, or the middle of the stop or cork being pulled out of the bottle and the outer part of the stop or cork adhering to the inner wall of the bottle opening. Cork bits in the contents and other effects of such stop damage can be undesirable. Another device used to remove stops or corks from bottles is a device commonly referred to as an “ah-so.” The ah-so has two elements, one typically longer than the other, connected to a handle. Using the handle, the longer element is inserted between the stop and bottle opening inner wall. As the shorter element is then similarly inserted, the handle is rocked and a downward force is applied, first on one element and then on the other, until both of the elements are substantially along the length of the stop. The elements are then twisted and pulled upward using the handle and the stop is removed by and with the elements. Conventional “ah-so” devices, however, may sometimes push the stop or cork, particularly older or fragile corks, into the bottle when the elements are being inserted. Another device used to remove stops from bottles is a hollow needle that is punched through the stop and air is inserted through the hollow needle. The increasing air pressure in the bottle pushes the stop out of the bottle opening. The stop, however, may be pushed into the bottle in the effort to punch the needle through the stop. Additionally, some find that the liquid contents may be adversely affected by the increased pressure used to remove the cork. Therefore, a need exists for a device for removing bottle stops that is less likely to, among other things, sever or damage the stop, leave the outer part of the stop adhering to the side of the bottle opening, or push the stop into the bottle. SUMMARY OF THE INVENTION The present invention includes new devices and methods for removing stops from bottles. Such devices and methods allow removal of the entire stop, even if the stop is old and fragile, and with little risk that the stop might be pushed into the bottle. Various aspects and embodiments of the present invention provide a stabilizer for gaining purchase or gaining grip within the stop, together with an integrated or connected element that is preferably greater in at least one dimension than the inner diameter of the bottle opening for preventing the stop from being pushed into the bottle. Insert members may also be provided and may be inserted between the stop and the inner wall of the bottle. In some embodiments of the present invention, a handle may be connected directly to the insert members and/or connected detachably to the stabilizer for applying a force to insert the stabilizer and/or to insert the insert members and/or to extract the stop. In particular embodiments of the invention, the stabilizer may prevent the stop from being pushed into the bottle when the insert members are inserted. The insert members may extract the stop without leaving the outside of the stop remaining on the inner wall of the bottle opening. In certain embodiments of the present invention, a portion of the stabilizer is helically shaped, similar to a corkscrew, and may be essentially round and/or oval in cross section. In particularly preferred embodiments, the stabilizer is not used to extract the stop. Instead, the stabilizer prevents the stop from being pushed into the bottle. The stabilizer cross element may be an elongated structure with a length longer than the inner diameter of the bottle opening in order to prevent the stop from being pushed into the bottle by the insert members. In preferred embodiments of the present invention, the cross element may rest against the top of the bottle and does not interfere with the insert members being inserted between the stop and inner wall of the bottle opening. Furthermore, the cross element may be smaller than the handle of a conventional corkscrew. A particular method of the present invention for removing a stop from a bottle includes providing a stabilizer with a first portion for gaining purchase on a stop in a bottle and a second portion with at least one dimension greater than the inner diameter of the bottle opening. A separate device such as a prong may also be provided having a first portion that includes insert members for inserting between the stop and the inner wall of the bottle opening and a second portion with a handle to apply a force to insert the insert members and/or to extract the stop from the bottle. The stabilizer may be inserted into the stop, with a first portion gaining purchase and the prong insert members may then be inserted between the stop and the bottle inner wall. The stabilizer is preferably inserted until the second portion rests against the top of the bottle opening. The stabilizer preferably stabilizes the stop and prevents the stop from being pushed into the bottle when the insert members are inserted. The stop may then be removed by using the prong handle to retract the insert members, stabilizer, and the stop from the bottle opening. An advantage of certain aspects and embodiments of the present invention is to provide a bottle stop remover that does not push the stop into the bottle. A further advantage of certain aspects and embodiments of the present invention is to provide a bottle stop remover that removes the whole stop and does not leave part of the cork adhering to the bottle opening inner wall. A still further advantage of certain aspects and embodiments of the present invention is to provide devices and methods for removing a bottle stop without causing the stop to be severed or damaged in a way that adversely affects the liquid contained in the bottle. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a bottle stop remover stabilizer according to one embodiment of the invention. FIG. 2 shows, in perspective, the stabilizer of FIG. 1 detachably connected to a prong according to one embodiment of the invention. FIG. 3 is a perspective view of a bottle stop remover stabilizer embodying a particular cross element according to another embodiment of the invention. FIG. 4 is a perspective view of the bottle stop remover stabilizer shown in FIG. 3 connected to a prong according to another embodiment of the invention. FIG. 5 is a perspective view of a bottle stop remover stabilizer with a cross element adapted to be connected to a prong according to another embodiment of the invention. FIG. 6 is a perspective view of the bottle stop remover stabilizer shown in FIG. 5 connected to a prong through openings in the prong insert members. FIG. 7 is a perspective view of a bottle stop remover stabilizer with an elongated cross element according to another embodiment of the invention. FIG. 8 shows the bottle stop remover stabilizer of FIGS. 1 and 2 being inserted into the stop of a bottle using the prong handle and insert members of FIG. 2 according to one embodiment of the invention. FIG. 9 shows the prong insert members and handle of FIG. 8 being disengaged from the stabilizer of FIG. 8 . FIG. 10 shows the prong insert members of FIG. 8 inserted between the stop and inner wall of the bottle opening. FIG. 11 shows the stop being removed from the bottle with the prong insert members of FIG. 8 . DETAILED DESCRIPTION OF THE INVENTION Referring initially to FIG. 1 , illustrated is a stabilizer 110 with a first portion 112 and second portion 114 according to one embodiment of the present invention. The first portion 112 may include a sharp-tipped end 116 for gaining purchase on the stop and a substantially helical shaped body portion 118 . The body portion 118 preferably has a helical shape for gaining purchase on a bottle stop. Alternatively, the body portion 118 may have a helical shape with a substantially flat top surface or the body portion 118 may be of any shape or configuration adapted to gain purchase on a stop when it is inserted. The second portion 114 includes a cross element 122 for connecting with insert members from a prong. The cross element 122 may be essentially perpendicular to the stabilizer body portion 118 and include an elongated portion 124 and openings 126 , 128 , 130 for receiving the prong insert members. Alternatively, cross element may include openings 126 , 130 or any number of openings for receiving prong insert members. The cross element 122 preferably features at least one dimension greater than the inner diameter of the bottle opening to, as discussed in more detail below, prevent the stop from being pushed into the bottle. As an example of the greater dimension, the cross element 122 may be longer than that dimension. FIG. 2 shows the stabilizer 110 of FIG. 1 detachably connected to a prong 212 . The prong 212 preferably includes insert members 214 , 216 that may be inserted into the cross element openings 126 , 128 , 130 of the stabilizer 110 . Alternatively, insert members 214 , 216 may be inserted into openings 126 , 130 , for example when the cross element 124 includes only openings 126 , 130 , or otherwise. The prong 212 may also include a handle 218 connected to the insert members 214 , 216 . The handle 218 may be used to rotate the stabilizer 110 into and thus gain a purchase on a bottle stop, as well as to insert the insert members 214 , 216 between a stop and a bottle's inner wall. FIG. 3 shows an alternative embodiment of a stabilizer 300 with a first portion 312 having a sharp-tipped end 314 and a substantially helical body portion 316 according to one embodiment of the present invention. The body portion 316 is preferably connected to a cross element 318 which may, for example, be made from a plastic, metal, or other material and includes openings 320 , 322 to receive the insert members of the prong. The cross element 318 may further include an indented area 324 for receiving a portion of a prong handle. The cross-element 318 is preferably longer in length than the inner diameter of the bottle's opening with the indented area 324 having a length such that cross-element 318 does not interfere with the insertion of insert members between the stop and inner wall of the bottle opening. FIG. 4 shows a bottle stop remover 400 according to one embodiment of the present invention including the stabilizer 300 of FIG. 3 detachably connected to a prong 410 having a handle 416 with prong insert members 412 , 414 inserted through stabilizer cross-element slots 320 , 322 . The handle 416 includes a handle lower portion 418 that may preferably be located, and in some instances fitted, in the cross-element indented area 324 of the cross element 318 and may be, for example, initially retained in the indented area 324 by side members 325 , 327 in the upper portion of the stabilizer cross element 318 . The insert members 412 , 414 are preferably inserted in the openings 320 , 322 of the cross element 318 in FIG. 3 . The handle 416 may preferably be used to rotate and insert the stabilizer 300 into a stop, detach the insert members 412 , 414 from the stabilizer 300 and insert the prong insert members 412 , 414 between a stop and the inner wall of a bottle opening. Finally, the handle 416 may be used to remove the stabilizer 300 , insert members 412 , 414 , and stop from the bottle opening. FIG. 5 shows another alternative embodiment of a stabilizer 500 according to the present invention, this embodiment having a first helical shaped portion 510 and a second cross element portion 512 . The cross element 512 includes a body portion 514 that is preferably greater in at least one dimension than the inner diameter of the bottle opening. The cross element 512 also includes first 516 and second 518 ends that may be attached to insert members of the prong by any method or structure or otherwise. FIG. 6 shows a bottle stop remover 600 , which uses the stabilizer 500 of FIG. 5 detachably connected to a prong 610 by prong insert members 612 , 614 . The insert members 612 , 614 have openings 618 , 620 along the length of the insert members 612 , 614 . The openings 618 , 620 allow the insert members 612 , 614 to be detachably connected to the stabilizer 500 at the cross element ends 516 , 518 by sliding the insert member openings 618 , 620 along the cross element ends 516 , 518 . In some embodiments of the present invention, the openings 618 , 620 may be slotted. The ends 516 , 518 are configured to prevent the insert members 612 , 614 from becoming accidentally detached from the stabilizer 500 when the stabilizer 500 and insert members 612 , 614 are connected. A prong handle 616 may preferably be used to rotate and insert the stabilizer 500 into a stop, detach the prong insert members 612 , 614 from the stabilizer 500 , insert the prong insert members 612 , 614 between a stop and the inner wall of a bottle opening, and remove the stabilizer 500 , prong insert members 612 , 614 , and stop from the bottle opening. FIG. 7 shows another alternative embodiment of a stabilizer 1100 according to one embodiment of the present invention. The stabilizer 1100 may include a first portion 1102 and an integrated, connected, or otherwise second portion 1104 . The first portion 1102 may include a sharp-tipped end 1103 for insertion into the stop and a substantially helical shaped body portion 1108 . The body portion 1108 preferably has a helical shape for gaining purchase of a bottle stop. Alternatively, the body portion 1108 may be of any shape adapted to gain purchase of a stop or the helical body portion may have flattened top and/or bottom cross section. The second portion 1104 includes a cross element 1112 for inserting the stabilizer 1100 into a stop preferably until, for example, the second portion 1104 rests on the top of the bottle opening. The cross element 1112 may be essentially perpendicular to the stabilizer body portion 1108 and include an elongated portion 1114 . The cross element 1112 is preferably longer than the diameter of the bottle opening to facilitate inserting the stabilizer 1100 into the stop and then, after gaining purchase on the stop, to prevent the stop from being pushed into the bottle. The stabilizer 1100 may be rotated into the stop and gain a purchase on the stop. The stabilizer 1100 may be manually rotated into the stop using the fingers or any desired tool or device. Alternatively, a handle may be detachably, or otherwise, connected to the stabilizer 1100 for inserting the stabilizer into the cork. The stop and stabilizer 1100 may then be removed using a separate device. FIGS. 8–11 are a sequence of illustrations that show a bottle stop remover 700 according to one embodiment of the present invention ( FIGS. 1 and 2 ) removing a stop 701 from a bottle 703 . As shown in FIG. 8 , a stabilizer 710 is provided with a first helical shaped portion 712 and a second cross-element portion 714 . The helically shaped portion 712 may include a sharp-tipped end (not shown) and a body portion 716 for gaining purchase on the stop 701 . Alternatively, the stabilizer 710 may be of any configuration to gain purchase on the stop 701 . The cross element portion 714 includes an elongated portion 720 that is longer than the inner diameter of the bottle opening 705 . The elongated portion 720 includes end openings 722 , 724 , 726 for detachably connecting to a prong 728 . The prong 728 is provided having insert members 730 , 732 connected to a handle 734 . In some embodiments of the present invention, one insert member 732 is preferably longer than the other insert member 730 . As illustrated in FIG. 8 , the insert members 730 , 732 are inserted in the stabilizer end openings 722 , 724 , 726 and the stabilizer end is located approximately in the center of the stop 701 . The handle 734 may then be used to rotate the prong and thus the stabilizer 710 (here as an example in the clockwise direction) and with a slight force downward with respect to the stop 701 to gain purchase in the stop. The stabilizer 710 is inserted and rotated into the stop until the cross element 714 is at the top of the bottle opening 705 , and preferably against the top of the bottle opening 705 as shown in FIG. 9 . Alternatively, the stabilizer 710 may be inserted and rotated into the stop manually. The prong 728 is then removed from the stabilizer end openings 722 , 724 , 726 by pulling upward on the handle 734 . The handle 734 and prong 728 are then rotated, preferably 90 degrees with respect to cross element 714 , but may be rotated as desired to allow the insert members 730 , 732 to be inserted between the stop 701 and the inner wall of the stop opening 705 . Using the handle, the insert members 730 , 732 are inserted between the stop 701 and the inner wall of the bottle opening 705 by partially inserting one insert member 732 , preferably the longer insert member, pressing down and rocking the insert member 732 , as needed, to partially insert it, and then inserting the other insert member 730 and pressing down slightly. Using the handle 734 , the insert members 730 , 732 may be alternately pressed down, as needed, until the bottom of the handle is located at the top of the bottle opening 705 and the insert members 730 , 732 extend along the stop 701 , as illustrated in FIG. 10 . In one embodiment, the insert members 730 , 732 are preferably attached to the stabilizer 710 . The stabilizer 710 is inserted into the stop 701 . The insert members 730 , 732 are preferably inserted between the stop 701 and the inner wall of the bottle opening 705 without detaching the insert members 730 , 732 from the stabilizer 710 and/or rotating the insert members 730 , 732 . As illustrated in FIG. 11 , the handle 734 may be twisted slightly and pulled upward, thereby removing the insert members 730 , 732 , stabilizer 710 , and stop 701 from the bottle 703 . The stop 701 , removed from the bottle 703 with the insert members 730 , 732 , is separated from the stabilizer 710 for reuse by preferably holding the stop to prevent the stop from rotating and rotating the stabilizer 710 counter-clockwise relative to the top of the stop. The following is an example of a particularly preferred embodiment of the bottle stop remover and specifically an embodiment for removing a cork from most wine bottles. The stop remover illustrated in FIGS. 3 and 4 includes a stabilizer 300 having a body portion 316 and a cross element 318 . The body portion 316 is made from spring or annealed steel, has a helical shape, a sharp-tipped point 314 , and is approximately 2.35 inches in length. At least a part of the cross element (not shown) is also made from steel and connected directly to the body portion 316 . A cross element body 326 made from plastic or metal encloses the cross element portion that is connected directly to the body portion 316 and they together form the cross element 318 . An indented area 324 is included within the cross element 318 to permit insert members 412 , 414 to be inserted between the stop and inner wall of a bottle opening while the stabilizer is preferably gaining purchase on the stop. In addition, the indented area 324 may receive and retain a prong handle. Below the indented area 324 , the cross element 318 has a top to bottom dimension 329 that is at least equal to the difference in length between insert member 412 and insert member 414 . The cross-element 318 also includes openings 320 , 322 through which the insert members 412 , 414 are located. The openings 320 , 322 are approximately 0.1 inches wide, 0.25 inches long, and 0.7 inches apart. The preferred bottle stop remover also includes a handle 416 and insert members 412 , 414 . The handle 416 is made from metal while the insert members 412 , 414 are made from one piece of spring or annealed steel that is shaped in an essentially squared U-shape and connected to the handle 416 . One prong 412 is longer than the other prong 414 . Prong 412 has a length of 2.3 inches while prong 414 has a length of 2.45 inches. Unless otherwise stated, terms used herein such as “top,” “bottom,” “upper,” “lower,” “left,” “right,” “front,” “back,” and the like are used only for convenience of description and are not intended to limit the invention to any particular orientation.
The present invention relates to devices and methods for removing a stop from a bottle. In certain embodiments of the present invention, a stabilizer is provided to prevent the stop from being pushed into the bottle and insert members are provided for removing the stop without the outside of the stop adhering to the inner wall of the bottle. Such embodiments allow, among other things, removal of the stop from the bottle without destruction or partial destruction of the stop, as is sometimes the case with conventional corkscrews, yet without the risk of pushing the stop into the bottle as is sometimes the case with non-corkscrew bottle stop removers.
1
BACKGROUND [0001] The invention relates to a device and a method for continuous chemical vapour deposition under atmospheric pressure on substrates. The device is hereby based on a reaction chamber, along the open sides of which the substrates are guided, as a result of which the corresponding coatings can be effected on the side of the substrates which is orientated towards the chamber interior. [0002] The production of thin layers made of gaseous starting materials (so-called precursors) is implemented with a large number of technical realisations. It is common to all methods that a gaseous precursor or a precursor brought into the gas phase is conducted into a reaction chamber, is decomposed there by the coupling in of energy and components of the gas are deposited on the parts to be coated. One of these methods is atmospheric pressure chemical vapour deposition (termed APCVD). It is characterised in that the precursor and the process chamber are almost at atmospheric pressure. An example of APCVD is APCVD epitaxy of silicon layers made of chlorosilanes. In this case the chlorosilane, normally mixed with hydrogen, is degraded in the reaction chamber at temperatures around 1000-1200° C. and silicon is deposited on a crystalline silicon substrate with the same crystal orientation. This process is used inter alia for solar cells which comprise thin, crystalline Si layers. In particular for this application case, silicon deposition reactors are required, which can deposit an approx. 10-20 μm thick Si layer very economically (under 30 ε/m 2 ) and at a high throughput (>20 m 2 /h). The reactors corresponding to the state of the art cannot achieve these requirements because they a) have too little throughput (e.g. ASM Epsilon 3000:1 m 2 /h) and b) use the silicon contained in the precursor only very incompletely (a few percent). A new development concerns the production of a high throughput reactor for chemical vapour deposition/epitaxy of silicon (Hurrle, S. Reber, N. Schillinger, J. Haase, J. G. Reichart, “High Throughput Continuous CVD Reactor for Silicon Deposition”, in Proc. 19 th European Conference on Photovoltaic Energy Conversion (WIP—Munich, ETA—Florence 2004, p. 459). In addition to the deposition of silicon, also all other layers which can be deposited under atmospheric pressure are in principle thereby producible in this reactor. [0003] The reactor embodies the following principle (see FIG. 1 ): 2 parallel rows of substrates 1 , 1 ′ are moved into a pipe 2 through a gas lock. In the interior of the pipe there is a chamber 3 which is open on the left and on the right. These openings of the chamber are also termed subsequently “deposition zone”. One row of substrates respectively is moved past on an open side of the chamber, closes the opening and thereby seals the chamber volume relative to the pipe volume. The precursor is introduced into the chamber from the front (i.e. the side of the inlet gas lock) through a gas inlet 4 and is suctioned-off through a gas outlet 5 in the rear region of the chamber. A special feature of the deposition chamber is that, relative to the volume situated outside the chamber, a small low pressure is maintained. This prevents large quantities of process gas escaping from the chamber. At the above-mentioned temperatures, the precursor (here: SiHCl 3 /H 2 ) is degraded and silicon is deposited principally on the continuously rearwardly-moving inner sides of the rows of substrates. The process gas mixture is preferably chosen such that the gas is completely depleted at the rear end of the chamber and no further deposition takes place. As a result, a deposition profile (i.e. a profile or a different deposition thickness) is produced naturally, which is however completely compensated for by the movement of the substrates. The substrates leave the unit at the rear end of the pipe again through a gas lock. A further feature of the reactor is that the substrates can be coated continuously at a uniform feed rate, i.e. a cycled operation which is complex to control is not required. [0004] At the parts 6 of the chamber which are produced from graphite and also at other surfaces, undesired “parasitic” depositions are produced. These must be removed regularly in order that all the cross-sections are maintained and hence no disturbing flakes are formed. In addition to the chamber surfaces, for example also the gas inlet nozzle or the gas outlet opening is affected by parasitic depositions. [0005] The described principle must scale-up in throughput to a plant suitable for the production of solar cells and also must optimise as far as possible the operating time of the plant, i.e. ensure an interruption-free permanent operation as far as possible. The present invention takes this requirement into account. SUMMARY OF THE INVENTION [0006] Starting herefrom, it was the object of the present invention to provide a deposition plant for chemical vapour deposition, with which the throughput can be significantly increased relative to the method known from prior art. [0007] According to the invention, a device is provided for continuous chemical vapour deposition under atmospheric pressure on substrates, which has a reaction chamber open on two oppositely situated sides. The substrates to be coated can be transported along the open sides, as a result of which the reaction chamber is sealed. The reaction chamber is thereby constructed such that it has respectively a front- and rear-side wall or another sealing means relative to the transport direction of the substrates, which are connected via two oppositely situated side walls. It is essential for the present invention now that the side walls of the device according to the invention have respectively at least two inlets and outlets for process gases which are disposed alternatingly at least in regions in the transport direction of the substrates. As a result of the alternating arrangement of gas inlets and outlets, the gas flows pass through the device in the counter-flow principle. As a result, the formation of parasitic coatings in the device, i.e. at places which are not intended to be coated, can be minimised or entirely prevented. Interruption of the continuous operation is not required for this purpose, in contrast to the state of the art, as a result of which a significantly higher throughput is achievable. [0008] The concept according to the invention is hereby based on the following approaches: [0009] The number of rows of substrates which are transported in parallel through the device can be increased. [0010] The length of the deposition zone is increased. [0011] In the proceeding deposition operation, the formation of parasitic coatings can be prevented or parasitically coated surfaces can be cleaned during continuous operation. [0012] These approaches can be achieved by the following measures: [0013] By means of skilled arrangement of the gas inlets and gas outlets and also of the associated gas flow. [0014] By means of skilled displacement of the reaction equilibrium present in the gas mixture. [0015] The gas inlets and gas outlets are preferably disposed in the form of nozzles on the side walls. [0016] In this variant, the gas inlet is disposed on a first side wall, whilst the gas outlet is disposed on the oppositely situated side wall. Consequently, the result is formation of a gas flow which extends essentially perpendicular to the transport direction. If these are now disposed alternately, the result is application of the counter-flow principle since the gas flows of the successive gas inlets or gas outlets extend in the opposite direction. [0017] Preferably, the device has at least one gas inlet for the introduction of a precursor for deposition on the substrates. In a further preferred embodiment of the device according to the invention, this likewise has at least one gas inlet for introduction of an etching gas in order to eliminate parasitic depositions. [0018] A second variant of the device according to the invention is based on the fact that the gas inlets and the gas outlets are configured in the form of pipes which extend perpendicular to the transport direction and have a plurality of nozzles which spread out over the length of the pipe. Hence a system is used here with at least one gas inlet pipe and one gas outlet pipe. The individual pipes are thereby disposed preferably in the form of blocks. A preferred variant thereby provides that one block comprises two gas inlet pipes with gas outlet pipes situated therebetween. The device can thereby have in total a large number of blocks of this type which are disposed sequentially in the transport direction. It is likewise possible that an additional gas inlet pipe is also disposed in the block for an etching gas. [0019] As substrates to be coated, preferably silicon, ceramic, glass and/or composites thereof or layer systems are used. [0020] According to the invention, a chemical vapour deposition reactor is also provided, which contains a heating furnace in which at least two devices which are disposed parallel to each other are disposed according to one of the preceding claims. A further chemical vapour deposition reactor likewise contains a heating furnace in which however the devices according to the invention are disposed sequentially. [0021] According to the invention, a method for continuous chemical vapour deposition under atmospheric pressure on substrates is likewise provided, in which the device according to the invention is used. The gas supply is thereby controlled such that, during the deposition on the substrates, parasitic depositions in the device are prevented and/or removed at the same time. [0022] Preferably, at least one precursor is supplied via at least one gas inlet and is deposited then on the substrates during the coating process. Gas is thereby suctioned out of the device via at least one gas outlet. The suctioning-off can thereby be effected preferably via a pump. [0023] A preferred variant of the method according to the invention now provides that, by means of periodic change of the composition of the at least one supplied gas, parasitic depositions in the device can be prevented and/or removed during the deposition process. If parasitic depositions are to be removed, then preferably at least one etching gas is supplied in order to remove these. This is then effected via a gas inlet for at least one etching gas. It is hereby possible both that the etching gas is supplied via a separate gas inlet and that the etching gas and the precursor are supplied via the same gas inlets, which is then effected in a temporal cycle. [0024] In the method according to the invention it is particularly preferred to supply the at least one precursor and the at least one etching gas to the device periodically alternating via different gas inlets. In addition, is it preferred that the at least one etching gas and the at least one precursor are chemically compatible with each other. [0025] Preferably, the gas inlets in the side walls or the nozzles into the gas inlet should be positioned such that they are directed towards the substrates so that a gas flow can be produced in the direction of the substrates. In contrast, the gas inlets or the nozzles of the gas inlet pipes for the at least one etching gas should be directed towards the surfaces of the device with parasitic depositions so that the parasitic depositions on these components of the device can be etched back. [0026] In addition, it is preferred that, in the previously described block-wise construction, different process gases are supplied within the device, so that different layers or layer compositions can be deposited on the substrates during transport of the latter. [0027] The method according to the invention can be implemented according to two different variants. In a first variant, slots are present between the delimitations of the process chamber and the substrates, the dimension of which changes substantially at no time. As a result, both continuous transport of the substrates through the device is made possible (i.e. at no time is there standstill of the substrate) and a cycled transport, comprising a transport cycle and a stationary cycle. Emergence of process gases is prevented by a suitable purge gas control. Alternatively, also sliding seals can be used in order to achieve a seal between substrate and process chamber. However problems can occur with respect to such a seal at high temperature and with high purity requirements. [0028] A second preferred embodiment provides that the width of the slots is changed periodically during the process and the substrates are transported in a pulsed manner through the device. During a deposition cycle, the substrates rest on the delimitations of the process chamber and seal the same in an adequately gas-tight manner. During a short transport cycle, the substrates are raised from the chamber, are further transported and placed down again. The gas emergence from the slots produced during the transport cycle is prevented by suitable purge gas control. This is effected as in the previously described variant in that the pressure in the chamber is lowered relative to the ambient pressure until an adequate purge gas flow is made possible or at least a flow to the exterior is prevented. The advantages of this second variant reside, on the one hand, in a higher tolerance relative to pressure- or flow variations and, on the other hand, in a lower-contamination deposition volume, e.g. with respect to the purge gas and the contamination entrained therewith. [0029] The subject according to the invention is intended to be explained in more detail with reference to the subsequent examples without wishing to restrict the latter to the special embodiments represented here. BRIEF DESCRIPTION OF THE DRAWING [0030] FIG. 1 shows a chemical vapour deposition reactor known from prior art. [0031] FIG. 2 shows a preferred embodiment of the device according to the invention with gas inlets and gas outlets alternating in the transport direction. [0032] FIG. 3 shows an embodiment of the device according to the invention in which gas inlet pipes and gas outlet pipes which are disposed in blocks are used. [0033] FIG. 4 shows the embodiment variant, which is represented in FIG. 3 , in plan view. [0034] FIG. 5 shows a further embodiment of the device according to the invention with a block-wise arrangement of gas inlet pipes and gas outlet pipes and also additional etching-back pipes. [0035] FIG. 6 shows an arrangement according to the invention in which a plurality of devices according to the invention and according to FIG. 5 are disposed parallel to each other. DETAILED DESCRIPTION OF THE INVENTION Example 1 [0036] In a first preferred embodiment, the precursor in conveyed through inlet nozzles into the deposition chamber 1 , said inlet nozzles being located on the longitudinal sides of the deposition chamber which is not formed by the substrates (see FIG. 2 ). One gas inlet 2 and gas outlet 3 respectively are situated approximately opposite each other, two successive pairs (e.g. pair 1 and pair 2 from FIG. 2 ) are disposed in mirror image. The gas flows of the successive pairs then run in counter-flow. According to the invention, the system is operated such that the precursor from the gas inlet to the gas outlet of one pair is used at a high percentage of the theoretically possible value, i.e. a profile is produced in which, because of gas depletion, almost no more deposition takes place at some point. Etching-back of parasitic layers takes place by using chemically compatible etching gas in one or more inlet pairs whilst the remaining pairs are still in the deposition operation. Alternatively, etching back can be achieved by changing the gas composition of the precursor (e.g. raising the CI/H ratio in the case of chlorosilanes). The gas flow is changed during etching back such that the parasitically coated surfaces are preferably attacked and the layer to be used subsequently is saved as far as possible. At least the parasitically coated surface which is assigned to one pair of nozzles must thereby be etched back effectively. After conclusion of etching back, the pair of nozzles is again supplied with precursor for deposition and etching back begins again on a different pair of nozzles. This process is further continued periodically. [0037] If it is advantageous for the process, the role of gas inlets and outlets can be exchanged periodically. [0038] m pairs respectively form one deposition chamber. Example 2 [0039] A second form of the invention is characterised in the following: instead of an inlet-/or outlet nozzle at the side of the deposition chamber, gas inlet pipes with a plurality of inlet-/outlet nozzles which are distributed on the length of the pipe traverse the deposition chamber perpendicular to the direction of movement. A gas inlet pipe at the front and at the back respectively are assigned to one gas outlet pipe (see FIGS. 3 and 4 ) The gas is preferably blown out of the gas inlet pipes in the direction of the substrates. In the following, this arrangement is termed “block”. During the deposition operation, precursor is introduced into both gas inlet pipes, the consumed gas is suctioned off by the gas outlet pipe therebetween. In the deposition chamber, any number of these blocks are disposed in succession. For etching back, one or more blocks is operated with etching gas which is chosen in its flow such that the parasitically coated surfaces are preferably gassed and hence etched back. Form 2 is extended as follows: instead of 2 gas inlet pipes per etching-back pipe respectively, the block is supplemented by additional gas inlet pipes in front of or behind the gas outlet pipe (“extended block”). Respectively m (extended blocks) form one deposition chamber. Example 3 [0040] In a third form, the block of form 2 is supplemented by a preceding, separate etching-back pipe (see FIG. 5 ). This etching-back pipe can be supplied with etching gas and etch back the respectively adjacent gas inlet- and outlet pipes. The direction of the etching gas flow is chosen such that the locations of the parasitic depositions are etched preferentially. Etching back can take place both in a cycle as in form 1 and 2 (i.e. the supply of precursor to the adjacent gas inlet pipes is interrupted during etching back) and in the proceeding deposition operation of all the gas inlet pipes. An essential feature of this operation is that the gas composition at the location of the gas inlet- and gas outlet pipes is changed by the etching gas such that the reaction equilibrium is displaced from deposition in the direction of etching. By means of direction and the quantity of etching gas, it is most extensively prevented that etching takes place on the substrate itself. Also the blocks of form 3 can be extended by additional gas inlet pipes, as in form 2. Respectively m of the blocks are disposed successively in series for one deposition chamber, an etching-back pipe after the m th block sealing a deposition chamber.
The invention relates to a device and a method for continuous chemical vapour deposition under atmospheric pressure on substrates. The device is hereby based on a reaction chamber, along the open sides of which the substrates are guided, as a result of which the corresponding coatings can be effected on the side of the substrates which is orientated towards the chamber interior.
2
BACKGROUND OF THE INVENTION This invention relates to a process wherein a fluid stream containing hydrogen sulfide is contacted with an aqueous solution containing a polyvalent metal chelate and the hydrogen sulfide in said steam is removed. It is known from U.S Pat. No. 4,123,506 dated Oct. 31, 1978 and U.S. Pat. No. 4,202,864, dated May 13, 1980 that geothermal steam containing H 2 S can be purified by contacting the steam with a metal compound that forms insoluble metallic sulfides. It is also known from U.S. Pat. No. 4,196,183, dated Apr. 1, 1980 that geothermal steam containing H 2 S can be purified by adding oxygen and passing it through an activated carbon bed. Various processes for hydrogen sulfide control in geothermal steam are outlined in the U.S. Department of Energy Report #DOW/EV-0068 (March, 1980) by F. B. Stephens, et al. U.S. Pat. No. 4,009,251, dated Feb. 22, 1977 discloses the removal of hydrogen sulfide from gaseous streams with metal chelates to form sulfur substantially without the formation of sulfur oxides. In U.S. Pat. No. 4,414,817 dated Nov. 15, 1983, there is disclosed a process for the removal of hydrogen sulfide from geothermal steam. However, this process generates free sulfur or sulfur solids which must be removed. The instant process is superior in that the sulfur solids are minimized by being converted to soluble sulfur compounds. In U.S. Pat. No. 4,451,442, dated May 29, 1984, there is disclosed a process for the removal of hydrogen sulfide from geothermal streams with minimum solid sulfer production. In this process, hydrogen sulfide is removed from fluid streams containing the same using a polyvalent metal chelate and an oxidizing agent. The oxidizing agent is preferably sulfur dioxide which can be generated by oxidizing a side stream of the hydrogen sulfide. However, in this process, the production of SO 2 also forms CO 2 which results in the formation of insoluble carbonates. These insoluble salts are troublesome and costly in geothermal power plants and other applications where solids free operation is necessary or desirable. In U.S. Pat. No. 4,622,212, dated Nov. 11, 1986, there is described a hydrogen sulfide removal method using a chelating solution containing thiosulfate as a stabilizer. In U.S. Pat. No. 3,446,595, dated May 27, 1969, there is described a gas purification process in which hydrogen sulfide is absorbed with bisulfite to form elemental sulfur and sulfite. This sulfite is regenerated to form bisulfite by contact with sulfur dioxide which in turn is formed by combustion of the elemental sulfur. U.S. Pat. No. 3,859,414, dated Jan. 7, 1975, describes a process in which sulfite is reacted with hydrogen sulfide in a gas stream at thiosulfate forming conditions, e.g. a pH between 6 and 7, to form soluble sulfur compounds. Other references which may be relevant to the instant disclosure include U.S. Pat. Nos. 4,629,608; 3,447,903; and 3,851,050. SUMMARY OF THE INVENTION The present invention is directed to a process wherein fluid streams containing H 2 S are purified by converting the H 2 S to soluble sulfur compounds by using a polyvalent metal chelate and a sulfite oxidizing agent. The process of this invention has the following steps: (a) incinerating hydrogen sulfide to form sulfur dioxide; (b) selectively absorbing said sulfur dioxide without substantial carbon dioxide absorption in a basic aqueous solution to form sulfites in said solution essentially free of insoluble carbonates; (c) contacting said fluid stream in a first reaction zone with aqueous solution at a pH range suitable for hydrogen sulfide removal wherein said solution contains an effective amount of polyvalent metal chelate to convert said hydrogen sulfide to sulfur and to reduce said polyvalent metal chelate to a lower oxidation state; (d) contacting said sulfur with said sulfites to form soluble sulfur compounds; (e) contacting said reduced polyvalent metal chelate in a second reaction zone with oxygen to reoxidize said metal chelate; and (f) recirculating said reoxidized solution back to said first reaction zone. Advantages of the process described herein are the substantial elimination of sulfur solids and insoluble carbonate salts which foul piping, heat-exchanger surfaces, cooling tower basins and the like. Such fouling of equipment in geothermal power plants, for example, leads to costly downtime for maintenance and loss of power production. Advantages of the process, when used for gas scrubbing are elimination of the need for expensive mechanical equipment such as settlers, frothers, filters, centrifuges, melters and the like for sulfur removal. This is particularly advantageous when treating streams having low sulfur content and recovery of the sulfur does not warrant the equipment required for its removal from the process. Furthur advantages of the process described herein include the minimization of sulfur emissions and the ability to optimize the hydrogen sulfide removal process by formation of a sulfur-solubilizing agent (sulfites) under controlled conditions to further assure complete sulfur solubilization and to minimize the use of makeup reagents such as chelating solution and caustic. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates a process in which this invention is applied for the oxidation of hydrogen sulfide contained in a liquid stream produced by the condensation of geothermal steam. FIG. 2 illustrates a process in which this invention is applied to the removal of hydrogen sulfide form a sour gas stream such as a natural gas stream, refinery gas, synthesis gas, or the like. In FIG. 1 the geothermal steam from line 2 is used to power a steam turbine 4 which is connected to an electric power generator 6. Line 18 directly supplies steam from line 2 to the steam turbine 4. The turbine 4 exhausts through line 8 to a condenser 10. Cooling water containing chelated iron (ferric chelate) and sulfites from line 28 is sprayed into condenser 10 for this condensation and passes from the condenser 10 through line 14 to the hot well 16 operating at 100°-125° F. Non-condensable gases such as CO 2 , H 2 , CH 4 , N 2 , O 2 and part of the H 2 S are removed from the main condenser 10 through line 36. If desired, a conventional steam ejector or ejectors may be employed in line 36 to create a partial vacuum or low pressure zone. The exhaust steam from line 36, including the H 2 S and non-condensable gas is fed to an incinerator or SO 2 generator 54 for oxidation of the H 2 S to SO 2 . An oxygen-containing gas such as air, oxygen, or mixtures thereof is supplied to the generator 54 by line 55. The SO 2 generator 54 is a conventional catalytic incinerator, however, a thermal incinerator may be used if desired. Sufficient amounts of polyvalent metal chelate is added after start-up to the cold well 66 by line 56 to make up for the amounts lost by continuous blow down through line 76. In a similar manner, caustic solutions such as aqueous sodium hydroxide are added, if needed, by line 78 to the cold well 66 to adjust or maintain the pH of the recirculating solution within the desired range of 5 to 11 and preferably 7 to 9. The aqueous solution in the cold well 66 is withdrawn by line 63 into pump 60 and pumped through line 58 to the static mixer 50 and thence to condenser 10 via line 28. The aqueous solution in the hot well 16 is withdrawn by line 64 into pump 62 and pumped through line 70 to the cooling tower 72 where the solution is sprayed into the tower and oxidized by air circulation. Line 76 is provided for continuous solution withdrawal. About 10-20 percent of the steam from line 2 is continuously withdrawn from line 76 which is typically reinjected into the underground steam-bearing formation. Line 74 is provided to allow the cooled solution to recycle back to the cold well 66. The cooling tower 72 is vented to the atmosphere at 80 with substantially no H 2 S being present. The SO 2 generated in the incinerator, along with the non-condensable gases and combustion products thereof, is fed via line 52 to optional quench vessel 81 and thence through line 82 to a first-stage scrubbing vessel 84 where it is absorbed by contact with alkali metal and sulfite/bisulfite solution at a pH of 4-7 circulated via pump 83 and recirculation loop 85. Unabsorbed gases from scrubber 84 are fed through line 86 to second-stage scrubber 88 where residual SO 2 is absorbed to less than 10 ppm in the gas which is then vented through line 87. A solution of alkali metal, bisulfite and sulfite at a pH of 8.5-9.5 is circulated through scrubber 88 by means of pump 89 and second-stage recirculation loop 90. Make-up alkali metal hydroxide is added through line 91 to recirculation loop 90 to maintain the desired pH and also to ensure that the alkali metal is reacted with sulfite in the recirculation loop 90 to form bisulfite, so that absorption of Co 2 in scrubber 88 and the resultant formation of carbonates therein is substantially avoided. Absorption solution is fed from recirculation loop 90 through line 92 to recirculation loop 85 to maintain the desired pH and scrubbing liquor level in scrubber 84. Scrubbing liquor containing sulfite and/or bisulfite is fed from recirculation loop 85 through line 93 to line 58 in a sufficient amount to maintain soluble sulfur-forming conditions in condenser 10. In FIG. 2, a sour gas feed is led by line 110 where it is combined with the aqueous solution from line 158 and thence to a static mixer 112 for good gas-liquid contact. The combined streams are fed into the first separator 114. The gaseous effluent from the separator 114 is led overhead by line 116 where it is combined with the recycled aqueous solution in line 126 and fed by line 118 to a static mixer 120 and then to a second gas-liquid separator 122. The overhead gas from the second separator 122 which is the purified or sweetened gas product of this process is removed by line 124 while the liquid bottoms are removed by line 156, pump 154, and recycled by line 158 to the first separator 114. The bottoms from the first separator 114 are removed by line 164 to the pump 160 and pumped through line 162 where it is mixed, with or without static mixer 150, with aqueous solution from line 184. The mixed bottoms and liquid effluent from lines 162 and 184 respectively are passed through line 152 into an oxidation rector 146. An oxygen-containing gas is supplied to the oxidizer 146 by the line 144 so that the polyvalent metal chelate is oxidized to its higher state of oxidation. The non-absorbed gases are purged overhead by line 148. The bottoms from the oxidizer 146 are removed by line 143 to pump 142. A purge line 135 is provided for the continuous removal of a portion of the aqueous solution from the pump line 136. The pump line 136 feeds into a mixing tank 132 where a mixer 134 stirs the chemicals that are added. Line 138 is provided for the addition of aqueous caustic solution to the tank 132 so that the pH can be adjusted within the desired range. Line 140 is provided for the addition of make up polyvalent metal chelate. The contents of the mixing tank 132 are removed by line 130 to the pump 128 for recycle back to the second separator 122 by line 126. Hydrogen sulfide is fed from any convenient source such as a pressurized tank or the like (not shown) through line 166, with an oxygen-containing gas such as air, oxygen, or a mixture thereof supplied through line 168, to SO 2 generator or incinerator 178. The SO 2 is routed through line 172 into an optional quench vessel 183 and thence through line 187 to a first scrubber 180. Scrubbing solution is circulated through scrubber 180 for contact with and absorption of the SO 2 by means of pump 179 and recirculation loop 181. Partially scrubbed SO 2 -containing gas is taken overhead by line 184 to a second scrubbing vessel 182 through which a scrubbing solution is circulated by means of pump 185 and recirculation loop 186. The scrubbed gas (less than 10 ppmv SO 2 ) is purged overhead from scrubber 182 by line 194. Makeup caustic or other alkali metal or ammonium hydroxide is introduced from line 190 into the recirculation loop 186 at a sufficient rate to maintain a pH in the range of about 8.6-9.5, and so that carbonate formation in the scrubbers 180,182 is substantially avoided by reaction of the alkali metal to form sulfite and/or bisulfite before being placed in contact with the SO 2 -containing gas which may also contain CO 2 . Scrubbing solution from scrubber 182 is introduced to recirculation loop 181 through line 192 from recirculation loop 186 at a sufficient rate to maintain a pH of about 4-7 in the scrubbing solution in first scrubber 180. Scrubbing solution containing sulfite and/or bisulfite is fed to line 152 through line 184 from recirculation loop 181 to maintain soluble sulfur-forming conditions in oxidizer 146 as described above. Alternatively, the sulfite and/or bisulfite solution or the the metal chelate solution may be fed to the process at points other than described above. DETAILED DESCRIPTION OF THE INVENTION The polyvalent metal chelates used herein are aqueous soluble, polyvalent metal chelates of a reducible polyvalent metal, i.e., a polyvalent metal which is capable of being reduced and a chelating or complexing agent capable of holding the metal in solution. As used herein, the term polyvalent metal includes those reducible metals having a valence of two or more. Representative of such polyvalent metals are chromium, cobalt, copper, iron, lead, manganese, mercury, molybdenum, nickel, palladium, platinum, tin, titanium, tungsten and vanadium. Of said polyvalent metals, iron, copper and nickel are most advantageously employed in preparing the polyvalent metal chelate, with iron being most preferred. The term "chelating agent" is well-known in the art and references are made thereto for the purposes of this invention. Chelating agents useful in preparing the polyvalent metal chelate of the present invention include those chelating or complexing agents which form a water-soluble chelate with one or more of the aforedescribed polyvalent metals. Representative of such chelating agents are the aminopolycarboxylic acids, including the salts thereof, nitrilotriacetic acid, N-hydroxyethyl aminodiacetic acid and the polyaminocarboxylic acids including enthylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, cyclohexene diamine tetraacetic acid, triethylene tetraamine hexaacetic acid and the like; aminophosphonate acids such as ethylene diamine tetra (methylene phosphonic acid), aminotri (methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid); phosphonate acids such as 1-hydroxy ethylidene-1, 1-diphosphonic acid 2-phosphonoacetic acid, 2-phosphono propionic acid, and 1-phosphono ethane-1, 2-dicarboxylic acid; polyhydroxy chelating agents such as monosaccharides and sugars (e.g., disaccharides such as sucrose, lactose and maltose), sugar acids (e.g., gluconic or glucoheptanoic acid); other polyhydric alcohols such as sorbitol and mannitol; and the like. Of such chelating agents, the polyaminocarboxylic acids, particularly ethylenediaminetetraacetic and N-hydroxyethylethylenediaminetriacetic acids, are most advantageously employed in preparing the polyvalent metal chelate used herein. Most preferably, the polyvalent metal chelate is the chelate of a ferric iron with a polyaminocarboxylic acid, with the most preferred polyaminocarboxylic acids being selected on the basis of the process conditions to be employed. Ethylenediaminetetraacetic acid and N-hydroxyethylethylenediaminetriacetic acid are generally particularly preferred. For the purpose of this invention, an effective amount of a polyvalent metal chelate is that amount ranging from about a stoichiometric amount based n the hydrogen sulfide absorbed to the amount represented by the solubility limit of the metal chelate in the solution. In like manner, an effective amount of an oxidizing agent (sulfite and/or bisulfite) is that amount ranging from about a stoichiometric amount based on the free sulfur formed to about five times the stoichiometric amount. Sulfite and/or bisulfite (collectively referred to herein as "sulfites") is employed as an oxidizing agent in the present process to maintain conditions in at least the second (oxidation-regeneration) reaction zone, and preferably also the first reaction zone, suitable for the formation of soluble sulfur compounds, e.g. thiosulfate, and to avoid the formation of solid elemental sulfur therein. The source of the sulfites employed is preferably the aqueous absorption effluent of H 2 S combustion products, and the combustion products are preferably obtained by combustion or catalytic incineration of a portion of the H 2 S-containing stream treated by the process. The aqueous absorption is preferably effected in a two-stage countercurrent scrubber using basic alkali metal hydroxide or ammonium hydroxide at conditions selective away from CO 2 absorption. This is accomplished, for example, by adding the makeup alkali metal hydroxide to a recirculation line or loop so that the alkali metal is contacted with the SO 2 containing gas in the form of sulfites so the absorption solution is essentially free of alkali metal hydroxide which could absorb CO 2 and concomitantly form carbonates which are undesirable in a desirably solidsfree system, and which are particularly undesirable where the aqueous chelating solution is cooled in a cooling tower. In such a two-stage scrubbing system, the first stage scrubber is preferably operated at a pH of about 4.5, e.g. about 4-5, while that of the second stage is about 9, e.g. about 8.5-9.5. This two-stage scrubbing is thus preferred because of no excess alkalinity in the sulfite/bisulfite effluent, i.e. a high proportion of bisulfite relative to sulfite which is economical by virtue of less makeup caustic being used, very low SO 2 slippage (usually less than 10 ppm) and substantially no alkali metal carbonates in the sulfite/bisulfite effluent due to the selectivity away from CO 2 . CONTROL 1 To a 1-liter agitated reactor in a constant temperature bath was added about 500 water, 14.8 (0.0448 mole) ferric iron-N(hydroxyethyl)-ethylene diaminetriacetic acid chelate (FE +2 .HEDTA), and 1.15 (0.0148 mole) of sodium sulfide as a stimulant for the absorption of 0.0148 mole of H 2 S. The pH was adjusted to 7.0 with NH 4 OH or HCl. The reaction was carried out for 30 minutes at 20° C during which time substantially all of the sulfide was oxidized by the ferric iron to elemental sulfur. The iron was reduced to the ferrous state. The total reaction solution was then weighed and filtered onto a tared filter paper for gravimetric determination of weight percent sulfur solids. The tared filter paper was dried and weighed. The weight percent sulfur solds, based on solution weights, was calculated. The filtrate was analyzed for weight percent thiosulfate (S 2 O 3 = ) and sulfate (SO 4 = ) by ion chromatography. Analytical results showed 966 ppm sulfur solids and 164 ppm sodium thiosulfate (Na 2 S 2 O 3 ). Sulfate (SO 4 = ) was below detectable limits, i.e., less than 110 ppm. EXAMPLE I The reaction was carried out using the method and conditions of Control 1 except that 2.95 of sodium sulfite was added. This represents a stoichiometric amount of 50% excess with respect to the sodium sulfide of Control 1. Analytical results showed 149 ppm sulfur solids and 3440 ppm sodium thiosulfate. EXAMPLE II & CONTROL 2 The reaction was carried out using the method and conditions of control 1 except the pH was controlled at 8.0. With no sulfite addition (Control 2) analysis showed 953 ppm sulfur solids and 232 ppm sodium thiosulfate. With sulfite addition, (Example II) analysis showed only 53 ppm sulfur solids and 3412 ppm sodium thiosulfate. EXAMPLE III & CONTROL 3 The reaction was again carried out using the method and conditions of Control 1 except the pH was controlled at 6.0. With no sulfite addition, (Control 3 ) analysis showed 968 ppm sulfur solids and 149 ppm sodium thiosulfate. With sulfite addition, (Example III) analysis showed 163 ppm sulfur solids and 3370 ppm sodium thiosulfate. CONTROL 4 The reaction was again carried out using the method and conditions of Control 1, except that pH was not controlled. The pH fell to about 3.6 resulting in nearly complete loss of H 2 S abatement efficiency and loss of SO 2 absorption. Most of the Na 2 S 2 O 3 was probably formed initially at the higher pH. Results of the Examples and Controls are shown in Table 1. TABLE I______________________________________ ppm ppm pH Solids Na.sub.2 S.sub.2 O.sub.3 Remarks______________________________________Control 1 7.0 966 164 No sulfite additionExample I 7.0 149 3440 With sulfite additionControl 2 8.0 953 232 No sulfite additionExample II 8.0 53 3412 With sulfite additionControl 3 6.0 968 149 With sulfite additionExample III 6.0 163 3370 With sulfite additionControl 4 3.6- 58 2054 No pH contr/with SO.sub.2 8.0 feed______________________________________ EXAMPLES IV A pilot scale two-stage countercurrent scrubber was used to scrub CO 2 and SO 2 -containing gas streams. The raw gas stream was fed consecutively through the first stage scrubber and then through the second stage scrubber. Makeup caustic was added to the recirculation line of the second stage scrubber to maintain a pH of approximately 9.0. Scrubbing solution from the second-stage scrubber was in turn added to the first stage scrubber to control the pH at approximately 4.5. The gases scrubbed contained 1% SO 2 , 10% CO 2 , 4.5% O 2 and the balance N 2 , saturated with water at 140° F. (Example IV) and at 180° F. (Example V); and 5% SO 2 , 10% CO 2 , 4.5% O 2 (Example VI). All streams were scrubbed to less than 1 ppmv SO 2 , and the aqueous effluent of the first stage scrubber contained a high proportion of NaHSO 3 , and no detectable free NaOh which is required for efficient solids control.
Fluid streams containing hydrogen sulfide from a steam tubine or from a sour gas stream are contacted with an aqueous solution of a polyvalent metal chelate and a bisulfite whereby the hydrogen sulfide is converted to free sulfur and then to soluble sulfur compounds. The metal chelate is reduced to a lower oxidation state metal chelate and reduced metal chelate is subsequently oxidized with air back to the higher oxidation state and reused. The bisulfite is formed by combustion of a portion of the fluid stream and subsequent absorption of the sulfur dioxide formed thereby in a two-stage countercurrent scrubber operating at conditions favorable for high bisulfite and low sulfite formation and selective away from carbon dioxide absorption.
8
This application is a continuation of application Ser. No. 08/610,236 filed Mar. 4, 1996, now abandoned, which is a continuation of application Ser. No. 08/168,909 filed Dec. 17, 1993, to issue as U.S. Pat. No. 5,497,140, which is a continuation of application Ser. No. 07/928,899 filed Aug. 12, 1992, now abandoned. Application Ser. No. 08/610,236 is a continuation-in-part of application Ser. No. 08/489,185 filed Jun. 9, 1995, now abandoned, which is a continuation of application Ser. No. 08/123,030 filed Sep. 14, 1993, now U.S. Pat. No. 5,448,110, which is a continuation-in-part of application Ser. No. 07/899,777 filed Jun. 17, 1992, now abandoned. TECHNICAL FIELD This invention relates generally to electrically powered postage stamps and mailing labels which operate to transmit radio frequency (RF) identification signals to an interrogator either at the point of shipment origin, in transit, or upon reaching a point of destination. More particularly, this invention relates to such stamps and labels having an integrated circuit therein powered by a thin flat battery cell. RELATED APPLICATION AND BACKGROUND ART In my co-pending application Ser. No. (71-579) entitled "Radio Frequency Identification Device and Method of Manufacture, Including an Electrical Operating System and Method", filed Jun. 17, 1992, there are disclosed and claimed new and improved radio frequency identification (RFID) tags which may be affixed to various articles (or persons) so that these articles, when shipped, may be easily tracked from the point of shipment origin, then along a given route, and then readily located upon reaching a point of destination. These RFID tags are constructed within a small area on the order of one inch (1") square or less and of a thickness on the order of 30 mils. These tags include, among other things, an integrated circuit (IC) chip having transmitter, receiver, memory and control logic sections therein which together form an IC transceiver capable of being powered by either a small battery or by a capacitor charged from a remote RF source. The IC chip including the RF transmitter and receiver sections operates to provide for the RF signal transmission and reception to and from remote sources, and a thin film antenna is also constructed within the above small area. The above novel RFID system operates to receive, store, and transmit article-identifying data to and from the memory within the IC chip. This data is stored within the IC chip memory stage and may be subsequently called up and transmitted to an interrogating party at the above point of origin, points along a given shipment route, and then upon reaching a point of destination. This co-pending application is assigned to the present assignee and is incorporated herein by reference. The RFID device disclosed and claimed in my above identified co-pending application represents not only a fundamental breakthrough in the field of RF identification generally, but also represents significant specific advances over the prior art described in some detail in this co-pending application. This prior art includes relatively large hybrid electronic packages which have been affixed to railroad cars to reflect RF signals in order to monitor the location and movement of such cars. This prior art also includes smaller passive RFID packages which have been developed in the field of transportation and are operative for tracking automobiles. These reflective passive RFID packages operate by modulating the impedance of an antenna, but are generally inefficient in operation, require large amounts of power to operate, and have a limited data handling capability. The above mentioned prior art still further includes bar code identification devices and optical character recognition (OCR) devices which are well known in the art. However, these bar code identification and OCR devices require labor intensive operation and tend to be not only very expensive, but highly unreliable. However, all of the above mentioned prior art devices described in my above co-pending application are only remotely related to the present invention as will become more readily apparent in the following description thereof. SUMMARY OF INVENTION The general purpose and principal object of the present invention is to provide still further new and useful improvements in the field of radio frequency identification (RFID) generally and improvements which are particularly adapted and well-suited for operation with electrically powered postage stamps and mailing labels. These new and useful improvements are made both with respect to the novel devices and processes described and claimed in my above identified co-pending application, and also with respect to all of the prior art described therein. To accomplish the above purpose and object, there have been developed both an electrically powered postage stamp and an electrically powered mailing label, each of which include, in combination, an integrated circuit chip having an RF transceiver constructed therein; a thin flat battery cell connected to the IC chip for providing power thereto; and a thin film RF antenna connected to the IC chip for transmitting data to and from the IC chip. All of the above components are connected in a very thin array and mounted between opposing major facing surfaces of either a postage stamp or a larger mailing or shipping label in a substantially two dimensional planar configuration. These components are operative to store data in the IC chip memory, which data includes such things as the destination address, return address, and descriptions of the contents of the article being mailed or shipped. These components are further operative in a novel system combination to transmit the stored data to an interrogating party upon receipt of RF interrogation signals transmitted to the stamp or label, or to receive data from same. Accordingly, it is another object of this invention to provide a new and improved RFID stamp or label of the type described which is uniquely constructed in an essentially two dimensional configuration which is easily scalable to the two dimensional major surface area of either a postage stamp or a mailing label. Another object of this invention is to provide a new and improved electronically powered stamp or label of the type described and process for making the stamp or label which employs certain novel, thin film fabrication techniques capable of producing device thicknesses on the order of a fraction of a millimeter. These thicknesses are typically within the range of one to five mils, thereby being extremely well suited and adapted for use with corresponding postage stamp or mailing label thickness dimensions. A further object of this invention is to provide a new and improved electronically powered postage stamp or mailing label of the type described including RFID integrated circuitry which is operatively powered by a flat and very thin battery and imparts a high and sophisticated degree of RF communication capability to these stamps or labels without significantly increasing the overall size and volume of the stamps or labels. The above brief summary of the invention, together with its various objects, novel features and attendant advantages, will become more readily apparent in the following description of the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an exploded perspective view of the electrically powered mailing or shipping label embodiment of the invention, including the novel radio frequency identification system mounted on the label base member. However, it should be understood that there is no basic functional difference in the label and stamp embodiments of the invention, and that the label cover and label base members shown in FIG. 1 apply equally as well to the smaller stamp cover or stamp base members which, for sake of brevity, have not been shown in the drawings. FIG. 2 is an enlarged perspective view of an RFID device and label or stamp package constructed in accordance with a preferred embodiment of the present invention. FIG. 3 is a plan view showing the conductive patterns on the base and cover members used in FIG. 2, including dotted line outlines for the locations of the IC chip and batteries which form the FIG. 2 structure. FIGS. 4A through 4D are cross sectional views taken along lines 4--4 of FIG. 3 showing the four (4) major processing steps which are used in constructing the RFID device and system array in accordance with a preferred process embodiment of the invention. FIG. 5 is a greatly enlarged perspective view of one suitable, very thin lithium/vanadium-oxide/copper battery or cell useful in the label and stamp embodiments and perspective views shown in FIGS. 1 and 2 above. FIG. 6 is a functional block diagram showing the major signal processing stages within the RFID integrated circuit chip described herein and shown in FIGS. 1 and 2 above. These major signal processing stages are also used within the interrogation unit (not shown) which is operative to interrogate the IC chip shown in FIGS. 1 and 2 above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to FIG. 1, the electrically powered, RF operative label or stamp includes a cover member 10 and a base member 12 upon which a radio frequency identification system has been constructed using thin film deposition techniques of the type described in my above identified co-pending application Ser. No. (71-579) filed Jun. 17, 1992. Functionally speaking, the RFID system 14 will include one or more thin flat battery cells 16 and 18 which are connected in series as indicated by line 20 and are both connected via line 22 to drive an integrated circuit transceiver chip 24. The IC transceiver chip 24 will preferably be connected to a dipole antenna consisting of thin film antenna strips 26 and 28, and the dipole antenna 26 and 28 is operative to both transmit RF signals from the IC chip 24 to a controller and to receive incoming RF signals from an external RF source controller and operative to encode this data in IC chip memory in a manner more particularly described below with reference to FIG. 6. This data will typically include information on the article to which the label or stamp are affixed, such as an identification number, the sender's name, point of origin, weight, size, route, destination, and the like. In addition, the RFID system 14 may be used to automatically RF communicate with postage meters and with automatic sorting machines to thereby completely eliminate the need for human intervention for such automatic sorting, thereby greatly reducing automatic mail sorting costs while simultaneously greatly increasing the speed and accuracy of the mail sorting process. The thin flat battery cells 16 and 18 can be made of various materials and typically include an anode, a collector, a cathode material, and a battery separator including a polymer and electrolytes of the type described below so as to not exceed a total battery thickness of 1 to 10 mils, while simultaneously being flexible and in some cases rechargeable. Furthermore, imminent commercialization of solid thin flat batteries having useful current levels at low temperatures makes the present invention commercially viable. Thus, since the IC chip 24 can also be made of thicknesses of no greater than 8 mils and since the thin film metal dipole antenna strips 26 and 28 may be held to thicknesses less than 1 to 2 mils, it is seen that the total added thickness between the label cover and base layers 10 and 12 will be negligible and not significantly affecting the bulk or the volume of the stamp or label into which the RFID system 14 is incorporated. Referring now to FIG. 2, there is shown in a perspective view a preferred device embodiment of the present invention wherein the RFID tag includes a base support layer 30 upon which an integrated circuit chip 32 is disposed on the near end of the layer 30 and connected to a dipole antenna consisting of a pair of conductive strips 34 and 36 extending laterally from the chip 32. These conductive strips 34 and 36 will typically be screen printed on the upper surface of the base support layer 30. A pair of rectangularly shaped batteries 38 and 40 are positioned as shown adjacent to the IC chip 32 and are also disposed on the upper surface of the base support member 30. The two rectangular batteries 38 and 40 are electrically connected in series to power the IC chip 32 in a manner more particularly described below. The device or package shown in FIG. 2 is then completed by the folding over of an outer or upper cover member 42 which is sealed to the exposed edge surface portions of the base member 30 to thereby provide an hermetically sealed and completed package. When the cover member 42 is folded over on the base member, the contact 50 which is attached to batteries 38 and 40 using conductive epoxy, provides the back side series electrical connection for the two batteries 38 and 40. The integrated circuit chip 32 has transmitter, memory, control, logic, and receiver stages therein and is powered by the two batteries 38 and 40 during the transmission and reception of data to and from an interrogator to provide the interrogator with the various above information and identification parameters concerning the article, animal or person to which the RFID tag is attached. Referring now to FIG. 3, there is shown a plan view of the geometry of the base support member 30 and the cover member 42 which, during the initial manufacturing stage for the RFID device, are joined at an intersecting line 44. The dipole antenna strips 34 and 36 are shown positioned on each side of the IC chip 32, and the two conductive strips 46 and 48 serve to connect the tops of the batteries 38 and 40 into the IC chip 32. A conductive strip 50 is provided on the upwardly facing inside surface of the top cover 42, so that when the cover 42 is folded by 180° at intersecting line 44, its outer boundary 52 is ready to be sealed with the outer boundary 54 of the base support member 30. Simultaneously, the conductive strip 50 bonded by the conductive epoxy to the batteries 38 and 40, completes the series electrical connection used to connect the two batteries 38 and 40 in series with each other and further in the series circuit with the integrated circuit chip 32 through the two conductors 46 and 48. Referring now to FIGS. 4A through 4D taken at the 4A--4D cross section indicated in FIG. 3, FIG. 4A shows in cross section view the IC chip 32 bonded to the base support member 30 by means of a spot or button of conductive epoxy material 56. The conductive strip 48 is shown in cross section on the upper surface of the base support member 30. Referring now to FIG. 4B, the battery 40 is aligned in place as indicated earlier in FIG. 2 and has the right hand end thereof bonded and connected to the upper surface of the conductive strip 48 by means of a spot of conductive epoxy applied to the upper surface of the conductive strip 48, but not numbered in this figure. Referring now to FIG. 4C, a stiffener material 58 is applied as shown over the upper and side surfaces of the IC chip 32, and the stiffener material will preferably be an insulating material such as "glob-top" epoxy to provide a desired degree of stiffness to the package and protection for the integrated circuit as completed. Next, a spot of conductive epoxy is applied to each end of the conductive strip 50, and then the cover layer material 42 with the conductive epoxy thereon is folded over onto the batteries 38 (of FIG. 2) and 40 and the base member 30 to cure and heat seal and thus complete and seal the package in the configuration shown in FIG. 4D. This figure corresponds to the remaining stations 22, 24, and 26 in FIG. 1. Referring now to FIG. 5, there is shown in a greatly enlarged perspective view a lithium/vanadium-oxide/copper battery including a lithium anode 60 as a top plate for the battery, an intermediate polymerized vanadium oxide electrolyte and separator layer 62 and a copper collector 64. However, the layer 62 is not limited to the use of vanadium oxide (V 2 O 5 or V 6 O 13 ), but may use other oxides such as magnesium oxide, MnO 2 . The intermediate layer 62 is formed and polymerized on the upper surface of the copper collector 64 and may be obtained from outside manufacturers or vendors as a one piece sheet (62, 64) and then assembled in house with lithium top anode sheets. Alternatively, the thin flat battery structure shown in FIG. 5 may be obtained as a completed battery cell from outside vendors or manufacturers. The thickness of these thin flat batteries will typically be in the range of 1 to 10 mils, and as previously indicated may be made as thin as a fraction of a mil. The components are assembled in an argon or other inert dry atmosphere using state of the art thin dry cell fabrication techniques. The use of conductive polymer layers as separators in thin flat battery cells is generally known in the art and is described, for example, in an article by M. G. Kanatzibis entitled "Conductive Polymers", Chemical and Engineering News-American Chemical Society, Dec. 3, 1990, incorporated herein by reference. Referring now to FIG. 6, the rectangular outer boundary 66 in this figure defines the active area on the integrated circuit chip (e.g. 24 in FIG. 1) in which the novel integrated circuit transceiver has been formed using state of the art MOS planar processing techniques. These MOS planar processing techniques are well known in the art and are, therefore, not described in detail herein. Within the chip active area 66 there is provided an RF receiver stage 68 and an RF transmitter stage 70, both connected through a common line or connection 72 to an off-chip antenna 74 of any planar type. A sleep/wake up circuit 76 is also connected via line 78 to the antenna 74 and operates in response to signals received from the antenna 74 to activate the necessary remaining circuitry and stages on the IC chip 66 described below. The receiver 68 is connected through a line 80 to a control logic stage 82, and a first output line 84 from the control logic stage 82 is connected as an input to the memory stage 86. A return output line 88 from the memory stage 86 connects back to the control logic stage 82, and a second output line 90 from the control logic stage 82 connects as a second input to the transmitter 70 for providing memory or stored input data to the transmitter 70 via the control logic stage 82. In a data encoding operation, the data received concerning ID number, name, route, destination, size, weight, etc. is processed through the receiver 68 and through the control logic stage 82 and encoded into the memory stage 86. As an example of a data call-up operation, when the RFID package in the above figures is placed on the outside surface of a piece luggage by the airlines or on a package for shipment by the postal service, either the airline agent or the postal worker will transmit information to the receiver 68 via an RF communication link concerning data such as the owner's name ID number, point of origin, weight, size, route, destination, and the like. This information received at the receiver stage 68 is then transmitted over line 80 and through the appropriate control logic stage 82 which sorts this information out in a known manner and in turn transmits the data to be stored via lines 84 into a bank of memory 86. This data is stored here in memory 86 until such time that it is desired to call up the data at one or more points along the shipment route. For example, upon reaching a point of shipment destination, an interrogator may want to call up this data and use it at the point of destination for insuring that the item of shipment or luggage is most ensuredly and efficiently put in the hands of the desired recipient at the earliest possible time. Thus, an interrogator at the destination point will send interrogation signals to the RFID chip 66 where they will be received at the antenna 74 and first processed by a sleep/wake up circuit 76 which operates to bring the FIG. 6 circuitry out of the sleep mode and allow the receiver stage 68 to process this received data to the control logic stage 82 via line 80. At the same time, the requestor will be operating an interrogation electronic unit having therein the same circuitry as that shown in FIG. 6, less the sleep/wake up circuit 76. With all stages in the FIG. 6 circuitry now awake, the memory stage 86 will produce the above six pieces of information relating to the shipped article and generate this data on line 88 and back through the control logic stage 82 into the transmitter 70 so that the transmitter 70 can now transmit this data to the interrogator. The receiver and transmitter sections 68 and 70 in FIG. 6 will preferably be operated in one of the well known spread spectrum (SS) modes using one of several available SS types of modulation which include: (1) direct sequence, (2) frequency hopping, (3) pulsed FM or chirped modulation, (4) time hopping, or time-frequency hopping used with pulse amplitude modulation, simple pulsed amplitude modulation or binary phase shift keying. The spread spectrum mode of operation per se is generally well known in the art and must conform to the frequency band separation requirements of the FCC Regulations, Part 15, incorporated herein by reference. The circuitry for the interrogation unit (not shown) will be similar to the functional system shown in FIG. 6 as will be understood by those skilled in the art, and therefore the interrogation unit will not be described herein. Various modifications may be made in and to the above described embodiment without departing from the spirit and scope of this invention. For example, various modifications and changes may be made in the antenna configurations, battery arrangements (such as battery stacking), device materials, device fabrication steps, and the system block diagram in FIG. 6 without departing from the scope of this invention. In addition, the various off chip components such as the antenna, battery, capacitor, and even inductors can be manufactured on-chip within the claims herein. In the case where RF charging is used, a battery will not be required. Accordingly, these and other constructional modifications are within the scope of the following appended claims. In addition, still other modifications may be made in and to the above described cell fabrication and device fabrication procedures without departing from the spirit and scope of this invention. For example, the present invention is not limited to the use of any particular types of thin flat battery cells or materials or cell fabrication processes, nor is it limited to the particular preferred fabrication technique for the RFID system as shown in FIGS. 2, 3, and 4 above. Moreover, the present invention is not strictly limited to the use of radio frequency communication and may, in environments where RF signals are not allowed, be modified so that the IC chip transceiver is capable of communicating with light waves using certain state of the art electro-optical coupling techniques which are not described herein, but are clearly within the scope of the following appended claims. Finally, it will be understood and appreciated by those skilled in the art that the present invention also includes forming an optical detector on the IC chip as a means of receiving and detecting signals carried by light and also as a means of powering the RFID transceiver as an alternative to using a battery. Accordingly, these and other systems and constructional modifications are clearly within the scope of the broad claims filed herein.
The present application describes an electronically powered postage stamp or mailing label and including a radio frequency identification (RFID) device and system mounted between the opposing and facing major surfaces thereof. The RFID device and system includes an integrated circuit transceiver chip which is connected to and powered by a thin flat battery cell and is operated with a thin film RF antenna, all of which are mounted in side-by-side relationship on a thin base or support layer. These thin flat components are mounted in an essentially two dimensional planar configuration well suited for incorporation into the planar structure of a postage stamp or a mailing label. In addition, the RFID transceiver chip may be replaced with an electro-optically operated IC chip using, for example, LEDs or laser diodes for the propagation of light signals to an interrogator.
8
This application claims the benefit of U.S. Provisional Application Ser. No. 60/058,146, filed Sep. 8, 1997. FIELD OF THE INVENTION The invention relates to a method of separating chemical mixtures. More particularly, the invention relates to a method of separating chiral and achiral chemical mixtures through capillary electrochromatography wherein an immobilized carbohydrate polymer is used as a chemical selector. BACKGROUND OF THE INVENTION Capillary electrochromatography (CEC) is a hybrid method of capillary electrophoresis (CE) and high performance liquid chromatography (HPLC). Though CEC was first demonstrated more than two decades ago, the advent of sophisticated CE instrumentation, expanded use and understanding of CE, and the continuing quest for more efficient separation methods has recently intensified interest in CEC. CEC involves the application of an electric field between the ends of a 50-110 μm capillary containing a stationary phase. “Open tubular” CEC describes a technique where the stationary phase is bonded to the capillary wall, while “packed” CEC describes a method involving capillaries filled either with a polymer gel stationary phase or a small particle (about 1-10 μm) silica-based stationary phase. In all CEC techniques, a liquid phase is transported through the capillary by electroosmosis or a combination of electroosmosis and pressure, and solutes are separated based on their partitioning between the stationary and mobile phases and on their charge to frictional drag. As shown in FIG. 1, the electroosmotic flow originates from the electrical double layer at the surface of the stationary phase as well as the capillary wall and generates a plug-like flow profile which is independent of the geometry and size of the channels between the particles. This phenomenon can provide very high efficiencies, limited primarily by the solute diffusion coefficient. In contrast to capillary liquid chromatography, CEC can utilize long capillaries of small, very efficient particles since there is no column back pressure. It has been shown in Dittmann et al., LC - GC, 13: 800 (1995) that CEC has the potential to provide column plate numbers 5 to 10 times greater than HPLC columns. The high efficiencies attainable make CEC a very attractive technique for chiral separations since it is theoretically possible to obtain baseline resolution for solutes with very small enantioselectivities. Polysaccharide derivatives coated onto porous derivatized silica have proven to be among the most versatile and widely used chiral stationary phases in HPLC. They have been used in both normal and reversed phase mode and have shown extremely high enantioselectivity for many solutes. Unfortunately, unlike several other chiral selectors, their use as buffer additives in CE is precluded by their poor solubility in suitable electrolytes and high UV cut-off. However, these characteristics do not preclude their use as chiral stationary phases in CEC, and open tubular electrochromatography using 50 μm I.D. fused silica capillaries coated with a cellulose derivative has been investigated by E. Francotte and M. Jung, Chromatographia, 42: 521-527 (1996). Resolution was found to be heavily dependent on the thickness of the coating, and the highest efficiency achieved was a disappointingly low 60,000 plates/m. OBJECTS OF THE INVENTION Accordingly, it is an object of the invention to provide a novel capillary electrochromatographic separation method which provides improved resolutions, particularly for chiral separations. Other objects will become apparent from the following description of the invention. SUMMARY OF THE INVENTION The invention is a chemical separation method involving capillary electrochromatography (CEC) or a combination of CEC and capillary liquid chromatography (CLC). The method comprises packing a capillary, preferably a fused silica capillary, with a packing material, preferably silica particles. The packing material is coated with one or more linear carbohydrate polymer chiral selectors, preferably cellulose, cellulose derivatives, amylose and/or amylose derivatives, and more preferably cellulose tris(3,5-dimethylphenylcarbamate). The packing process first involves loading a frit material into the capillary, the frit material being distinct from the packing material and preferably being an octadecyl silica product. The frit material is then sintered to form the first of two retaining frits, with the unsintered frit material thereafter being removed from the capillary. The packing material is then loaded into the capillary to form a stationary phase, with the retaining frit defining one end of the stationary phase. The packing material is preferably pumped into the capillary as a slurry at a pressure of about 430 bar or less. More frit material is then loaded and sintered to form a second retaining frit adjacent to the stationary phase at the end opposite from the first retaining frit. A sample of analytes (a chemical mixture) is introduced into the capillary, after which a voltage is applied across the length of the capillary to achieve bulk transport of the analyte. A pressure gradient is also preferably applied to promote bulk transport of the analyte. The components (analytes) of the sample are separated during transport across the stationary phase by the differing flow velocities of the components, the component flow velocities being determined by the differing degrees of retention by the stationary phase and mass/frictional drag. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic representation of a standard flow profile produced during CEC. FIG. 2 is a schematic diagram of a CEC packing apparatus. FIG. 3 is a graph of a CEC separation of 4-phenyl-2-butanol performed in accordance with the invention. FIG. 4 is a graph of a CEC run to determine a suitable t o marker. FIG. 5 is a graph of a CEC separation of 4-phenyl-2-butanol performed in accordance with the invention. FIG. 6 is a graph of a CEC separation of benzoin performed in accordance with the invention. FIG. 7 is a graph of a CEC separation of indapamide performed in accordance with the invention. DETAILED DESCRIPTION OF THE INVENTION We have discovered a novel CEC method of separating chiral and achiral mixtures which produces surprisingly efficient separations. In particular, the invention for the first time provides a CEC separation method which produces symmetrical peaks and reduced plate heights below four for chiral compounds. The invention can be used for the separation of charged, ionogenic or neutral chiral compounds, and all types of achiral compounds including structural isomers and other closely related compounds. The invention utilizes one or more linear carbohydrate polymers as chemical selectors in a packed capillary format. The linear carbohydrate polymer selector is preferably a polysaccharide, and more preferably a cellulose, cellulose derivative, amylose or amylose derivative. One or more selectors is coated onto a substrate to form a packing material. The substrate material is not particularly limited and may be any material known in the art, and may be of any size, morphology and porosity suitable for coating and capillary packing purposes. Preferably, the substrate comprises a particulate silica product, more preferably a silylated particulate silica product, and has a preferable particle diameter of approximately 5 μm. The capillary may be of any suitable material known in the art. Examples of capillary materials include fused silica, nylon, polyurethane, polytetrafluoroethylene, and polyethylene. Of the known capillary materials, fused silica is preferred. An important element of the invention is the packing procedure, particularly the frit formation. The frits are sintered into the inlet and outlet of the capillary to hold the packing material, thereby holding the stationary phase inside the capillary. Conventionally, the frit material has been the same as the packing material. However, the high sintering temperatures required to form the frit can melt the chemical selector coating which would negatively affect flow properties at the frit, thus reducing the separation efficiencies associated with the system. As a result, the invention utilizes materials other than the packing material for frit formation. Preferably, octadecyl silica particles are used as the frit material. Any method known in the art for packing substrate materials coated with linear carbohydrate polymers into a capillary may be used, examples of which include moderate and high pressure slurry packing, and electrokinetic packing. One or more selector-compatible packing solvents are used in these processes, i.e., solvents that do not dissolve the selector. Preferred packing solvents included acetonitrile (ACN) and MeOH, with ACN being most preferred. Moderate packing pressures of about 430 bar or less are preferred because higher packing pressures could fracture the packing material. Fractured particles can obstruct flow pathways within the capillary, thereby creating very low flow or no flow conditions. The mobile phase may include any compatible buffer. Organic buffers such as morpholinoethanesulfonic acid (MES), tris(hydroxymethyl)methane (TRIS) and N-2-hydroxyethylpiperazine-N′-3-propanesulfonic acid (HEPES) are preferred since they provide lower currents and reduce bubble formation. The invention will now be described through illustrative examples. The examples are not intended to limit the scope of the invention defined in the appended claims. EXAMPLES In accordance with the invention, fused silica capillaries (50 μm I.D., 363 μm O.D., 50 cm length, manufactured by Polymicro Technologies of Phoenix, Ariz.) were packed with a 5 μm chiral selector of cellulose tris(3,5-dimethylphenylcarbamate) coated onto silylated silica particles (5 μm CHIRALCEL OD manufactured by Chiral Technologies of Exton, Pa.). The method used for all of the examples will now be described, with points of variation being first described generically and later specified for each example. Prior to packing, a detection window of about 0.5 cm was burned in a capillary approximately 10 cm from one end. The capillary was then slurry packed at 430 bar with frit material using a HPLC pump (manufactured by DuPont Instruments, USA) connected to a 5 cm×4.6 mm reservoir loaded with a slurry of 3 μm octadecyl silica particles (3 μm Hypersil ODS2 manufactured by Hypersil of Runcorn, UK). See FIG. 2 for a schematic diagram of the apparatus. The capillary was packed with the octadecyl silica slurry to a height of approximately 5 cm above the detection window. Acetonitrile (ACN) was used as a packing solvent. After pumping the packed capillary with H 2 O for a few minutes, an outlet frit was produced by sintering directly above the detector window. The frit was sintered using a gas torch flame aimed through a 3 mm diameter hole in a metal sheet, whereby the packed capillary was heated for approximately 5 seconds to produce a frit with a diameter of approximately 2 mm. The octadecyl packing material on either side of the frit was then removed. After loading the slurry reservoir of the HPLC pump with the 5 μm chiral selector and reconnecting the capillary to the slurry reservoir, the capillary was packed with the chiral selector (slowly at first so as not to blow out the formed outlet frit) to a height of approximately 25 cm. ACN was again used as a packing solvent. The packed capillary was then flushed overnight with an ACN/H 2 O buffer to allow the bed to pack down and form a chiral stationary phase. Subsequently, more 3 μm octadecyl silica particles were packed on top of the chiral stationary phase, and an inlet frit was sintered from the octadecyl particles close to the chiral stationary phase in the same manner as the outlet frit. The resulting packed CEC capillary was flushed with the ACN/H 2 O buffer for at least 2 hours before use. Chromatographic studies using the packed capillaries produced as described above were then undertaken using an HP 3D CE capillary electrophoresis instrument manufactured by Hewlett Packard, Waldbronn, Germany, which can provide pressurization up to 12 bar of the inlet/outlet buffer vials. Electrolyte combinations are listed for each example. The aqueous buffer was prepared first and the pH was adjusted to various values (specified below for particular examples). The appropriate amount of acetonitrile (specified below for particular examples) was then added and the solution was mixed and thoroughly degassed by sonication and application of a vacuum for 2-3 minutes until no bubbles were observed. Once the packed CEC capillary had been installed in the capillary electrophoresis instrument, the electrolytes were changed using a high pressure flush with electroosmosis (10 bar, 10 kV) for 45 minutes. Between different inlet/outlet vials containing the same electrolyte, a short (15 minute) high pressure flush (10 bar, 10 kV) was applied. Occasionally, if the column was left unused for more than 24 hours, the capillary was reconnected to the HPLC pump and flushed using a pressure of 100 bar for 2 hours to remove any gas that may have built up. During the separation, 10 bar external pressure was applied to the inlet and outlet vials and, unless otherwise noted in specific examples, 20 kV was applied to induce electroosmotic flow. The temperature of the system was set at 22° C. Sample solutions of 4-phenyl-2-butanol, benzoin and indapamide were prepared by dissolving them in acetonitrile (10 mg/ml) and then diluting with electrolyte to produce a 1 mg/ml solution. A small amount of thiourea was also added to define the approximate region for the appearance of a t o marker/artifact. Unless otherwise specified, injection was accomplished by electromigration, 5 kV for 10 seconds. Generally, four separations were performed, and detection was monitored at 214 nm. Efficiencies and resolutions were provided by the Hewlett Packard CHEM STATION software and were calculated using the following equations: N= 5.545( t R /w 0.5 ) 2 and Rs= 2( t 2 −t 1 )/( w 1 +w 2 ); where t R is the migration time of the peak, w 0.5 is the peak width at half height, t 1 and t 2 are the migration times of the first and second enantiomers, w 1 and w 2 are the width at the base for peaks 1 and 2. In addition, the following equations were used: k′ 1 =( t 1 −t o )/ t o ,″=k′ 2 /k′ 1 and h=H/d p where k′ 1 and k′ 2 are the capacity factors for the first and second enantiomers; t o , t 1 and t 2 are the migration times of the perturbation, first enantiomer and second enantiomer, respectively; h is the reduced plate height, H is the height equivalent to a theoretical plate and dp is the particle diameter. Example 1 A CEC separation of 4-phenyl-2-butanol, a neutral chiral compound, was performed on a packed capillary prepared as described above and run on the CE instrument described above. The mobile phase consisted of 20 mM morpholinoethanesulfonic acid (MES) at pH 6.9/ACN (20:80 v:v), and electroosmotic flow was created by applying a 20 kV potential with a 2 μA current. The results of the separation are shown in FIG. 3 . The efficiency of the first enantiomer was 20,000 (80,000 plates/m; h=2.5). This is significantly higher than the efficiencies obtained for previous chiral CEC capillaries. Example 2 In order to be able to evaluate the potential of various buffer systems on the stationary phase, potential t o markers (ACN, Thiourea and nitromethane) were evaluated in separations performed as described in Example 1 to see which would be most suitable for a capillary packed with a 5 μm chiral selector of cellulose tris(3,5-dimethylphenylcarbamate) coated onto silylated silica particles. The results are shown in FIG. 4 . Under the conditions tested, thiourea was less retained than nitromethane, but the perturbation (caused by the difference of ACN content between the sample solution and running electrolyte) was observed 0.8 min before thiourea. It had been known in the art that when using capillaries packed with hydroxypropyl-β-cyclodextrin (HPBCD), the elution order for the perturbation and thiourea switch depended on the concentration of acetonitrile (30 to 50%) such that the perturbation provided a more suitable t o marker. Over the typical % ACN concentrations used for the capillaries packed as described in Example 1 (50 to 90%), the perturbation always eluted slightly before thiourea and the consistent difference in migration times suggested that thiourea may not be retained by the chiral stationary phase. Despite the latter observation, we decided to use the perturbation as a t o marker in subsequent examples. Example 3 The reproducibility of migration time for both electromigration injection and pressure injection for a capillary packed as described in Example 1 were evaluated in this example. Four consecutive injections of benzoin were made by electromigration (12 kV for 10 sec), and likewise by pressure (10 bar for 9 sec), to provide two sets of four separations. Each set utilized different inlet/outlet vials. The separations were otherwise performed as described in Example 1, and the percent relative standard deviations (% RSD) are shown in Table 1. TABLE 1 % RSD for migration % RSD % RSD (3 areas per times (8 (4 areas per set; area from first Type of Injection injections) set) injection discarded) Electromigration 0.89 Set 1 - 11.2 Set 1 - 0.41 (12 kV for 10 sec) Set 2 - 13.8 Set 2 - 0.58 Pressure 0.97 Set 1 - 0.86 Set 1 - 0.52 (10 bar for 9 sec) Set 2 - 0.66 Set 2 - 0.43 The low % RSD for the migration times confirmed that there was reproducible EOF in the packed capillary. Surprisingly, the peak area precision for four consecutive electromigration injections was less than expected. A closer examination of the results revealed a significantly lower peak for the first separation as compared with the three subsequent separations. When the peak area from the first separation was rejected, the precision improved dramatically and was well within acceptable limits. The peak area precision for all four separations carried out using a pressure injection was within acceptable limits although, as with electrokinetic injection, the precision for pressure injection was slightly better when the peak area from the first separation was rejected. Example 4 The effect of MES buffer concentration, pH and percent acetonitrile on the separation of neutral chiral compounds 4-phenyl-2-butanol, benzoin and indapamide was investigated in this example. Four consecutive electromigration injections (5 kV for 10 sec) were made. In accordance with the results of Example 3, the first injection was rejected and the mean of the remaining three injections was calculated for each parameter. MES Concentration For the first study, the buffer concentration of MES (pH 6.9) was varied between 10 mM and 100 mM. After mixing with 80% ACN, total buffer concentrations of 2 to 20 mM MES were produced. The results of the buffer concentration study are presented in Table 2. TABLE 2 Concentration of MES in 4-phenyl-2-butanol Benzoin Indapamide MES/ACN t 2 t 2 t 2 Mobile Phase k 1 ″ Rs N 1 (min) k 1 ″ Rs N 1 (min) k 1 ″ Rs N 1 (min) 2 mM 0.403 1.14 1.19 15658 7.4 0.402 1.45 2.61 7763 8.1 0.461 1.27 2.20 11858 8.2 4 mM 0.413 1.14 1.20 15248 9.0 0.420 1.44 2.64 7712 8.7 0.468 1.26 2.20 11997 8.7 8 mM 0.409 1.13 1.24 17298 9.1 0.413 1.43 2.90 9674 9.9 0.457 1.27 2.41 14793 9.9 12 mM 0.419 1.13 1.34 19582 10.9 0.411 1.44 3.16 11533 12.0 0.458 1.27 2.58 16732 11.9 16 mM 0.410 1.14 1.40 21715 12.5 0.416 1.43 3.43 13769 14.0 0.456 1.27 2.74 18694 13.8 Table 2 reveals that as the MES concentration increased, the migration times (t 2 ), efficiency (N 1 ) and resolution (Rs) increased, while the capacity factors (k′ 1 ) and selectivity (″) remained substantially unaffected. Though not shown in Table 2, the current through capillary increased from 1.5 to 4.8 μA as the MES concentration increased. The current took a significant time to reach a steady state when the MES concentration was below 5 mM. Further, at an MES concentration of 20 mM the EOF was very erratic, indicating the formation of bubbles in the packed bed. The increase in migration time was likely a result of the increased buffer concentration causing a compression of the electrical double layer, thereby decreasing the zeta potential at the capillary wall and reducing the EOF. The consistency of the capacity factor and selectivity values indicated that the buffer was not influencing the analytes interaction with the chiral stationary phase. The increase in efficiency resulted in an increase in resolution (Rs) in accordance with Rs∝{square root over (N)}. The results demonstrate that, for the neutral compounds tested, higher MES concentrations provide better resolution. However, the amount of current and length of analysis time also need to be considered when choosing a suitable concentration. A total MES concentration of about 10 mM was believed to provide the best compromise between resolution, current and analysis time. Effect of pH To evaluate the effect of pH on the chiral separation of neutral compounds, 50 mM MES having pH ranging from 5.8 to 7.1 was mixed with 80% ACN to produce a mobile phase with an MES concentration of 10 mM. The results of the chiral separations of 4-phenyl-2-butanol, benzoin and indapamide using the various mobile phases and otherwise performed in accordance with Example 1 are shown in Table 3. TABLE 3 pH of MES 4-phenyl-2-butanol Benzoin Indapamide in MES/ACN t 2 t 2 t 2 Mobile Phase k 1 ″ Rs N 1 (min) k 1 ″ Rs N 1 (min) k 1 ″ Rs N 1 (min) 5.8 0.443 1.14 1.15 13361 13.2 0.504 1.26 * 2672 14.4 0.444 1.45 2.76 8047 14.5 6.2 0.430 1.14 1.10 12575 10.7 0.489 1.25 * 2403 11.6 0.435 1.44 2.74 7609 11.9 6.7 0.412 1.13 1.21 15557 9.8 0.467 1.26 2.09 10760 10.4 0.422 1.46 2.87 8604 10.8 7.1 0.413 1.13 1.31 18787 9.4 0.467 1.26 2.54 16090 10.0 0.419 1.44 3.05 10146 10.1 *extremely poor peak shape, hence very low resolution Table 3 reveals that as pH increased, resolution and efficiency increased, migration times decreased, and capacity factors and selectivity were unaffected. Though not shown in Table 3, the increasing pH had no significant effect on the current, which stayed at approximately 2.7 μA. The decrease in migration times as the pH increased can be attributed to the increase in zeta potential from the increased silanol density. The stability of the capacity factors and selectivity indicates that in the range investigated, pH played no role in chiral recognition. The increase in efficiency resulted in increased resolution in accordance with Rs∝{square root over (N)}. The cause(s) of the extremely poor peak shapes and efficiencies for the enantiomers of benzoin when the pH was 5.8 or 6.2 is unknown. These results demonstrate that a higher pH provides faster analysis times and higher resolution. However, the pH chosen for the separation is limited by the buffering capacity of the mobile phase CEC system. Effect of % ACN The effect of percent acetonitrile (% ACN) in the mobile phase was studied by performing separations on 4-phenyl-2-butanol, benzoin and indapamide as described in Example 1, except that (1) the % ACN in the mobile phase was varied, and (2) the mobile phase contained 10 mM MES (pH 6.9). The results are shown in Table 4. TABLE 4 Percentage ACN in 4-phenyl-2-butanol Benzoin Indapamide MES/ACN t 2 t 2 t 2 Mobile Phase k 1 ″ Rs N 1 (min) k 1 ″ Rs N 1 (min) k 1 ″ Rs N 1 (min) 80% 0.417 1.13 1.36 20830 11.4 0.470 1.26 2.63 18070 12.3 0.426 1.42 3.31 12662 12.4 70% 0.600 1.13 1.50 16782 14.3 0.741 1.25 3.05 14515 16.7 0.481 1.42 3.71 9316 17.4 60% 0.948 1.13 1.82 14193 18.4 1.308 1.26 3.77 12442 23.4 1.295 1.44 4.71 7588 26.5 Table 4 reveals that as the % ACN decreased, migration times, capacity factors and resolution increased, efficiency decreased, and selectivity was substantially unchanged. Though not shown in Table 4, the current was not affected by decreasing % ACN, and remained at approximately 2.8 μA. The increase in migration times and capacity factors can be attributed to increased interaction of the mobile phase with the stationary phase as the % ACN is decreased. Although the efficiency decreased as the % ACN was reduced, the resolution increased in accordance with the relation Rs∝k′/(k′+1). As shown in FIGS. 5-7, the % ACN needs to be as low as 60% in order to achieve baseline resolution for 4-phenyl-2-butanol (see FIG. 5 ), whereas for benzoin and indapamide, 80% ACN provides short analysis times and baseline resolution (see FIGS. 6 and 7, respectively). Though the invention has been described with reference to specific forms of apparatus and method steps, various changes, modifications, additions and omissions may be made without departing from the spirit and scope of the invention defined in the appended claims.
A method for separating a mixture of at least two chemical compounds which first involves loading and sintering a frit material in a capillary to form a first retaining frit. After removing substantially all unsintered frit material from the capillary, a packing material made up of a substrate coated with a linear carbohydrate polymer is loaded into the capillary adjacent to the first retaining frit to form a stationary phase. More frit material is loaded in the capillary and is sintered to form a second retaining frit adjacent to the packing material on the side opposite from the first retaining frit. Substantially all unsintered frit material is again removed from the capillary. The chemical mixture is then introduced into the capillary at one of the retaining frits, and migration of the mixture across the packing material is induced by applying a voltage across the capillary. Differences in electroosmotic flow velocity between the compounds cause them to separate during migration.
6
RELATED APPLICATION [0001] This application claims priority to and the benefit of the prior filed copending and commonly owned patent application, assigned U.S. patent application Ser. No. 60/442,241, entitled “Tunable Adaptive Vibration Absorber Employing Magnetics with Variable Gap Length”, filed on Jan. 24th, 2003, and incorporated herein by reference. FIELD OF THE INVENTIONS [0002] The inventions relate to vibration absorbers, and more particularly, the inventions relate to adaptive vibration absorbers including methods and systems related thereto. BACKGROUND [0003] A vibration absorber generally is a device used to reduce vibration in a structure whose motion is undesirable or whose motion is sought to be minimized. Vibration absorbers are commonly used in vehicles, aircraft, and other mechanisms that carry passengers—at least to provide the passengers with a more comfortable ride as well as for other reasons. [0004] A type of vibration absorber referred to as a tuned vibration absorber (TVA) is used in many applications for the suppression of a specific vibration frequency. TVAs are used in many applications because of their relative low cost and well-established vibration absorption capabilities. TVAs, however, suffer the drawbacks of being passive devices and of being effective only for a relatively narrow bandwidth. [0005] Another type of vibration absorber is the active vibration controller (AVC). An AVC typically includes real-time property-changing characteristics and therefore can be highly effective. But uses of AVCs as vibration control mechanisms have been limited because AVCs have been costly to implement. Another problem that may arise in the use of AVC is that of an AVC adding energy to the system (and possibly driving the system into instability) in the event of an unanticipated excitation or improper control of the AVC. [0006] Thus, there is a need for a vibration absorber that includes the advantages, but does not suffer the drawbacks of the TVAs nor the limitations of the AVCs. There is a need for a vibration absorber that effectively and essentially eliminates vibration in structures and that is available at low cost with well-established vibration absorption capabilities. There is a need for a vibration absorber that may adaptively operate over a frequency range without the problems associated with adding energy to the system. Further, there is a need for a vibration absorber that is lightweight and compact. SUMMARY [0007] Stated generally, the inventions include an adaptive vibration absorber (AVA), and methods and systems therefore. Advantageously, the inventions provide an AVA that may effectively and essentially eliminate vibration in structures. The inventions provide an AVA that may operate adaptively over an appropriate relatively wide bandwidth or frequency range without adding energy to the system and the problems associated with such energy addition. Further, the inventions provide an AVA that may be of low cost as well as lightweight and compact. BRIEF DESCRIPTION OF THE DRAWINGS [0008] FIG. 1 is a block diagram illustrating by function an exemplary embodiment of the inventions in use with a vibrating device. [0009] FIG. 2 is a drawing of an exemplary embodiment of the inventions. [0010] FIG. 3 is a drawing of another exemplary embodiment of the inventions. [0011] FIG. 4 is a drawing of another exemplary embodiment of the inventions. [0012] FIG. 5 is a drawing of another exemplary embodiment of the inventions. DETAILED DESCRIPTION [0013] Several exemplary embodiments of the invention are described below in detail. The disclosed embodiments are intended to be illustrative only since numerous modifications and variations therein will be apparent to those of ordinary skill in the art. In reference to the drawings, like numbers indicate like parts continuously throughout the views. As utilized in the description herein and throughout the claims that follow, the meaning of “a,” “an,” and “the” include plural references also, unless the context of use clearly dictates otherwise. Additionally, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise as the term is utilized in the description herein and throughout the claims that follow. [0014] Generally stated, the inventions include adaptive vibration absorbers (AVAs) and methods and systems therefor. An AVA of the inventions may be considered a hybrid between a tuned vibration absorber (TVA) and an active vibration controller (AVC). The AVA includes the “active” characteristics of the AVC in that the AVA may be caused to operate selectively over a range of frequencies rather than a single frequency. One or more elements of the AVA is able to almost instantaneously and discretely change properties, thus increasing the effective bandwidth of vibration suppression by the AVA. The AVA operates like a TVA when the AVA has been set (via control algorithm or otherwise) to operate at a certain frequency. [0015] Advantageously, the hybrid nature of the AVA may make it superior to the AVC and the TVA. The AVA may be considered to be superior to an AVC because the AVA allows switching in frequency absorption to occur only at discrete times and to discrete states. Thus, the risk of adding energy to a system is virtually eliminated because the AVA behaves like a TVA between switches. The AVA may be considered superior to a TVA because the TVA may operate at more than one frequency. [0016] The ability of the AVA of the inventions to operative selectively over a range of frequencies is brought about, in part, by the lack of geometric restraints on the AVA, and particularly, with regard to the lack of geometric constraints on certain elements of the AVA as explained below. These elements may change properties thereby increasing the bandwidth of vibration suppression by the AVA. Rather than geometric boundary conditions, the AVA may operate through the principles of force balance with respect to its elements to achieve its advantages. [0017] FIG. 1 is a block diagram that is used to illustrate the functions of an exemplary embodiment of an AVA 10 of the inventions as used with a vibrating device 12 . The blocks illustrated in FIG. 1 correspond to functions of the involved elements and devices. The blocks are not to be interpreted as relative sizes of the elements or devices. In fact, reference to the other figures of this patent application demonstrates that the elements of the exemplary AVA 10 may vary in size, shape, and other characteristics. [0018] The exemplary AVA 10 is configured of the elements including a base mass 14 and an absorber mass 16 connected by a pair of switching elements 18 , 20 that function effectively as tunable springs and may be held responsible for the advantageous bandwidth increase in vibration suppression by the AVA 10 . [0019] The configuration and composition of the elements 14 , 16 , 18 and 20 of the exemplary AVA 10 provide a path (also referred to as magnetic circuit) for magnetic flux that may be induced by a magnetic field source 22 connected to, disposed on or around, or located close to the exemplary AVA 10 . Specifically, the magnetic circuit through the elements of the AVA 10 may originate with the magnetic field source 22 and pass through the absorber mass 16 , to one of the pair of switching elements 18 (referred to as switching element A or S.E. A), to the base mass 14 , to the other of the pair of switching elements 20 (referred to as switching element B or S.E. B), and so on. [0020] The switching elements 18 , 20 of the exemplary AVA are oriented in such a way that their static deflection lengths are determined by a force balance rather than geometric boundary conditions. When the source 22 provides the magnetic field and flux travels through the described magnetic circuit, the static deflection length in each of the pair of the switching elements 18 , 20 changes based on force balances and allowed at least in part because there are no geometric constraints on the elements 18 , 20 . Because the static deflection length is determined by a force balance, an increase in the magnetic attractive force causes the status deflection lengths of the switching elements 18 , 20 to decrease and achieves a larger natural frequency shift than the same system limited by geometric boundary conditions. In this manner, a change in the applied magnetic flux may be used to change the frequency of vibration absorption by the AVA 10 . This change may be controlled as necessary or desired via a control algorithm applied through a processor (not illustrated) or otherwise. [0021] As noted, FIG. 1 illustrates the functional configuration of the elements of the exemplary AVA 10 of the inventions. A description of exemplary compositions of the elements of the exemplary AVA 10 is now provided. [0022] The exemplary AVA 10 includes a base mass 14 that may serve as an attachment point to the vibrating device 12 . The exemplary AVA 10 may be hung in tension from the vibrating device 12 such as being hung from the vibrating device 12 by attachment to the base mass 14 of the AVA 10 . [0023] The base mass 14 as well as the absorber mass 16 in the exemplary embodiment are of made of relatively rigid, magnetically-conducting material such as iron or low carbon steel. One of the masses 14 , 16 may be a permanent magnet. The masses 14 , 16 may be of any appropriate shape such as the rectangular shapes illustrated in FIG. 1 , the half circle shapes illustrated in FIG. 2 , and the u-shapes illustrates in FIGS. 3 and 4 . The masses 14 , 16 may be of the same approximate size as illustrated in FIG. 2 , or the masses 14 , 16 may be of respectively different sizes as illustrated in FIGS. 3, 4 and 5 . [0024] As described above, in the exemplary AVA 10 of the inventions, the base mass 14 and the absorber mass 16 are not rigidly connected directly to each other. Rather, the base mass 14 and the absorber mass 16 are connected by two switching elements 18 , 20 that may be connected in parallel with respect to each other and between the masses 14 , 16 . The four elements, 14 , 16 , 18 , and 20 complete a magnetic circuit. When the magnetic field is applied by the magnetic field source 22 , the absorber mass 16 is attracted towards the base mass 14 . [0025] The switching elements 18 , 20 may be composed of “smart materials” to complete the magnetic circuit with the base mass 14 and the absorber mass 16 , and also to function as “springs”. The switching elements 18 , 20 may be any spring-like device with state-dependent static displacement lengths, such as bistable springs, or springs with variable numbers of active coils or close-wound springs. For example, the switching elements 18 , 20 may be discrete, noncontinuous iron paths with passive spring(s) used. As another example, any discrete magnetically-conducting path (for example, iron threads in cloth, where no one thread runs from the absorber mass to the base mass) can be placed in parallel with a spring to induce an increased stiffness effect. The switching elements 18 , 20 may “match” or be approximately the same in size and composition (or even other characteristics) as illustrated in FIGS. 1, 2 , 3 , and 4 . [0026] Alternatively, one of the switching elements 18 , 20 may be different from the other in size, composition or other characteristics as illustrated in FIG. 5 so long as the principles of the inventions are followed. Further, the Figures illustrate two switching elements 18 , 20 , but more or less switching elements may be used with compliance of the principles of the inventions. The Figures also illustrate the switching elements 18 , 20 to be disposed in parallel with respect to each other, but that does not have to be the case so long as the principles of the inventions are followed. [0027] In the exemplary AVA 10 , the switching elements 18 , 20 are made of a magnetorheological (MR) elastomer, which may be any elastomeric substance mixed with magnetically-conducting particles prior to curing. After the cure, the magnetically-conducting particles are no longer able to move freely as if they were in a fluid suspension. The MR elastomer may not be structurally rigid, nor may the elastomeric substance be magnetically-conducting. Examples of elastomeric substances include silicone gels, and natural or synthetic rubbers. The magnetically-conducting parties used with the elastomeric substance in the MR elastomer should be sufficiently small so as not to run the length (between the masses 14 , 16 ) of the MR elastomer's body. Examples of magnetically-conducting materials include iron micropowder, and low-carbon steel power or shavings. [0028] The MR elastomer of the exemplary embodiment uses a two-part silicone gel known as GE Silicone RTV6186. The silicone gel is embedded with iron particles that become aligned in chains. When a magnetic flux path flows through this composite material, the magnetic forces oppose any displacement the iron particles experience away from their magnetic equilibrium point. The magnetic strength forces the composite material to statically compress. This causes the effective stiffness of the silicone to increase. Another cause of the change in stiffness is due to the magnetic poles on the masses 14 , 16 . [0029] In the exemplary AVA 10 , the MR elastomer was prepared by mixing a desired percent iron to part B of a two-part silicone mixture. As noted, the silicone was GE Silicone RTV6186, and the iron was from ISP Technologies, R 1430. An equal mass part A was added to the mixture. The silicone was mixed for ten minutes on a hot plate heated to 50 degrees Celsius. The silicone mixture was then cured for thirty minutes at an elevated temperature while a large coil had 4.5 A current running through it, magnetically saturating the iron particles and forcing them to align in chains. The silicone produced was cylindrical. Once cured, the silicone was cut in half length-wise and each half was secured to the masses 14 , 16 using Loctite 454 epoxy. [0030] Also in the exemplary AVA 10 , and with respect to the percent of iron in the silicone mixture, a 5:1 maximum to minimum frequency ratio could be achieved by using the 30-35% iron by volume range with the best iron percent to be around 35% iron fraction by volume. Note: the design is iron-percentage dependent and “best” iron fraction may vary. [0031] In some cases, the absorber mass 16 may be too heavy for a silicone mixture in the switching elements 18 , 20 to support. Talc powder may be added to strengthen the silicone when not enough iron powder could otherwise be present, i.e., for small percentages of iron. Otherwise, the iron powder provides strengthening for the silicone and a means for magnetic flux to pass through what would otherwise be effectively an air gap. [0032] An MR elastomer of length 1 whose stiffness change is directly proportional to the magnetic flux that runs through it should have a maximum flux change for the least amount of power input. Therefore, two MR elastomers can be placed in parallel as seen in the exemplary AVA 10 . [0033] FIG. 1 illustrates a magnetic field source 22 for inducing and/or changing the magnetic flux in the magnetic circuit of the exemplary AVA 10 . The exemplary embodiment includes a coil of current-bearing wire (also referred to as magnet wire or a solenoid) as the magnetic field source 22 as illustrated in FIGS. 2 and 3 . The coil of current-bearing wire (and any other magnetic field source 22 ) may be disposed about the base mass 14 as illustrated in FIG. 2 or about the absorber mass 16 as illustrated in FIG. 3 . A design constraint on the magnetic field source 22 is that its placement should not affect the motion of the switching elements 18 , 20 . [0034] Changing the magnetic flux, as noted above, changes the frequency of vibration absorption by the AVA 10 . When the magnetic field is applied, the MR elastomer of the switching elements 18 , 20 of the exemplary AVA 10 is saturated. In other words, when current flows through the coils of the exemplary magnetic field source 22 , the exemplary AVA 10 experiences a relatively large stiffness increase. The large stiffness increase is generated because the elastomer motion is not limited by the geometric constraints. [0035] It should be emphasized that the above-described embodiments of the present invention are merely possible examples of implementations, merely set forth for a clear understanding of the principles of the invention. Many variations and modifications may be made to the above-described embodiments of the invention without departing substantially from the principles of the invention. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.
The inventions include an adaptive vibration absorber (AVA) and variation thereof including variations in methods and systems of usage. An exemplary AVA may operate adaptively over an appropriate relatively wide bandwidth or frequency range in vibration absorption without adding energy to the system and the problems associated with such energy addition. Further, the exemplary AVA may be of low cost as well sa lightweight and compact.
5
This application is a division of Ser. No. 287,387, filed Dec. 19, 1988, now U.S. Pat. No. 5,015,733, which is a division of Ser. No. 878,045, filed Jun. 24, 1986, now U.S. Pat. No. 4,849,513, which is a continuation-in-part of Ser. No. 709,579, filed Mar. 8, 1985, abandoned, which is a continuation-in-part of Ser. No. 565,010, filed Dec. 20, 1983, abandoned. The disclosures of all said prior applications are incorporated herein by reference. BACKGROUND OF THE INVENTION An oligonucleotide is a short polymer consisting of a linear sequence of four nucleotides in a defined order. The nucleotide subunits are joined by phosphodiester linkages joining the 3'-hydroxyl moiety of one nucleotide to the 5'-hydroxyl moiety of the next nucleotide. An example of an oligonucleotide is 5'>ApCpGpTpApTpGpGpC<3'. The letters A, C, G, and T refer to the nature of the purine or pyrimidine base coupled at the 1'-position of deoxyribose: A, adenine; C, cytosine; G, guanine; and T, thymine. "p" represents the phosphodiester bond. The chemical structure of a section of an oligonucleotide is shown in Structure 1. ##STR1## Synthetic oligonucleotides are powerful tools in modern molecular biology and recombinant DNA work. There are numerous applications for these molecules, including a) as probes for the isolation of specific genes based on the protein sequence of the gene product, b) to direct the in vitro mutagenesis of a desired gene, c) as primers for DNA synthesis on a single-stranded template, d) as steps in the total synthesis of genes, and many more, reviewed in Wm. R. Bahl et al, Prog. Nucl. Acid Res. Mol. Biol. 21, 101, (1978). A very considerable amount of effort has therefore been devoted to the development of efficient chemical methods for the synthesis of such oligonucleotides. A brief review of these methods as they have developed to the present is found in Crockett, G.C., Aldrichimica Acta 16(3), 47-55 (1983), and "Oligonucleotide Synthesis: A Practical Approach", ed. Gait, M.J., IRL Press, Oxford, England (1984). The best methodology currently available utilizes the phosphoramidite derivatives of the nucleosides in combination with a solid phase synthetic procedure, Matteucci, M.D. and Caruthers, M.H. J. Am. Chem. Soc. 103, 3185, (1981); and Beaucage, S.L., and Caruthers, M.H., Tet. Lett. 22(20), 1858-1862 (1981). In this chemistry, the 3'-nucleoside of the sequence to be synthesized is attached to a solid support via a base-labile linker arm. Subsequent nucleosides are attached sequentially to the previous nucleoside to generate a linear polymer of defined sequence extending off of the solid support. The general structure of a deoxyribonucleoside phosphoramidite is shown in Structure 2: ##STR2## and the chemical steps used in each cycle of oligonucleotide synthesis are shown in Structure 3: ##STR3## Oligonucleotides of length up to 40 bases may be made on a routine basis in this manner, and molecules as long as 106 bases have been made. Machines that employ this chemistry are now commercially available. There are many reasons to want a method for covalently attaching other chemical species to synthetic oligonucleotides. Fluorescent dyes attached to the oligonucleotides permit one to eliminate radioisotopes from the research, diagnostic, and clinical procedures in which they are used, and improve shelf-life and availability. As described in the assignees co-pending application for a DNA sequencing machine Ser. No. 570,973, filed Jan. 16, 1984) the synthesis of fluorescent-labeled oligonucleotides permits the automation of the DNA sequencing process. The development of appropriate techniques and instrumentation for the detection and use of fluorescent-labeled oligonucleotides allows the automation of other currently laborious laboratory and clinical techniques. The attachment of DNA cleavage chemicals such as those disclosed by Schultz et al, J. Am. Chem. Soc. 104, 6861 (1982); and Hertzberg, R.P., and Dervan, P.B., J. Am. Chem. Soc. 104, 313 (1982) permits the construction of synthetic restriction enzymes, whose specificity is directed by the oligonucleotide sequence. There are several reports in the literature of the derivitization of DNA. A modified nucleoside triphosphate has been developed wherein a biotin group is conjugated to an aliphatic amino group at the 5-position of uracil, Langer et al., Proc. Nat. Acad. Sci. U.S.A. 78, 6633-6637 (1981). This nucleotide derivative is effectively incorporated into double stranded DNA in a process referred to as "nick translation." Once in DNA it may be bound by anti-biotin antibody which can then be used for detection by fluorescence or enzymatic methods. The DNA which has had biotin-conjugated nucleosides incorporated therein by the method of Langer et al is fragmented into smaller single and double stranded pieces which are heterogeneous with respect to the sequence of nucleoside subunits and variable in molecular weight. Draper and Gold, Biochemistry 19, 1774-1781 (1980), reported the introduction of aliphatic amino groups by a bisulfite catalyzed transamination reaction, and their subsequent reaction with a fluorescent tag. In Draper and Gold the amino group is attached directly to a pyrimidine base. The amino group so positioned inhibits hydrogen bonding and for this reason, these materials are not useful in hybridization and the like. Also, this method does not permit amino groups to be inserted selectively at a desired position. Chu et al, Nucleic Acids Res. 11(18), 6513-6529 (1983), have reported a method for attaching an amine to the terminal 5'-phosphate of oligonucleotides or nucleic acids. This method involves a number of sequential reaction and purification steps which are laborious to perform and difficult to scale up. It also is restricted to the introduction of a single amino group at the 5'-terminus of the oligonucleotide. Subsequent to the filing of the original patent application of which the present case is a Continuation-In-Part, Takea and Ikeda, Nucl. Acids Res. Symp. Series 15, 101-104 (1984) have reported the synthesis and use of phosphotriester derivatives of putrescinyl thymidine for the preparation of amino-derivatized oligonucleotides. These materials differ from those reported herein in that the amino containing moiety is attached to the base moiety and not to the sugar moiety of the oligonucleotides, and also in that the DNA synthetic chemistry used was phosphotriester and not phosphoramidite. The present invention presents a general method for the introduction of one or more free aliphatic amino groups into synthetic oligonucleotides. These groups may be selectively inserted at any desired position in the oligonucleotide. They are readily and specifically reacted with a variety of amino reactive functionalities, and thereby permit the covalent attachment of a wide variety of chemical species in a position specific manner. This is illustrated by the preparation of a number of fluorescent oligonucleotide derivatives. The materials prepared in this fashion are effective in DNA hybridization methods, as illustrated by their use as primers in DNA sequence analysis, and also by a study of their melting behaviour in DNA duplex formation. According to the present invention, aliphatic amino groups are introduced into an oligonucleotide by first synthesizing a 3'-0-phosphoramidite derivative of a nucleoside analogue containing a protected aliphatic amino group attached to the sugar moiety of the nucleoside. This phosphoramidite is then reacted with the oligonucleotide being synthesized on a solid support. If the amino protecting group is base-labile, the process of oligonucleotide cleavage from the solid phase and deprotection of the base moieties and aliphatic amino group yields the amino-derivatized oligonucleotide. If the amino protecting group is acid-labile, it may be removed by treatment with anhydrous or aqueous acid prior to cleavage of the oligonucleotide from the support and deprotection of the base moieties, or it may be retained during cleavage and deprotection to simplify and improve the chromatographic purification of the oligonucleotide, and then removed subsequently by treatment with aqueous acid, yielding the amino-derivatized oligonucleotide in either case. More specifically, the present invention concerns modified deoxynucleoside phosphoramidites in which an aliphatic amino group, which has been suitably protected, is attached to the sugar moiety of the nucleoside. The chemical structure of a typical nucleoside is shown in Structure 4. ##STR4## It is characterized by a heterocyclic pyrimidine or purine base (B) linked by a carbon-nitrogen bond to the furanose (sugar) ring of ribose (R=R'=R"=OH) or deoxyribose (R=R'=OH; R"=H). The numbering of the sugar carbon atoms is 1' to 5' as indicated in the figure; thus, the base is connected to C-1' of the sugar. An aliphatic amino group may be attached in principle to any of the five ring carbons. It also comprises the respective phosphoramidite derivatives which are synthesized by reacting an appropriate phosphine with the free 3'-hydroxyl group of the suitably protected amino nucleosides. SUMMARY OF THE INVENTION Briefly, our invention includes novel protected amino nucleosides having the formula: ##STR5## wherein B is a common nucleoside purine or pyrimidine base, such as adenine, guanine, thymine, cytosine, uracil, or hypoxanthine, or their protected derivatives, especially those currently used in DNA chemical synthesis, namely N 6 -Benzoyladenine, N 2 -isobutyrylguanine, N 4 -benzoylcytosine, N 6 -di-n-butylformamidinyladenine, N 6 -(N-methyl-2-pyrrolidineamidinyl)-adenine, N 6 -succinyladenine, N 6 -phthaloyladenine, N 6 -dimethylacetamidinyladenine, or N 2 -di-n-butylformamidinylguanine; or an uncommon purine or pyrimidine base, such as purine, isocytosine, or xanthine (3,7-dihydro-1H-purine-2,6-dione), or their protected derivatives; or a substituted purine or pyrimidine base. Such substituents include, but are not limited to cyano, halo, haloalkyl, carboxy, formyl, hydroxy, alkoxy, aryl, azido, mercapto, nitro, carboxy esters, and carboxamides. Such bases include, but are not limited to, 6-chloropurine, 6-chloro-2-fluoropurine, 2,6-diaminopurine, 2-fluoro-N 6 -hydroxyadenine, 2,6-dihydroxyaminopurine, 8-bromoadenine, 2-chloroadenine, 8-azidoadenine, 8-mercaptoadenine, 8-aminoadenine, 6-thioguanine, 2,6-dichloropurine, N,N-dimethyl-6-aminopurine, N 6 -benzyladenine, 1,3-dimethylxanthine, 2-amino-6,8-dihydroxypurine, 6-methoxypurine, 6-mercaptopurine, 6-(2-hydroxyethyl)-aminopurine, N 6 -(2-isopentyl)-adenine, N 6 -furfuryladenine (kinetin), 5-bromomethyluracil, 5-dibromomethyluracil, 5-hydroxymethyluracil, 5-formyluracil, 5-fluorouracil, 5-bromouracil, 6-methyl-2-thiouracil, 5-hydroxymethyl-6-methyluracil, 5-hydroxyuracil (isobarbituric acid), 5-methoxyuracil, 5-methylcytosine, 5-trifluoromethyluracil, 5-nitrouracil, 5-aminouracil, 2-thiocytosine, 2-amino-4,6-dihydroxypyrimdine, 4-amino-2,6-dihydroxypyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, or 4-amino-6-hydroxy-2-mercaptopyrimidine, or their protected derivatives. B may also be a nucleoside base analog; such analogs are molecules that mimic the normal purine or pyrimidine bases in that their structures (the kinds of atoms and their arrangement) are similar to the normal bases, but may either possess additional or lack certain of the functional properties of the normal bases; such base analogues include, but are not limited to, imidazole and its 2-,4-, and/or 5-substituted derivatives (substituents are as defined above), indole and its 2-,3-,4-,5-,6-, and/or 7-substituted derivatives, benzimidazole and its 2-,4-,5-,6-, and/or 7-substituted derivatives, indazole and its 3-,4-,5-,6-, and/or 7-substituted derivatives, pyrazole and its 3-,4-, and/or 5-substituted derivatives, triazole and its 4- and/or 5-substituted derivatives, tetrazole and its 5-substituted derivatives, benzotriazole and its 4-,5-,6-, and/or 7-substituted derivatives, 8-azaadenine and its substituted derivatives, 8-azaguanine and its substituted derivatives, 6-azathymine and its substituted derivatives, 6-azauracil and its substituted derivatives, 5-azacytosine and its substituted derivatives, 8-azahypoxanthine and its substituted derivatives, pyrazolopyrimidine and its substituted derivatives, 3-deazauracil, orotic acid (2,6-dioxo-1,2,3,6-tetrahydro-4-pyrimidine carboxylic acid), barbituric acid, uric acid, ethenoadenine, and allopurinol (4-hydroxy-pyrazolo [3,4-d]pyrimidine), or their protected derivatives. B can also be a "C-nucleoside", in which the normal C--N bond between the base and C-1' of the sugar is replaced by a C--C bond; such bases include, but are not limited to, uracil (in the C-nucleoside pseudouridine), 1-methyluracil, 1,3-dimethyluracil, 5(4)-carbomethoxy-1,2,3-triazole, 5(4)-carboxamido-1,2,3-triazole, 3(5)-carboxymethylpyrazole, 3(5)-carbomethoxypyrazole, 5-carboethoxy-1-methylpyrazole, maleimide (in the C-nucleoside showdomycin), and 3(4)-carboxamido-4(3)-hydroxypyrazole (in the C-nucleoside pyrazomycin), or their protected derivatives. In Structure 5, R 1 , R 2 , R 3 , R 4 and R 5 (sometimes collectively referred to as R n ) are defined as follows: R 3 =H, R 4 =OH, and R 1 , R 2 and R 5 are either H, OR, or NHR', wherein R and R' are appropriate protecting groups; R is generally a lower alkyl or aryl ether, such as methyl, t-butyl, benzyl, o-nitrobenzyl, p-nitrobenzyl, o-nitrophenyl, or triphenylmethyl, or a lower alkyl or aryl ester, such as acetyl, benzoyl, or p-nitrobenzoyl, or an alkyl acetal, such as tetrahydropyranyl, or a silyl ether, such trimethylsilyl or t-butyl-dimethylsilyl, or a sulfonic acid ester, such as p-toluenesulfonyl or methanesulfonyl; R' is any common, standard nitrogen protecting group, such as those commonly used in peptide synthesis (R. Geiger and W. Konig, in "The Peptides: Analysis, Synthesis, Biology", E. Gross and J. Meienhofer, eds., v. 3, Academic Press, New York (1981), pp. 1-99); this includes, but is not limited to, acid-labile protecting groups such as formyl, t-butyloxycarbonyl, benzyloxycarbonyl, 2-chlorobenzyloxycarbonyl, 4-chlorobenzyloxycarbonyl, 2-4-dichlorobenzyloxycarbonyl, furfuryloxycarbonyl, t-amyloxycarbonyl, adamantyloxycarbonyl, 2-phenylpropyl (2)oxycarbonyl, 2-(4-biphenyl)propyl(2)-oxycarbonyl, triphenylmethyl, p-anisyldiphenylmethyl, di-p-anisylphenylmethyl, 2-nitrophenylsulfenyl, or diphenylphosphinyl; base labile protecting groups such as trifluoroacetyl, 9-fluorenylmethyloxycarbonyl, 4-toluene-sulfonylethyloxycarbonyl, methylsulfonylethyloxycarbonyl, and 2-cyano-t-butyloxycarbonyl; and others, such as chloroacetyl, acetoacetyl, 2-nitro-benzoyl, dithiasuccinoyl, maleoyl, isonicotinyl, 2-bromoethyloxycarbonyl, and 2,2,2-trichloroethyloxycarbonyl. At most one of R 1 , R 2 and R 5 may be NHR', and only R 4 may be OH. The "R" protecting groups referred to hereinabove, when containing carbon atoms, can contain from 1 to about 25 carbon atoms. CASES 1) If R 1 =NHR', then R 2 =H; R 5 may be either OR or H; the molecule in this case is termed a protected 2'-amino-2'-deoxyarabinonucleoside. 2) If R 2 =NHR', then R 1 =H; R 5 may either be OR or H; the molecule in this case is termed a protected 2'-amino-2'-deoxyribonucleoside. 3) If R 5' =NHR', then either R 1 or R 2 may be OR, with the other being H, or both may be H; if R 1 is OR, the molecule is termed a protected 5'-aminoarabinonucleoside; if R 2 is OR, the molecule is termed a protected 5'-amino-ribonucleoside; if both R 1 and R 2 are H, the molecule is termed a protected 5'-amino 2'-deoxyribonucleoside. The invention further includes novel phosphoramidites having the formula: ##STR6## wherein B, R 1 , R 2 and R 5 are as defined above, R 6 =lower alkyl, preferably lower alkyl such as methyl or isopropyl, or heterocyclic, such as morpholino, pyrrolidino, or 2,2,6,6-tetramethylpyrrolidino, R 7 =methyl, beta-cyanoethyl, p-nitrophenethyl, o-chlorophenyl, or p-chlorophenyl. Once again, the "R" groups referred to hereinabove, when containing carbon atoms, can contain from 1 to about 25 carbon atoms. It must be noted that the moiety symbolized by "B" in Structure 5 must also be appropriately protected prior to synthesis of the phosphoramidite symbolized by Structure 6, in order to render the phosphoramidite compatible with the DNA chain assembly chemistry. Such protection is thoroughly discussed in Gait, "Oligonucleotide Synthesis: A Practical Approach", and generally involves acylation or amidination of the exocyclic amino groups of "B"; such acyl groups include, but are not limited to, acetyl, benzoyl, isobutyryl, succinyl, phthaloyl, or p-anisoyl; such amidine groups include, but are not limited to dimethylformamidine, di-n-butylformamidine, or dimethylacetamidine; if "B" is substituted with other reactive groups, such as carboxyl, hydroxyl, or mercapto, these are appropriately protected as well. In another aspect, this invention comprehends the synthesis of oligonucleotides on a solid phase support, wherein the oligonucleotide is reacted with the protected amino-derivatized nucleoside phosphoramidite Structure 6. In addition, this invention includes the novel oligonucleotides having inserted therein at least one amino-derivatized nucleoside via phosphoramidite precursor of Structure 6. The present invention still further comprises the aforementioned novel aliphatic amino-derivatized single stranded oligonucleotides conjugated to a detectable moiety which is a chromophore, fluorescent agent, protein, enzyme, radioactive atom such as I 125 , or other "tag". It is an object of this invention to provide novel protected nucleosides. It is yet another object of this invention to provide novel phosphoramidites. In another important aspect of this invention, it is an object to provide novel oligonucleotides bound to a solid support which have been reacted with the aforementioned phosphoramidites. It is still another object of this invention to provide novel tagged oligonucleotides which are readily detectable by standard detection means. These and other objects and advantages of our invention will be apparent to those skilled in the art from the more elaborate and detailed description which follows. DETAILED DESCRIPTION OF THE INVENTION The following citations comprise a list of syntheses of amino nucleoside starting materials used in the preparation of the compounds of Structure 5 hereinabove. I) Synthesis of 5'-amino-5'-deoxythymidine and 5'-amino-5'-deoxyuridine and appropriate intermediates (embodiment of case 3): 1. Horwitz, J.P., Tomson, A.J., Urbanski, J.A., and Chua, J., J. Am. Chem. Soc. 27, 3045-3048 (1962). II) Synthesis of 2'-amino-2'-deoxyuridine and 2'-amino-2'-deoxycytidine and appropriate intermediates (embodiment of case 2): 1. Verheyden, J.P.H., Wagner, D., and Moffatt, J.G., J. Org. Chem. 36, 250-254 (1971). 2. Imazawa, M., and Eckstein, F., J. Org. Chem. 44, 2039-2041 (1979). 3. Torrence, P. F., and Witkop, B., in "Nucleic Acid Chemistry", vol. 2, Townsend, L.B., and Tipson, R.S., eds., pp. 977-989, J. Wiley and Sons, New York (1978). 4. Sasaki, T., Minamoto, K., Sugiura, T., and Niwa, M., J. Org. Chem. 41, 3138-3143 (1976). III) Synthesis of 2'-amino-2'-deoxyadenosine and 2'-amino-2'-deoxyguanosine and appropriate intermediates (embodiment of case 2): 1. Imazawa, M., and Eckstein, F. J. Org. Chem. 44, 2039-2041 (1979). 2. Hobbs, J.B., and Eckstein, F., J. Org. Chem. 42, 714-719 (1976). 3. Ranganathan, R., Tetrahedron Lett. 15, 1291-1294 (1977). 4. Mengel, R., and Wiedner, H., Chem. Ber. 109, 433-443 (1976). 5. Wolfrom, M.L., and Winkley, M.W., J. Org. Chem. 32, 1823-1825 (1967). 6. Ikehara, M., Maruyama, T., and Miki, H., Tetrahedron Lett. 49, 4485-4488 (1976). 7. Ikehara, M., and Maruyama, T., Chem. Pharm. Bull. Japan 26, 240-244 (1978). IV) Synthesis of some C-nucleoside analogs of natural nucleosides (relevant to all cases): 1. De Las Heras, F.G., Tam, S. Y-K., Klein, R S., and Fox, J.J., J. Org. Chem. 41, 84-90 (1976). 2. Trummlitz, G., Repke, D.B., and Moffatt, J.G., J. Org. Chem. 40, 3352-3356 (1975). 3. Chu, C.K., Reichman, U., Watanabe, K.A., and Fox, J.J., J. Heterocyclic Chem. 14, 1119-1121 (1977). 4. Ogawa, T., Pernet, A.G., and Hanessian, S., Tetrahedron Lett. 37, 3543-3546 (1973). 5. "Nucleosides, Nucleotides, and Their Biological Applications", J.L. Rideout, D.W. Henry, and L.M. Beacham III, eds., Academic Press, New York (1983). V) Synthesis of amino sugars and amino nucleosides by glycosylation and transglycosidation reactions (relevant to all cases): 1. Azuma, T., and Ishono, K., Chem. Pharm., Bull. Japan 25, 3347-3353 (1977). 2. Hashizume, T., and Iwamura, H., Tetrahedron Lett. 35, 3095-3102 (1965). 3. Anisuzzaman, A.K.M., and Whistler, R.L., J. Org. Chem. 37, 3187-3189 (1972). 4. Bishop, C.T., and Cooper, F.P., Can. J. Chem. 41, 2743-2758 (1963). 5. Unger, F.M., Christian, R., and Waldstatten, P., Tetrahedron Lett. 50, 4383-4384 (1977). 6. Unger, F.M., Christian, R., and Waldstatten, P., Tetrahedron Lett. 7, 605-608 (1979). 7. Bobek, M., and Martin, V., Tetrahedron Lett. 22, 1919-1922 (1978). 8. Wolfrom, M.L., Shafizadeh, F., Armstrong, R.K., and Shen Han, T.M., J. Am. Chem. Soc. 81, 3716-3719 (1959). 9. Wolfrom, M.L., Shafizadeh, F., and Armstrong, R.K., J. Am. Chem. Soc. 80, 4885-4888 (1958). 10. Wulff, G., Rohle, G., and Kruger, W., Angew. Chem. 82, 455-456 (1970). 11. Schroeder, L.R., and Green, J.W., J. Chem. Soc. C, 530-531 (1966). A preferred class of compounds within the scope of Structure 5 is given by the following. Composition of Matter No. 1: 5'-N-protected derivatives of 5'-amino-5'-deoxythymidine having the generic formula: ##STR7## wherein X=a standard nitrogen protecting group as defined in the generic description of the invention accompanying Structure 5; preferably, X=trifluoroacetyl (Tfa), 9-fluorenylmethyloxycarbonyl (Fmoc), triphenylmethyl (trityl), or p-anisyldiphenylmethyl (also referred to as monomethoxytrityl, MMT). The formula also encompasses a related class of compounds formed by reacting the compound wherein X=H with an activated appropriately protected amino acid derivative; in this case, X is represented by X=Y--NH--(CHQ)n--CO, wherein Y=a standard nitrogen protecting group as defined for X hereinabove, especially those listed as preferable for X hereinabove; and Q=any common amino acid side chain, with n=1 to about 12; generally n<=6; for n=1, Q includes, but is not limited to, such moieties as H (from the amino acid glycine), methyl (from the amino acid alanine), isopropyl (valine), benzyl (phenylalanine), p-hydroxybenzyl (tyrosine), carboxymethyl (aspartic acid), carboxyethyl (glutamic acid), 4-aminobutyl (lysine), imidazolylmethyl (histidine), indolylmethyl (tryptophan), mercaptomethyl (cystine), or hydroxymethyl (serine); for n>1, Q is generally H: for example, when n=2, the corresponding amino acid is beta-alanine; when n=3, 4-aminobutyric acid; when n=5, 6-aminohexanoic acid. If Q contains reactive moieties such as OH, SH, CO 2 H, or NH 2 , these are also appropriately protected with standard groups (see Geiger and Konig, "The Peptides: Analysis, Synthesis, Biology", for a thorough description of such groups). In this class of compounds, the protected amino group is spatially removed from the sugar ring of the nucleoside, either to improve its reactivity or to spatially separate the DNA chain from the "tag" that is to be affixed to the amino group. The formula also encompasses a class of compounds related to this latter class by having more than one amino acid linked in linear fashion (termed a peptide) attached to the compound wherein X=H; in this case, X is represented by X=Y--[NH--(CHQ i ) n --CO] m , wherein Y and n are as defined hereinabove, the various Q i are as defined for Q hereinabove, with i=1 to the maximum value of m, and m=1 to about 100; m=1 represents the class defined in the paragraph above. EXAMPLES The synthesis of the 5'-O-p-toluenesulfonylthymidine, 5'-azido-5'-deoxythmidine, and 5'-amino-5'-deoxythymidine starting materials are given in: Horwitz, J.P., Tomson, A.J., Urbanski, J.A., and Chua, J., J. Org. Chem. 27, 3045-3048 (1962). EXAMPLE 1 5'-N-trifluoroacetyl-5'-amino-5'-deoxythymidine having the formula: ##STR8## 5'-amino-5'-deoxythymidine (1.25 g, 5.0 mmoles) was dissolved in dry N,N-dimethylformamide (DMF) (25 ml). To this solution was added S-ethylthioltrifluoroacetate (1.3 ml, 10 mmoles; Aldrich Chemical Company). The reaction was gently stirred at room temperature. Thin layer chromatography (TLC) of the reaction mixture on silica gel 60 F-254 plates developed in acetone:methanol (1:1 v/v) showed a single spot of product by short wave UV. The product has a high mobility in this solvent system in contrast to the virtually immobile starting aminothymidine. The reaction mixture was rotary evaporated to dryness under reduced pressure, transferred to an Erlenmeyer flask with 2-propanol (30 ml), and recrystallized from boiling 2-propanol:methanol. Yield: 1.315 g (3.9 mmoles, 80% yield), mp. 261°-262° C.; analysis, 42.7%; H, 4.16%; N, 12.4%. The structure of the product was further confirmed by 1 H nuclear magnetic resonance (NMR) spectroscopy. Similarly, the following compounds are prepared: 1) 5'-N-trifluoroacetyl-5'-amino-2',5'-dideoxy-N 6 -benzoyladenosine from 5'-amino-2',5'-dideoxy-N 6 -benzoyladensosine. 2) 5'-N-trifluoroacetyl-5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine from 5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine. 3) 5'-N-trifluoroacetyl-5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine from 5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine. 4) 5'-N-trifluoroacetyl-5'-amino-2',5'-dideoxyuridine from 5'-amino-2',5'-dideoxyuridine. 5) 5'-N-trifluoroacetyl-5'-amino-2',5'-dideoxyinosine from 5'-amino-2',5'-dideoxyinosine. 6) 5'-N-trifluoroacetyl-5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine. 7) 5'-N-trifluoroacetyl-5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine. 8) 5'-N-trifluoroacetyl-5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine from 5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine. 9) 5'-N-trifluoroacetyl-5'-amino-2'-tetrahydropyranyl-N 4 -benzoyl-5'-deoxycytosine from 5'-amino-2'-tetrahydropyranyl-N 4 -benzoyl-5'-deoxycytosine. 10) 5'-N-trifluoroacetyl-5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine from 5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine. EXAMPLE 2 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine having the formula: ##STR9## Dry N,N-diisopropylethylamine (0.4 ml, 2.3 mmoles; Aldrich Chemical Company) was combined with dry DMF (3 ml) in a small round bottomed flask. 5'-amino-5'-deoxythymidine (0.5 g, 2.1 mmoles) was suspended in the mixture and 9-fluorenylmethylchloroformate (0.64 g, 2.5 mmoles; Aldrich Chemical Company) was added with stirring. The reaction rapidly became clear and TLC analysis on silica gel 60 F-254 plates developed in chloroform:ethanol:triethylamine (88:10:2 v/v) with short wave UV detection showed a single major spot of product and only a trace of unreacted starting aminothymidine. The product was precipitated by the addition of 1M aqueous sodium bicarbonate (25 ml), filtered, and the solid washed several times with, successively, 1M sodium bicarbonate, water, and a mixture of diethyl ether and hexanes (1:1 v/v). The product was dried overnight in a vacuum dessicator to give 0.88 g (1.9 mmoles, 90% yield) of a white solid. In some cases, the product was further purified by crystallization from absolute ethanol. The structure of the product was further confirmed by 1 H NMR spectroscopy. Similarly, the following compounds are prepared: 1) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideixy-N 6 -benzoyladenosine from 5'-amino-2',5'-dideoxy-N 6 -benzoyl-adenosine. 2) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine from 5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine. 3) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine from 5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine. 4) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxyuridine from 5'-amino-2',5'-dideoxyuridine. 5) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxyinosine from 5'-amino-2',5'-dideoxyinosine. 6) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine. 7) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine. 8) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine from 5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine. 9) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-N 4 -benzoyl-5'-deoxycytosine from 5'-amino-2'-tetrahydropyranyI-N 4 -benzoyI-5'-deoxycytosine. 10) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine from 5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine. EXAMPLE 3 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine having the formula: ##STR10## 5'-amino-5'-deoxythymidine (2.41 g, 10 mmoles) was coevaporated twice with anhydrous pyridine (25 ml each time) and then suspended in anhydrous pyridine (100 ml). Triethylamine (2.1 ml), N,N-dimethylaminopyridine (0.80 mg; Aldrich Chemical Company), and p-anisylchlorodiphenylmethane (4.68 g, 15.2 mmoles; Aldrich Chemical Company) were added. The reaction mixture was protected from moisture and light, and the yellow-orange solution stirred overnight at room temperature. The reaction was then cooled in ice, and cold saturated aqueous sodium bicarbonate (100 ml) was added to decompose excess tritylating agent. After thirty minutes, the mixture was transferred to a one liter separatory funnel and was extracted twice with ethyl acetate (200 ml portions). The combined ethyl acetate layers were washed twice with water (100 ml portions) and once with saturated aqueous sodium chloride (100 ml), dried over anhydrous magnesium sulfate, filtered, and rotary evaporated to dryness under reduced pressure. The gummy orange-yellow product was then coevaporated twice with anhydrous toluene (100 ml portions) to remove residual pyridine. The residue was dissolved in a minimum amount of ethyl acetate and applied to a column (100 cm by 3.0 cm) of neutral alumina (activity grade V, 15% water by weight; Woelm Pharma GmbH and Company) packed in hexanes. The column was first eluted with ethyl acetate:hexanes (1:1 v/v) until almost all of the bright yellow material had been eluted from the column, and then with pure ethyl acetate. The fractions containing product were pooled and rotary evaporated to dryness. The nearly colorless gummy residue was dissolved in a small volume of ethyl acetate and precipitated into hexanes (400 ml) at room temperature. The product was filtered and dried in a vacuum dessicator to give 4.53 g (8.8 mmoles, 88%) of a white powder, not crystallized. TLC analysis of the purified product on silica gel LQ6DF plates (Pierce Chemical Company) developed in acetonitrile:water (9:1 v/v) showed one spot by short wave UV detection, R f 0.87, that gave an orange-yellow color characteristic of the p-anisyldiphenylmethyl cation after spraying the plate with perchloric acid:ethanol solution (3:2 v/v). The structure of the product was further confirmed by 1 H NMR spectroscopy in perdeuterated dimethyl sulfoxide (Merck Isotopes). Similarly, the following compounds are prepared: 1) 5'-N-p-anisyldiphenylmethyl-5'-amino-2',5'-dideoxy-N 6 -benzoyladenosine from 5'-amino-2',5'-dideoxy-N 6 -benzoyl-adenosine. 2) 5'-N-p-anisyldiphenylmethyl-5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine from 5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine. 3) 5'-N-p-anisyldiphenylmethyl-5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine from 5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine. 4) 5'-N-p-anisyldiphenylmethyl-5'-amino-2',5'-dideoxyuridine from 5'-amino-2',5'-dideoxyuridine. 5) 5'-N-p-anisyldiphenylmethyl-5'-amino-2',5'-dideoxyinosine from 5'-amino-2',5'-dideoxyinosine. 6) 5'-N-(p-anisyldiphenylmethyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine. 7) 5'-N-(p-anisyldiphenylmethyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine. 8) 5'-N-(p-anisyldiphenylmethyl)-5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine from 5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine. 9) 5'-N-(p-anisyldiphenylmethyl)-5'-amino-2'-tetra-hydropyranyl- 4 -benzoyl-5'-deoxycytosine from 5'-amino-2'-tetrahydropyranyl-N 4 -benzoyl-5'-deoxycytosine. 10) 5'-N-(p-anisyldiphenylmethyl)-5'-amino-2'-tetra-hydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine from 5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine. 11) 5'-N-triphenylmethyl-5'-amino-2',5'-dideoxy-N 6 -benzoyladenosine from 5'-amino-2',5'-dideoxy-N 6 -benzoyladenosine. 12) 5'-N-triphenylmethyl-5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine from 5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine. 13) 5'-N-triphenylmethyl-5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine from 5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine. 14) 5'-N-triphenylmethyl-5'-amino-2',5'-dideoxyuridine from 5'-amino-2',5'-dideoxyuridine. 15) 5'-N-triphenylmethyl-5'-amino-2',5'-dideoxyinosine from 5'-amino-2',5'-dideoxyinosine. 16) 5'-N-triphenylmethyl-5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine. 17) 5'-N-triphenylmethyl-5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine. 18) 5'-N-triphenylmethyl-5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine from 5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine. 19) 5'-N-triphenylmethyl-5'-amino-2'-tetrahydropyranyl-N 4 -benzoyl-5'-deoxycytosine from 5'-amino-2'-tetrahydropyranyl-N 4 -benzoyl-5'-deoxycytosine. 20) 5'-N-triphenylmethyl-5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine from 5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine. EXAMPLE 4 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-5'-deoxythymidine having the formula: ##STR11## 5'-amino-5'-deoxythymidine (1.21 g, 5.0 mmoles) and N-benzyloxycarbonyl-6-aminohexanoic acid p-nitrophenyl ester (2.12 g, 5.5 mmoles; see note below) were dissolved in anhydrous DMF (25 ml) and stirred three days at room temperature. The solution was then rotary evaporated to dryness under reduced pressure to give a yellow solid, which was extensively triturated under several changes of dry ethyl ether. The powdery white product was then filtered, washed well with diethyl ether, and dried in a vacuum dessicator to give 2.31 g (4.7 mmoles, 95%). Note: N-benzyloxycarbonyl-6-aminohexanoic acid p-nitrophenyl ester was synthesized by standard techniques from N-benzyloxycarbonyl-6-aminohexanoic acid (Sigma Chemical Company), p-nitrophenol (Aldrich Chemical Company), and N,N 1 -dicyclohexylcarbodiimide (Aldrich Chemical Company) in ethyl acetate solution. Similarly, the following compounds are prepared: 1) 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-2',5'-dideoxy-N 6 -benzoyladenosine from 5'-amino-2',5'-dideoxy-N 6 -benzoyl-adenosine. 2) 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine from 5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine. 3) 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine from 5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine. 4) 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-2',5'-dideoxyuridine from 5'-amino-2',5'-dideoxyuridine. 5) 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-2',5'-dideoxyinosine from 5'-amino-2',5'-dideoxyinosine. 6) 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine from 5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine. 7) 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine from 5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine. 8) 5'-N-(N-benzyloxycarbonyl-6-aminohexanoyl)-5'-amino-2',5'-dideoxyuridine from 5'-amino-2',5'-dideoxyuridine. Composition of Matter No. 2: 3'-0-phosphoramidites of compounds described in composition of matter No. 1 having the generic formula: ##STR12## wherein X=as defined in previous section (composition of matter No. 1), R 6 =a lower alkyl, preferably a lower alkyl such as methyl or isopropyl, or a non-aromatic nitrogen-containing heterocycle, such as morpholino, piperidino, pyrrolidino or 2,2,6,6-tetramethylpiperidino, R 7 =methyl, beta-cyanoethyl, p-nitrophenethyl, o-chlorophenyl, or p-chlorophenyl. EXAMPLES NOTE: The phosphine starting materials used to synthesize the following phosphoramidite compounds were prepared according to literature procedures: 1) McBride, L.J., and Caruthers, M.H., Tetrahedron Lett. 245-248 (1983); and 2) Sinha, N.D., Biernat, J., McManus, J., and Koster, H., Nucl. Acids Res. 12. 4539-4557 (1984). EXAMPLE 5 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-0-methyl-N,N-diisopropylamino phosphoramidite having the formula: ##STR13## 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine (0.88 g, 1.9 mmoles) was suspended in dry dichloromethane (14 ml, dried by distillation from phosphorous pentoxide then calcium hydride). To this mixture was added N,N-diisopropylethylamine (0.5 ml, 2.9 mmoles). The suspension was stirred at room temperature under a dry argon atmosphere, and chloro-N,N-diisopropylaminomethoxyphosphine (0.4 ml, 2.1 mmoles) was added dropwise from a syringe. The solid starting material gradually dissolved, and TLC on silica gel 60 F-254 plates developed in chloroform:methanol: triethylamine (88:10:2.v/v) using short wave UV detection indicated that the reaction had gone to completion after sixty minutes. Ethyl acetate (50 ml) was added, and the organic phase was washed twice with cold saturated aqueous sodium bicarbonate (50 ml portions) and once with cold saturated aqueous sodium chloride (50 ml), dried over anhydrous magnesium sulfate, filtered, and the solvent removed by rotary evaporation under reduced pressure to yield a white foam (1.20 g, 100% crude yield). The product could be precipitated by dissolving it in few ml of dry toluene and adding this solution dropwise to several hundred ml of hexane at -78° C. (dry ice/acetone bath). The resulting white powder was obtained in 85-95% yield after precipitation and drying in a vacuum dessicator. The structure of the product was confirmed by 1 H NMR spectroscopy. Phosphorous ( 31 P) NMR spectroscopy in perdeuterated acetonitrile (Aldrich Chemical Company) showed two singlets at 148.77 and 148.34 ppm (relative to phosphoric acid in perdeuterated acetonitrile) as expected for the diastereomeric phosphoramidite product, and only traces (less than 5%) of other phosphorous-containing contaminants. TLC of the product using the system described above showed one major species (>=95%) and two minor species of slightly lower mobility. When 5'-N-trifluoroacetyl-5'-amino-5'-deoxythymidine is substituted for 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-0-methyl-N, N-diisopropylamino phosphoramidite was obtained. Similarly, the following compounds are prepared: 1) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-0-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 2) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-0-methyl-N,N-dimethylamino phosphoramidite. 3) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-0-methylmorpholino phosphoramidite. 4) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-0-beta-cyanoethylmorpholino phosphoramidite. 5) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-0-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 6) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-0-betacyanoethyl-N,N-dimethylamino phosphoramidite. 7) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxy-N 6 -benzoyladenosine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 8) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxy-N 2 -isobutyrylguanosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 9) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxy-N 4 -benzoylcytidine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 10) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxyuridine-3'-0-methylmorpholino phosphoramidite. 11) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxyinosine-3'-0-beta-cyanoethylmorpholino phosphoramidite. 12) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 13) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine-3'-O-beta-cyanoethyl-N,N-dimethylamino phosphoramidite. EXAMPLE 6 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-0-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite having the formula: ##STR14## 0 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine (0.785 g, 1.5 mmole) was dissolved in dry dichloromethane (10 ml, dried by distillation from phosphorous pentoxide and then calcium hydride) containing N,N-diisopropylethylamine (1.3 ml) under a dry argon atmosphere. Chloro-N,N-diisopropylamino-beta-cyanoethoxyphosphine (0.70 ml, 3.0 mmole) was added dropwise to the solution from a syringe over about one minute and the reaction stirred at room temperature. TLC on silica gel 60 F-254 plates developed in ethyl acetate: triethylamine (99:1 v/v) indicated that the reaction was complete after thirty minutes. Anhydrous methanol (0.1 ml) was then added to decompose excess phosphitylating agent, and the reaction stirred a few minutes longer. The reaction mixture was then transferred to a separatory funnel with ethyl acetate (50 ml, previously washed with 50 ml of cold 10% (w/v) aqueous sodium carbonate) and washed twice with cold 10% (w/v) aqueous sodium carbonate (80 ml portions) and twice with cold saturated aqueous sodium chloride (80 ml portions). The organic solution was then dried over anhydrous sodium sulfate, filtered, and rotary evaporated under reduced pressure to a clear foam. The foam was dissolved in dry ethyl acetate (10-15 ml) and this solution was added dropwise to hexane (200 ml) at -78° C. (dry ice/acetone bath). The precipitated product was filtered, washed well with -78° hexane, and dried in a vacuum dessicator to yield 0.932 g (1.31 mmoles, 87%) of a white powdery solid. The structure of the product was further confirmed by 1 H NMR spectroscopy in perdeuterated acetonitrile. 31 P NMR spectroscopy in perdeuterated acetonitrile showed two singlets at 147.74 and 147.53 ppm (relative to phosphoric acid in perdeuterated acetonitrile) as expected for the diastereomeric phosphoramidite product, and only traces (<5%) of other phosphorous-containing impurities. TLC in the above solvent system on silica gel LQ6DF plates showed two closely migrating spots under short wave UV detection, R.sub. f 0.87 and 0.92, once again due to the diastereomeric product. These spots gave an yellow-orange color characteristic of the p-anisyldiphenylmethyl cation when exposed to perchloric acid:ethanol solution (3:2 v/v). When the foregoing Example was repeated using chloro-N,N-diisopropylaminomethoxyphosphine in lieu of chloro-N,N-diisopropylamino-beta-cyanoethoxyphosphine, 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-methyl-N,N-diisopropylamino phosphoramidite was obtained. Similarly, the following compounds are prepared: 1) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 2) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 3) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-methylmorpholino phosphoramidite. 4) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-beta-cyanoethylmorpholino phosphoramidite. 5) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 6) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-betacyanoethyl-N,N-dimethylamino phosphoramidite. 7) 5'-N-p-anisyldiphenylmethyl 5'-amino-2',5'-dideoxyuridine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 8) 5'-N-p-anisyldiphenylmethyl 5'-amino-2',5'-dideoxyinosine-3'-O-methyl-N,N-diisopropylamidite. 9) 5'-N-p-anisyldiphenylmethyl 5'-amino-N 6 -benzoyl-2',5'-dideoxyadenosine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 10) 5'-N-p-anisyldiphenylmethyl 5'-amino-N 4 -benzoyl-2',5'-dideoxycytosine-3'-O-methylmorpholino phosphoramidite. 11) 5'-N-p-anisyldiphenylmethyl 5'-amino-N 2 -isobutyryl-2',5'-dideoxyguanosine-3'-O-beta-cyanoethylmorpholino phosphoramidite. 12) 5'-N-p-anisyldiphenylmethyl 5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 13) 5'-N-p-anisyldiphenylmethyl 5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine-3'-O-beta-cyanoethyl-N,N-dimethyl amino phosphoramidite. 14) 5'-N-p-anisyldiphenylmethyl 5'-amino-2'-tetrahydropyrenyl-N 6 -benzoyl-5'-deoxyadenosine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 15) 5'-N-p-anisyldiphenylmethyl 5'-amino-2'-tetrahydropyranyl-N 4 -benzoyl-5'-deoxycytosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 16) 5'-N-p-anisyldiphenylmethyl 5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine-3'-O-methyl-N,N-dimethylamino phosphoramidite. Composition of Matter No. 3: 2'-N-protected derivatives of 5'-O-protected 2'-amino-2'-deoxyuridine and 5'-O-protected 2'-N-aminoacyl-2'-amino-2'-deoxyuridine, a preferred class of compounds within the scope of Structure 5, having the generic formula: ##STR15## wherein R=triphenylmethyl (trityl), p-anisyldiphenylmethyl (monomethoxytrityl, MMT), di-p-anisylphenylmethyl (dimethoxytrityl, DMT), 9-phenylxanthenyl (pixyl), di-o-anisyl-1-napthylmethyl, p-anisyl-1-napthylphenylmethyl, or the like; wherein X=a standard nitrogen protecting group as defined in the generic description of the invention accompanying FIG. 5; preferably, X=trifluoroacetyl (Tfa), 9-fluorenylmethyloxycarbonyl (Fmoc), triphenylmethyl (trityl), or p-anisyldiphenylmethyl (also referred to as monomethoxytrityl, MMT). The formula also encompasses a related class of compounds formed by reacting the compound wherein X=H with an activated appropriately protected amino acid derivative; in this case, X is represented by X=Y--NH--(CHQ) n --CO, wherein Y=a standard nitrogen protecting group as defined for X hereinabove, especially those listed as preferable for X hereinabove; and Q=any common amino acid side chain, with n=1 to about 12, generally n<=6; for n=1, Q includes, but is not limited to, such moieties as H (from the amino acid glycine), methyl (from the amino acid alanine), isopropyl (valine), benzyl (phenylalanine), p-hydroxybenzyl (tyrosine), carboxymethyl (aspartic acid), carboxyethyl (glutamic acid), 4-aminobutyl (lysine), imidazolylmethyl (histidine), indolylmethyl (tryptophan), mercaptomethyl (cystine), or hydroxymethyl (serine); for n>1, Q is generally H: for example, when n=2, the corresponding amino acid is beta-alanine; when n=3, 4-aminobutyric acid; when n=5, 6-aminohexanoic acid. If Q contains reactive moieties such as OH, SH, CO 2 H, or NH 2 , these are also appropriately protected with standard groups (see Geiger and Konig, "The Peptides: Analysis, Synthesis, Biology", for a thorough description of such groups). In this class of compounds, the protected amino group is spatially removed from the sugar ring of the nucleoside, either to improve its reactivity or to spatially separate the DNA chain from the "tag" that is to be affixed to the amino group. The formula also encompasses a class of compounds related to this latter class by having more than one amino acid linked in linear fashion (termed a peptide) attached to the compound wherein X=H; in this case, X is represented by X=Y--[NH--(CHQ i ) n --CO] m , wherein Y and n are as defined hereinabove, the various Q i are as defined for Q hereinabove, with i=1 to the maximum value of m, and m=1 to about 100; m=1 represents the class defined in the paragraph above. EXAMPLES The syntheses of the starting compounds 2'-azido-2'-deoxyuridine, 2'-amino-2'-deoxyuridine, 2'-N-(N-benzyloxy-carbonylglycyl)-2'-amino-2'-deoxyuridine, 2'-N-glycyl-2'-amino-2'-deoxyuridine, and 2'-trifluoroacetamido-2'-deoxyuridine are given in: Verheyden, J.P.H., Wagener, D., and Moffatt, J.G., J. Org. Chem. 36, 250-254 (1971). Sharma, R.A., Bobek, M., and Bloch, A., J. Med. Chem. 18, 955-957 (1975). Imazawa, M., and Eckstein, F., J. Org. Chem. 44, 2039-2041 (1979). Generally, the procedures found therein were followed with only minor modifications to the workups, except: 1) 2'-azido-2'-deoxyuridine was purified on a column of neutral alumina in methanol:acetone (1:1 v/v) instead of on silica gel; 2) 2'-amino-2'-deoxyuridine was obtained by reduction of 2'-azido-2'-deoxyuridine with hydrogen in the presence of 5% palladium on carbon catalyst, instead of using triphenylphosphine and ammonia; 3) N-trifluoroacetylation of 2'-amino-2'-deoxyuridine was carried out using p-nitrophenyl trifluoroacetate followed by column chromatography on silica gel in chloroform:methanol (6:1 v/v), instead of using S-ethylthioltrifluoroacetate. EXAMPLE 7 5'-O-di-p-anisylph,enylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine having the formula: ##STR16## 2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine (1.25 g, 3.8 mmoles) was dissolved in anhydrous pyridine (50 ml), and di-p-anisylphenylethyl chloride (1.42 g, 4.2 mmoles; American Bionuclear Corporation) was added. The orange solution was then stirred overnight at room temperature in the dark. Water (10 ml) was added, and the mixture stirred an additional hour. The solvent was removed by rotary evaporation at 40° C. to give a resinous product, which was co-evaporated twice with toluene (100 ml portions). The foamy product was partitioned between water (50 ml) and ethyl acetate (100 ml), the layers separated, and the organic layer extracted with water (50 ml) and saturated aqueous sodium chloride (50 ml). The ethyl acetate solution was dried over anhydrous sodium sulfate, filtered, and evaporated to a yellow foam. This foam was then dissolved in an minimum volume of ethyl acetate:triethylamine (9:1 v/v), and applied to a column of silica gel (3 cm×25 cm) poured in the same solvent mixture. The column was eluted with ethyl acetate:triethylamine (9:1 v/v); fractions containing product were pooled and evaporated to a clear glassy solid. The product was dissolved in a minimum volume of ethyl acetate (about 10 ml) and precipitated into hexane (200 ml) at room temperature. The gelatinous precipitate was filtered and dried in a vacuum dessicator to give 2.06 g (3.3 mmoles, 86%) of a white power, not crystallized. TLC analysis of the purified product on silica gel 60 F-254 plates developed in chloroform: ethanol (9:1 v/v) showed one spot by short wave UV detection, R f 0.60, that gave a bright orange color characteristic of the di-p-anisylphenylmethyl cation after spraying the plate with perchloric acid:ethanol solution (3:2 v/v). The structure of the product was further confirmed by 1 H NMR spectroscopy in perdeuterated dimethyl sulfoxide. Fluorine ( 19 F) NMR spectroscopy in deuterated chloroform (Aldrich Chemical Company) showed one singlet at 6.03 ppm (relative to trifluoracetic acid in deuterated chloroform) as expected for the single trifluoroacetyl group. Similarly, the following compounds are prepared: 1) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyinosine. 2) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-N 6 -benzoyl-2'-deoxyadenosine. 3) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-N 4 -benzoyl-2'-deoxycytosine. 4) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-N 2 -isobutyryl-2'-deoxyguanosine. 5) 5'-O-di-p-anisylphenylmethyl-2'-N-(9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyinosine. 6) 5'-O-di-p-anisylphenylmethyl-2'-N-(9-fluorenylmethyloxycarbonyl)-2'-amino-N 6 -benzoyl-2'-deoxyadenosine. 7) 5'-O-di-p-anisylphenylmethyl-2'-N-(9-fluorenylmethyloxycarbonyl-2'-amino-N 4 -benzoyl-2'-deoxycytosine. 8) 5'-O-di-p-anisylphenylmethyl-2'-N-(9-fluorenylmethyloxycarbonyl-2'-amino-N 2 -isobutyryl-2'-deoxyguanosine. 9) 5'-O-di-p-anisylphenylmethyl-2'-N-(9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine. EXAMPLE 8 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine having the formula: ##STR17## 2'-N-glycyl-2'-amino-2'-deoxyuridine (1.2 g, 4.0 mmole) and p-nitrophenyl trifluoroacetate (1.2 g, 5.1 mmole; Aldrich Chemical Company) were dissolved in anhydrous DMF (20 ml) and the mixture was stirred overnight at room temperature. The reaction mixture was then rotary evaporated to dryness at 50° C., and the gummy yellow residue flash chromatographed (see Still, W.C., Kahn, M., and Mitra, A., J. Org. Chem. 43, 2923-2925 (1978)) on a column of silica gel 60 (2.5 cm×10 inches) in ethyl acetate:methanol (95:5 v/v). Fractions containing product were evaporated to dryness to give a white foam (1.5 g, 3.7 mmoles, 93%) which was not crystallized, but used directly in the next step. The above material (1.5 g, 3.7 mmoles) was evaporated twice with dry pyridine (30 ml portions), and the residue dissolved in dry pyridine (50 ml). N,N-dimethylaminopyridine (23 mg, 0.19 mmoles), triethylamine (0.8 ml, 5.2 mmoles), and di-p-anisylphenylmethyl chloride (1.54 g, 4.4 mmoles) were added, and the orange mixture stirred overnight at room temperature. Aqueous sodium bicarbonate (5% w/v, 50 ml) was then added, and the mixture stirred fifteen minutes more. The mixture was extracted twice with ethyl acetate (100 ml portions), and the combined ethyl acetate layers washed once with saturated aqueous sodium chloride (50 ml), dried over anhydrous sodium sulfate, filtered, and evaporated to dryness. After two co-evaporations with toluene (100 ml portions), the foamy yellow product was purified by chromatography on a column (3 cm×25 cm) of silica gel 60 using chloroform:methanol: triethylamine (89:10:1 v/v) as the eluant. Fractions containing product were pooled and evaporated to dryness to give a clear glassy solid. This material was dissolved in a minimum of ethyl acetate (about 10 ml) and precipitated into hexane (300 ml) at room temperature. The product was filtered and dried in a vacuum dessicator to give 1.62 g (2.3 mmoles, 62 %) of a powdery white solid, which could be crystallized from benzene/hexane. TLC analysis of the purified product on silica gel 60 F-254 plates developed in dichloromethane:methanol (92:8 v/v) showed one spot by short wave UV detection, R f 0.33, that gave a bright orange color characteristic of the di-p-anisylphenylmethyl cation after spraying the plate with perchloric acid:ethanol solution (3:2 v/v). The structure of the product was further confirmed by 1 H NMR spectroscopy in perdeuterated dimethyl sulfoxide. 19 F NMR spectroscopy in deuterated chloroform showed one singlet at 5.98 ppm (relative to trifluoroacetic acid in deuterated chloroform) as expected for the single trifluoroacetyl group. Similarly, the following compounds are prepared: 1) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.2 -isobutyryl-2'-deoxyguanosine. 2) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyinosine. 3) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.6 -benzoyl-2'-deoxyadenosine. 4) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.4 -benzoyl-2'-deoxycytosine. 5) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-N 2 -isobutyryl-2'-deoxyguanosine. 6) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-2'-deoxyuridine. 7) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-2'-deoxyinosine. 8) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-N 6 -benzoyl-2'-deoxyadenosine. 9) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-N 4 -benzoyl-2'-deoxycytosine. Composition of Matter No. 4: 3'-O-phosphoramidites of compounds described in composition of matter No. 3 having the generic formula: ##STR18## wherein R=as defined in the previous section (composition of matter No. 3); X=as defined in the previous section (composition of matter No. 3); R 6 =a lower alkyl, preferably a lower alkyl such as methyl or isopropyl, or a non-aromatic nitrogen-containing heterocycle, such as morpholino, piperidino, pyrrolidino, or 2,2,6,6-tetramethylpiperidono, R 7 =methyl, beta-cyanoethyl, p-nitrophenethyl, o-chlorophenyl, or p-chlorophenyl. EXAMPLES NOTE: The procedures described in this section are essentially the same as those described in the section entitled "Composition of Matter No. 2". The phosphine starting material used to synthesize the following phosphoramidite compounds were prepared according to the literature references given in that section. EXAMPLE 9 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-diisopropylamino phosphoramidite having the formula: ##STR19## 5!-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine (0.95 g, 1.5 mmoles) was dissolved in dry dichloromethane (10 ml, dried by distillation from phosphorous pentoxide and then calcium hydride) containing N,N-diisopropylethylamine (1.3 ml, 5.0 mmoles). The solution was stirred at room temperature under a dry argon atmosphere, and chloro-N,N-diisopropylaminomethoxyphosphine (0.45 ml, 2.4 mmoles) was added dropwise from a syringe over about one minute. TLC on silica gel 60 F-254 plates developed in ethyl acetate:triethylamine (99:1 v/v) indicated that the reaction was complete after thirty minutes. Anhydrous methanol (0.1 ml) was then added to decompose excess phosphitylating agent, and the reaction stirred a few minutes longer. The reaction mixture was then transferred to a separatory funnel with ethyl acetate (50 ml, previously washed with 50 ml of cold 10% (w/v) aqueous sodium carbonate) and washed twice with cold 10% (w/v) aqueous sodium carbonate (80 ml portions), and twice with cold saturated aqueous sodium chloride (80 ml portions). The organic solution was dried over anhydrous sodium sulfate, filtered, and rotary evaporated under reduced pressure to a clear foam. The foam was dissolved in dry ethyl acetate (10-15 ml) and this solution was added dropwise to hexane (200 ml) at -78° C. (dry ice-acetone bath). The precipitated product was filtered, washed well with -78° C. hexane, and dried in a vacuum dessicator to yield 1.04 g (1.3 mmoles, 87%) of a white powdery solid. The structure of the product was confirmed by 1 H NMR spectroscopy in perdeuterated acetonitrile. 31 P NMR spectroscopy in perdeuterated acetonitrile showed two singlets at 152.11 and 150.43 ppm (relative to phosphoric acid in perdeuterated acetonitrile) as expected for the diastereomeric phosphoramidite product, and only very slight traces (<1%) of other phosphorus-containing impurities. 19 F NMR spectroscopy in deuterated chloroform also showed two singlets at 0.42 and 0.38 ppm (relative to trifluoroacetic acid in deuterated chloroform), due to a slight influence of the neighboring chiral phosphorous. TLC in the above solvent system on silica gel LQ6DF plates showed only one spot under short wave UV detection, R f 0.96. This spot gave a bright orange color characteristic of the di-p-anisylphenylmethyl cation when exposed to perchloric acid:ethanol (3:2 v/v). Similarly, the following compounds are prepared: 1) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 2) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 3) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-methyl-morpholino phosphoramidite. 4) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-morpholino phosphoramidite. 5) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 6) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-N,N-dimethyl amino phosphoramidite. 7) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyinosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 8) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-N 6 -benzoyl-2'-deoxyadenosine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 9) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-N 4 -benzoyl-2'-deoxycytosine-3'-O-methyl-morpholino phosphoramidite. 10) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-N 2 -isobutyryl-2'-deoxyguanosine-3'-O-beta-cyanoethylmorpholino phosphoramidite. 11) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyinosine-3'-O-betacyanoethyl-N,N-dimethyl amino phosphoramidite. 12) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 13) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 14) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 15) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine-3'-O-methylmorpholino phosphoramidite. 16) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethylmorpholino phosphoramidite. 17) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 18) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine-3'-O-beta cyanoethyl-N,N-dimethylamino phosphoramidite. 19) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyinosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 20) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-N 6 -benzoyl-2'-deoxyadenosine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 21) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-N 4 -benzoyl-2'-deoxycytosine-3'-O-methylmorpholino phosphoramidite. 22) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-N 2 -isobutyryl-2'-deoxyguanosine-3'-O-beta-cyanoethyl morpholino phosphoramidite. 23) 5'-O-di-p-anisylphenylmethyl-2'N-(-9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyinosine-3'-O-beta-cyanoethyl-N,N-dimethylamino phosphoramidite. EXAMPLE 10 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-diisopropylamino phosphoramidite having the formula: ##STR20## 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine (1.07 g, 1.5 mmoles) was dissolved in dry dichloromethane (10 ml, dried by distillation from phosphorous pentoxide and then calcium hydride) containing N,N-diisopropylethylamine (1.3 ml, 5.0 mmoles). The solution was stirred at room temperature under a dry argon atmosphere, and chloro-N,N-diisopropylaminomethoxyphosphine (0.45 ml, 2.4 mmoles) was added dropwise from a syringe over about one minute. TLC on silica gel 60 F-254 plates developed in ethyl acetate:triethylamine (99:1 v/v) indicated that the reaction was complete after thirty minutes. Anhydrous methanol (0.1 ml) was added to decompose excess phosphitylating agent, and the reaction stirred a few minutes longer. The reaction mixture was then transferred to a separatory funnel with ethyl acetate (50 ml, previously washed with 50 ml of cold 10% (w/v) aqueous sodium carbonate) and washed twice with cold 10% (w/v) aqueous sodium carbonate (80 ml portions), and twice with cold saturated aqueous sodium chloride (80 ml portions). The organic solution was dried over anhydrous sodium sulfate, filtered, and rotary evaporated under reduced pressure to a clear foam. The foam was dissolved in dry ethyl acetate (10-15 ml) and this solution was added dropwise to hexane (200 ml) at -78° C. (dry ice-acetone bath). The precipitated product was filtered, washed well with -78° C. hexane, and dried in a vacuum dessicator to yield 1.23 g (1.4 mmoles, 93%) of a white powdery solid. The structure of the product was confirmed by 1 H NMR spectroscopy in perdeuterated acetonitrile. 31 P NMR spectroscopy in perdeuterated acetonitrile showed two singlets at 151.25 and 148.96 ppm (relative to phosphoric acid in perdeuterated acetonitrile) as expected for the diastereomeric phosphoramidite product, and only very slight traces (<2%) of other posphorous containing impurities. 19 F NMR spectroscopy in deuterated chloroform showed one singlet at 0.66 ppm (relative to trifluoroacetic acid in deuterated chloroform). TLC in the above solvent system on silica gel LQ6DF plates showed only one spot under short wave UV detection, R f 0.91. This spot gave a bright orange color characteristic of the di-p-anisylphenylmethyl cation when exposed to perchloric acid:ethanol (3:2 v/v). Similarly, the following compounds are prepared: 1) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 2) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 3) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-morpholino phosphoramidite. 4) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethylmorpholino phosphoramidite. 5) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 6) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-betacyanoethyl-N,N-dimethylamino phosphoramidite. 7) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyinosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 8) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.6 benzoyl-2'-deoxyadenosine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 9) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.4 -benzoyl-2'-deoxycytosine-3'-O-methylmorpholino phosphoramidite. 10) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyinosine-3'-O-beta-cyanoethyl-N,N-dimethylamino phosphoramidite. 11) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.6 -benzoyl-2'-deoxyadenosine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 12) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.4 -benzoyl-2'-deoxycytosine-3'-O-betacyanoethyl morpholino phosphoramidite. 13) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-N,N-dimethylamino phosphoramidite. 14) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-2'-deoxyinosine-3'-O-beta-cyanoethyl-N,N-dimethylamino phosphoramidite. 15) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-N 6 -benzoyl-2'-deoxyadenosine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 16) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-N 4 -benzoyl-2'-deoxycytosine-3'-O-beta-cyanoethyl-morepholino phosphoramidite. USES OF THE INVENTION 1) Synthesis of oligodeoxyribonucleotides containing a 5'-amino terminus. The steps involved in the use of protected 5'-amino-nucleoside phosphoramidites for the synthesis of oligodeoxyribonucleotides containing a 5'-amino terminus are shown in the Figure of Example 11, and are described in the following text. The protected 5'-amino-nucleoside-3'-O-phosphoramidites, preferably those in which Bn=thymine, X=Fmoc or MMT, R 6 =isopropyl, and R 7 =methyl or beta-cyanoethyl, most preferably beta-cyanoethyl, are coupled to the 5'-hydroxyl of a growing oligodeoxyribonucleotide attached to a solid support using standard phosphoramidite DNA synthesis techniques (see Atkinson, T., and Smith, M., in "Oligonucleotide Synthesis: A Practical Approach," Gait, M.J., pp. 35-82, IRL Press, Oxford, England (1984) and the references cited therein). Briefly, this procedure consists of reacting a protected 5'-amino-nucleoside 3'-O-phosphoramidite in anhydrous acetonitrile solution with the support-bound oligonucleotide in the presence of 1H-tetrazole under inert atmosphere, washing away excess reactants from product on the support, and then oxidizing the phosphite product to the desired phosphate with a solution of iodine in basic aqueous tetrahydrofuran. Generally, a ten-to-twenty-fold excess of phosphoramidite and a fifty-to-one hundred-fold excess of tetrazole over support-bound oligonucleotide are used; for the synthesis using the protected 5'-amino phosphoramidites, a twenty-fold excess of phosphoramidite and a one hundred-fold excess of tetrazole are preferred. Under these conditions, both the Fmoc-protected (Example 5) and the MMT-protected (Example 6) phosphoramidites routinely couple in better than 90% yield, generally in better than 95% yield. The couplings can be performed manually utilizing a six minute coupling reaction time and a three minute oxidation reaction time, or on an Applied Biosystems Model 380A automated DNA synthesizer (or similar instrument designed to accomodate the phosphoramidite chemistry) utilizing the accompanying pre-programmed synthesis cycles. The 5'-amino oligonucleotide is then obtained by cleaving the DNA from the support by treatment for at least four hours with concentrated ammonium hydroxide solution at room temperature, followed by deprotection of the DNA bases in the same solution at 55° C. for twelve to sixteen hours. When R 7 =methyl, a treatment with triethylammonium thiophenoxide in dioxane for one hour at room temperature is also required prior to cleavage of the DNA from the support. When X=Fmoc, the ammonium hydroxide treatments further serve to remove the base-labile Fmoc amino-protecting group and to yield an oligonucleotide product with a free 5'-amino terminus. The DNA-containing ammonium hydroxide solution is then lyophilized to dryness. This material can be further purified either by reverse phase high performance liquid chromatography (RP HPLC) on an octadecylsilyl silica (C18) column utilizing an increasing acetonitrile gradient in triethylammonium acetate buffer at near neutral pH (6.5 - 7.0), or by preparative polyacrylamide gel electrophoresis, a somewhat longer and more laborious procedure. For long oligonucleotides (>20 nucleotide subunits) the RP HPLC purification is generally unsatisfactory for the free 5'-amino DNA, due both to the increase in the amount of failure sequences (that is, a decreased overall yield of correct sequence DNA due to the large number of couplings) to be separated from the desired product, and the reduction in the resolving power of the C18 column for long DNA sequences. When X=MMT, the cleavage and deprotection treatments in ammonium hydroxide do not affect the base-stable, acid-labile MMT amino-protecting group. Thus, the desired product retains the MMT moiety on the 5'-amino group. This MMT group imparts an increased hydrophobicity to the desired product DNA, resulting in a marked increase in retention time during RP HPLC on a C18 column. The contaminating failure DNA sequences elute from the column much earlier than the desired oligonucleotide, which subsequently elutes in a clean and well-resolved fashion. The MMT protecting group can then be removed by mild acid treatment with acetic acid/water (80:20 v/v) solution at room temperature for twenty to thirty minutes, yielding highly purified free amino oligonucleotide. EXAMPLE 11 Synthesis of 3'>HO-CpApTpGpCpTpGpT-NH 2 5' using 5'-N (9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-O-methyl-N,N-diisopropylamino phosphoramidite and 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-methyl-N,N-diisopropylamino phosphoramidite ##STR21## The oligodeoxyribonucleotide 3'>HO-CpApTpGpCpTpG-OH<5' was synthesized manually on an aminopropyl silica support (containing about 4 micromoles of bound 5'-O-dimethoxytrityl-N 4 -benzoyl-2'-deoxycytidine) using standard phosphoramidite DNA synthesis techniques (Caruthers, M.H., Beaucage, S.L., Becker, C., Efcavitch, W., Fisher, E.F., Gallupi, G., Goldman, R., deHaseth, F., Martin, F., Mateucci, M., and Stabinsky, Y., in "Genetic Engineering", Setlow, A., and Hollander, J.K., eds., vol. 4, pp. 1-17, Plenum Press, New York (1982)). The 3'-O-methyl-N,N-diisopropylamino phosphoramidites of 5'-O-dimethoxytritylthymidine, 5'-O-dimethoxytrityl-N 6 -benzoyl-2'-deoxyadenosine, 5'-O-dimethoxytrityl-N 4 -benzoyl-2'-deoxycytidine, and 5'-O-dimethoxytrityl-N 2 -isobutyryl-2'-deoxyguanosine were synthesized according to published procedures (McBridge, L.J., and Caruthers, M.H., Tetrahedron Lett. 24, 245-248 (1983)). Spectroscopic analysis of the yield of dimethoxytrityl cation after each cycle of the synthesis indicated an overall yield of 88.8% for the heptamer, for a stepwise yield of 97.7%. The support was then split into two equal portions. One portion was treated with the Fmoc-protected phosphoramidite, and the other the MMT-protected phosphoramidite. In each case, a twenty-fold excess of phosphoramidite and a one hundred-fold excess of 1H-tetrazole over support-bound oligodeoxyribonucleotide was used, with a six minute coupling reaction time and a three minute oxidation reaction time. After washing and drying, each aliquot of the support was treated for one hour with triethylammonium thiophenoxide in dioxane, washed well, dried, and treated for four hours at room temperature with concentrated ammonium hydroxide in a tightly capped conical centrifuge tube. The supernatant was then decanted from the support, another aliquot of concentrated ammonium hydroxide added, and the solution heated at 55° C. for 16 hours in a tightly sealed tube (rubber septum). The DNA-containing solutions were then aliquoted into 1.5 ml Eppendorf tubes, lyophilized, and the resulting pellets dissolved in water. An aliquot of each oligonucleotide solution was then chromatographed on a RP HPLC system consisting of two Altex 110A pumps, a dual chamber gradient mixer, a Rheodyne injector, a Kratos 757 UV-VIS detector, and an Axxiom 710 controller. A Vydac C18 column (5 micron, 25 cm) was used. Amino oligonucleotide derived from Fmoc-protected 5'-amino-5'-deoxythymidine phosphoramidite was chromatographed using a linear gradient of 10% buffer B/90% buffer A to 30% buffer B/70% buffer A over forty minutes, where buffer A is aqueous 0.1 M triethylammonium acetate, pH 7/acetonitrile (98:2 v/v), and buffer B is aqueous 0.1 M triethylammonium acetate, pH 7/ acetonitrile (50:50 v/v). The desired oligonucleotide eluted from the column at 17.5 minutes (1 ml/minute flow rate) under these conditions (260 nm UV detection). Amino oligonucleotide derived from MMT-protected 5'-amino-5'-deoxythymidine phosphoramidite was first chromatographed as the dimethoxytritylated adduct, using a linear gradient of 20% buffer B/80% buffer A to 60% buffer B/40% buffer A over forty minutes (buffers A and B as described above). The product eluted at 39 minutes under these conditions (1 ml/minute flow rate). A preparative run of the MMT product was performed, the product collected and lyophilized, and the pellet treated with acetic acid/water (80:20 v/v) at room temperature for twenty minutes. Following lyophilization and re-dissolution in water, an aliquot was chromatographed using the same conditions as for the Fmoc-derived oligonucleotide. As expected, the product eluted at 17.5 minutes, the same retention time as was obtained for the Fmoc-derived oligonucleotide. Both purified amino oligonucleotides had UV spectra typical of DNA (major peak at 260 nm). The following compounds may be employed in a similar fashion to prepare the corresponding 5'-amino oligonucleotides: 1) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxyuridine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 2) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxyinosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 3) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-N 6 -benzoyl-2',5'-dideoxyadenosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 4) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-N 4 -benxoyl-2',5'-dideoxycytosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 5) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-N 2 -isobutyryl-2',5'-dideoxyguanosine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 6) 5'-N-(9-fluorenylmethylxxycarbonyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyuridine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 7) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-5'-deoxyinosine-3'-O-methyl morpholino phosphoramidite. 8) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-N 6 -benzoyl-5'-deoxyadenosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 9) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-N 4 -benzoyl-5'-deoxycytosine-3'-O-beta-cyanoethyl morpholino phosphoramidite. 10) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2'-tetrahydropyranyl-N 2 -isobutyryl-5'-deoxyguanosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 11) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-5'-deoxythymidine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 12) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxyuridine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 13) 5'-N-(9-fluorenylmethyloxycarbonyl)-5'-amino-2',5'-dideoxyinosine-3'-O-betacyanoethyl-N,N-dimethylamino phosphoramidite. 14) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 15) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 16) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-methyl morpholino phosphoramidite. 17) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-beta-cyanoethyl morpholino phosphoramidite. 18) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 19) 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-betacyanoethyl-N,N-dimethylamino phosphoramidite. 2) Synthesis in aqueous solution of oligodeoxyribonucleotides containing a fluorescent moiety on the 5'-terminus. The presence of a nucleophilic aliphatic amino group on the 5'-end of an oligonucleotide allows for further reaction of the amino DNA with a variety of electrophilic reagents, notably amino reactive fluorescent dye derivatives. Such dye derivatives include, but are not restricted to, fluorescein isothyiocyanate, tetramethylrhodamine isothiocyanate, eosin isothiocyanate, erythrosin isothiocyanate, rhodamine X isothiocyanate, lissamine rhodamine B sulfonyl chloride, Texas Red, Lucifer Yellow, acridine-9-isothiocyanate, pyrene sulfonyl chloride, 7-diethylamino-4-methylcoumarin isothiocyanate, and 4-fluoro-and 4-chloro-7-nitrobenz-2-oxa-1,3-diazole and their derivatives, such as succinimidyl 12-(N-methyl-N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)) aminododecanoate. The resultant dye-oligonucleotide conjugates may then be used for a variety of diagnostic or detection purposes. The basic procedure used for attaching dye molecules to an amino oligonucleotide is to combine the amino DNA and the dye in an aqueous (or aqueous/organic) solution buffered at pH 9, allow it to stand at room temperature for several hours, and then to purify the product in two stages. Excess unreacted dye is removed from dye-DNA conjugate and unreacted DNA by gel filtration. After lyophilization, pure dye-DNA conjugate is obtained using RP HPLC. EXAMPLE 12 Conjugation of fluorescein-5-isothiocyanate with 3'>HO-CpApTpGpCpTpGpT-NH 2 <5' ##STR22## 5'-amino oligonucleotide was synthesized as described in Example 11. The purified amino oligonucleotide (75 ul of a 1200 ug/ml solution in water) is diluted with water (105 ul) and 1 M aqueous sodium bicarbonate/sodium carbonate buffer, pH 9 (50 ul). A solution of fluorescein-5-isothiocyanate (FITC) in DMF (20 mg/ml, 20 ul) is added, and the yellow solution mixed well and allowed to sit in the dark overnight at room temperature (about 12-16 hours). The reaction mixture was then applied to a column (10 ml) of Sephadex G-25 (Pharmacia Fine Chemicals) packed in water in a 10 ml disposable plastic pipet, and the column was eluted with water. The fast moving yellow band (fluorescent under long wave UV) that eluted with the void volume of the column was collected. Unreacted dye remained nearly immobile at the top of the column. The crude dye-DNA conjugate was then lyophilized, dissolved in water, and subjected to RP HPLC. A Kratos FS970 LC fluorometer was used in conjunction with the UV detector in the system described in Example 11 to identify the desired product. A linear gradient of 10% buffer B/90% buffer A to 30% buffer B/70% buffer A over thirty minutes was used (buffers A and B are as described in Example 11). A small amount (<10%) of the starting amino oligonucleotide was eluted at 17.5 minutes (1 ml/minute flow rate), followed by a small amount of a fluorescent species at 29 minutes and the desired fluorescent product (the major product) at 33 minutes (UV detection at 260 nm, fluorescent excitation at 240 nm and detection using a 525 nm band pass filter). The purified fluorescent oligonucleotide had a UV absorbance maximum at 260 nm (characteristic of DNA) and a visible absorbance maximum at 496 nm (characteristic of fluorescein). Similar conjugates can be obtained by using Texas Red, tetramethyl rhodamine isothiocyanate, eosin isothiocyanate, erythrosin isothiocyanate, rhodamine X isothiocyanate, lissamine rhodamine B sulfonyl chloride, pyrene sulfonyl chloride, 7-diethylamino-4-methylcoumarin isothiocyanate, Lucifer Yellow, acridine-9-isothiocyanate, 4-fluoro-7-nitrobenz-2-oxa-1,3-diazole, and 4-chloro-7-nitrobenz-2-oxa-1,3-diazole. 3) Synthesis of oligodeoxyribonucleotides containing a fluorescent moiety on the 5'-terminus utilizing a solid support. The two step purification described in Example 12 can be avoided by reacting the fluorescent dye directly with the oligonucleotide containing a free 5'-amino group while it is still covalently linked to the support. In this case, experience has determined that the oligonucleotide must be assembled using the beta-cyanoethyl phosphorous-protected phosphoramidite monomers. This is necessary as the beta-cyanoethyl groups may be removed from the oligonucleotide phosphate triesters to give phosphate diesters under basic, anhydrous conditions, such as 20% (v/v) tertiary amine in anhydrous pyridine or 0.5 M 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) in anhydrous pyridine, at room temperature. Such treatment does not otherwise affect the DNA, nor does it cleave appreciable amounts from the support if strictly anhydrous conditions are observed. Generation of diesters is critical as the triester-containing oligonucleotide having a free amino group is unstable to the basic conditions needed to effect rapid reaction with the dye, and degrades to an as yet uncharacterized DNA-like species no longer having an accessible amino terminus. Conversion to the diester form retards this degradation. It is also necessary to employ an acid-labile protecting group such as p-anisyldiphenylmethyl (MMT) on the 5'-amino-5'-deoxythymidine phosphoramidite to introduce the 5'-amino terminus into the oligonucleotide. This is required as the MMT group is stable to the basic conditions needed to remove the phosphate protecting groups, where it is needed to prevent the basic degradation of the DNA described previously, but can subsequently be removed using mildly acidic conditions under which the DNA remains linked to the support, thus affording a free amino oligonucleotide for reaction with dye. Dye conjugation to the amino oligcnucleotide is carried out using an excess of dye (ten-to-one hundred-fold) in concentrated solution in anhydrous N,N-dimethylformamide/tertiary amine, preferably N,N-diisopropylethylamine (90:10 v/v) or triethylamine (80:20 v/v). After twelve to twenty-four hours, the excess dye is washed away, the dye-DNA conjugate is cleaved from the support, and the base-protecting groups are removed using concentrated ammonium hydroxide under the standard conditions described in Example 11. The product is then purified by RP HPLC. EXAMPLE 13 Conujugation of eosin-5-isothiocyanate and Texas Red with 3'>HO-TpTpTpTpTpTpT-NH 2 <5' on a solid support ##STR23## The oligodeoxyribonucleotide 3'>HO-TpTpTpTpTpT-OH<5' was synthesized as described in Example 11 on a controlled pore glass support on a one micromole scale using beta-cyanoethyl-protected phosphoramidites (obtained from American BioNuclear Corporation or synthesized as described in Example 6). Analysis of the yield of dimethoxytrityl cation after each cycle indicated an overall yield of 89.6% for the hexamer, for a stepwise yield of 97.8%. The final addition of 5'-N-p-anisyldiphenylmethyl-5'-amino-5'-deoxythymidine-3'-O-beta-cyanoethyl-N,N-diisopropyl-amino phosphoramidite was performed as described in Example 11. An aliquot of the fully protected, support-bound amino oligonucleotide containing about 0.5 umole of DNA (about 20 mg of support) was then treated with a mixture of a 5% (w/v) solution of N,N-dimethylaminopyridine (Aldrich Chemical Company) in anhydrous pyridine (500 ul) and a 10% (w/v) solution of p-anisyldiphenylmethyl chloride in anhydrous pyridine (500 ul) for one hour at room temperature. This was done in order to insure that all terminal amino groups were protected, and is probably unnecessary if the dye conjugation is to be performed soon after the oligonucleotide synthesis. The support was next washed well with dry pyridine and treated for two hours with 0.5 M DBU in anhydrous pyridine at room temperature. The support was again washed well with pyridine and then with diethyl ether and air dried. An aliquot (about 4 mg) was taken and cleaved, deprotected, and subjected to RP HPLC as usual as a control. The dry support-bound MMT-protected amino oligonucleotide was detritylated for twenty minutes at room temperature with acetic acid/water (80:20 v/v). The support was then washed with water and methanol, and treated for two minutes with triethylamine in anhydrous pyridine (20:80 v/v) to generate the free amine from the acetate salt. It was washed with pyridine and ether and air and vacuum dried. An aliquot (4 mg) was taken and cleaved, deprotected, and subjected to RP HPLC as usual as a control. The dye conjugation reactions were carried out in 1.5 ml Eppendorf tubes. Dyes were obtained from Molecular Probes Inc., Junction City, Oregon. About 0.1 umole of support-bound amino oligonucleotide (4-5 mg) was treated with either eosin-5-isothiocyanate (3.5 mg, a 50-fold excess) or Texas Red (2.4 mg, a 38-fold excess) in anhydrous DMF containing 10% (v/v) N,N-diisopropylethylamine (50 ul). The reactions were allowed to proceed in the dark for 12 to 16 hours at room temperature. The reaction mixture was then transferred to a small glass-fritted funnel and washed well with DMF, methanol, and ether, and air dried. At this point, the eosin-conjugated support was pink and the Texas Red-conjugated support was purple. Both supports fluoresced strongly under long wave UV light. Each dye-DNA conjugate was cleaved from its support as described in Example 11 (four hours at room temperature in concentrated ammonium hydroxide), and subjected to base-deprotection conditions (twelve hours at 55° C. in concentrated ammonium hydroxide). Although unnecessary for a poly-T oligonucleotide, this latter treatment was performed to test the effect of the treatment on the dye moiety and the dye-DNA linkage. The strongly fluorescent orange (eosin) and pink-red (Texas Red) dye-DNA solutions were then lyophilized, dissolved in water, and each fluorescent oligonucleotide purified by RP HPLC using a linear gradient of 10% buffer B/90% buffer A to 30% buffer B/70% buffer A over ten minutes, then 30% buffer B/70% buffer A to 60% buffer B/40% buffer A over ten minutes (buffers A and B as described in Example 11). HPLC analysis of the two dye-oligonucleotide conjugates indicated that, in the case of eosin-5-isothiocyanate, the reaction had proceeded to about 80% completion, as judged from the disappearance of starting amino oligonucleotide, while in the case of Texas Red, a sulfonyl chloride, the reaction had proceeded to only about 20-30% completion. In each chromatogram, a peak representing underivatized amino oligonucleotide was observed at 16 minutes. The desired eosin-DNA conjugate eluted from the column at 25 minutes, and the Texas Red-DNA conjugate at 29.5 minutes. Control HPLC analyses of the starting amino oligonucleotide and of each fluorescent oligonucleotide separately synthesized using the solution method described in Example 8 confirmed the above assignment. In addition, while the Texas Red-oligonucleotide appeared unharmed by the deprotection conditions, the eosin-oligonucleotide did appear to have suffered a small amount of degradation. However, in both cases, the overall yield of dye-DNA conjugate using the solid phase method was as good or better than that using the solution method, and the workup and purification was much simpler. The UV-visible spectrum of each purified dye-DNA conjugate showed two major peaks, as anticipated: for the eosinoligonucleotide, one at 262 nm (DNA absorbance), and one at 524 nm (dye absorbance); and for the Texas Red-oligonucleotide, one at 262 nm (DNA absorbance), and one at 596 nm (dye absorbance). Similar conjugates can be obtained by using fluorescein isothiocyanate, tetramethyl rhodamine isothiocyanate, eosin isothiocyanate, erythrosin isothiocyanate, rhodamine X isothiocyanate, lissamine rhodamine B sulfonyl chloride, pyrene sulfonyl chloride, 7-diethylamino-4-methylcoumarin isothiocyanate, 4-fluoro-7-nitrobenz-2-oxa-1,3-diazole, 4-chloro-7-nitrobenz-2-oxa-1,3-diazole, acridine-9-isothiocyanate, and Lucifer Yellow. 4) Synthesis of oligodeoxyribonucleotides containing one or more internal aliphatic amino groups. The trifluoracetyl-protected (Tfa-protected) 2'-amino-2'-deoxyuridine-3'-O-phosphoramidites described in the section entitled "Composition of Matter No. 4" can be used to synthesize oligodeoxyribonucleotides containing one or more free amino groups at internal positions in the DNA oligomer. This is possible since the position of the amino group (that is, on the 2'-carbon atom of the sugar ring) in these compounds is not involved in the formation of the 3',5'-phosphodiester backbone of the DNA chain. As such, these compounds may be coupled to the 5'-hydroxyl of a growing oligodeoxyribonucleotide attached to a solid support using the standard phosphoramidite DNA synthesis techniques described in Example 11. Unlike the protected 5'-amino-5'-deoxythymidine compounds, whose use forces the termination of the growing DNA chain due to the presence of the amino group on the 5'-terminus, the 5'-O-di-p-anisylphenylmethyl group present on the 5'-hydroxyl of the Tfa-protected 2'-amino-2'-deoxyuridine compounds may be removed in the next cycle of the synthesis allowing for further elongation of the synthetic oligonucleotide by the usual procedure. Since a Tfa-protected 2'-amino-2'-deoxyuridine unit can be inserted at any position in the chain, the resultant oligomer can contain any desired number of reactive amino groups. These compounds can be coupled to a growing DNA chain using the chemistry outlined in Example 11; however, the presence of a group other than hydrogen at the 2'-position necessitates the use of longer coupling times to achieve a coupling efficiency similar to that observed using normal deoxyribonucleotide phosphoramidites. Once again, a ten-to-twenty-fold excess of phosphoramidite and a fifty-to-one hundred-fold excess of 1H-tetrazole over support-bound oligonucleotide are required; the larger excesses are strongly preferable in this case. Coupling times using these quantitites are generally one to one and one-half hours, as opposed to the six minutes used for normal phosphoramidite couplings. Since the Tfa-protected 2'-amino-2'-deoxyuridine phosphoramidites appear to undergo some degradation during this longer coupling time, two or three shorter couplings (twenty to thirty minutes each) are preferable to one extended coupling. Under these conditions, the Tfa-protected 2'-amino-2'-deoxyuridine-3'-O-phosphoramidites (Examples 9 and 10) routinely couple in better than 80% yield, and generally in better than 85% yield. The oligonucleotide product containing one or more internal amino groups is then obtained using the standard cleavage and deprotection conditions outlined in Example 11. Since the Tfa group is baselabile, it is easily removed during the concentrated ammonium hydroxide treatments, yielding an oligonucleotide product containing the desired number of free amino groups. After lyophilization, the product DNA may be purified either by RP HPLC or by gel electrophoresis, as described previously. Furthermore, the crude product DNA can be obtained containing a 5'-O-di-p-anisylphenylmethyl group, thus simplifying RP HPLC purification in a manner analogous to that described for the 5'-N-p-anisyldiphenyl-methyl group. EXAMPLE 14 Synthesis of 3'>HO-CpApTpGpCpU(2'-NH 2 )pGpT-OH<5' using 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-diisopropylamino phosphoramidite, and of 3'>HO-CpApTpGpCpU(2'-NHCOCH 2 NH 2 ) pGpT-OH<5' using 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoracetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-diisopropylamino phosphoramidite ##STR24## The oligodeoxyribonucleotide 3'>HO-CpApTpGpC-OH<5' was synthesized manually on an aminopropyl silica support as described in Example 11. The support was then split into two equal portions. One portion was used in a coupling with 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine (DMT-TfaNHdU) phosphoramidite, and the other in a coupling with 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine (DMT-TfaGlyNHdU) phosphoramidite. In each case, two sequential couplings of thirty minutes each were performed prior to the oxidation reaction, with the support being washed well with anhydrous acetonitrile between couplings. In each coupling, a twenty-fold excess of phosphoramite and a one-hundred-fold excess of lH-tetrazole were used. Under these conditions, both the DMT-TfaNHdU phosphoramidite and the DMT-TfaGlyNHdU phosphoramidite coupled in 83-85% yield (as judged by the yield of dimethyoxytrityl cation after this cycle). After a three minute oxidation reaction and a three minute capping reaction, the last two nucleotide phosphoramidites were coupled to the amino uridine-containing oligonucleotide. In each case, the first of these two couplings proceeded in better than 98% yield; the final di-p-anisylphenylmethyl group was retained on the 5'-end of each oligonucleotide in order to simplify RP HPLC purification. After washing and drying, each aliquot of the support-bound oligonucleotide was treated under the standard cleavage and deprotection conditions described in Example 11, lyophilized, and dissolved in water. An aliquot of each solution was then subjected to RP HPLC analysis using the system described in Example 11. A linear gradient of 20% buffer B/80% buffer A to 60% buffer B/40% buffer A (buffers A and B as described in Example 11) over forty minutes was used to purify each tritylated adduct. Both the U(2'-NH 2 )-containing oligonucleotide and the U(2'-NHCOCH 2 NH 2 )-containing oligonucleotide eluted at 39 minutes under these conditions (1 ml/minute flow rate). A preparative purification was performed for each oligonucleotide, the product collected and lyophilized, and the pellet treated with acetic acid/water (80:20 v/v) for thirty minutes at room temperature to remove the 5'-di-p-anisylphenylmethyl group. Following lyophilization and re-dissolution in water, an aliquot of each solution was chromatographed using a linear gradient of 10% buffer B/90% buffer A to 30% buffer B/70% buffer A over thirty minutes. Under these conditions (1 ml/minute flow rate), the U(2'-NH 2 )-containing octamer eluted cleanly at 18 minutes (UV detection at 260 nm), while the U(2'-NHCOCH 2 NH 2 )-containing octamer eluted slightly less cleanly at 19 minutes. No peak eluting at 18 minutes was seen in this latter chromatogram, indicating that little if any of the glycine moiety had been hydrolyzed from the DNA by any chemical treatment during the synthesis. Both purified 2'-amino oligonucleotides had UV spectra typical of DNA (major peak at 260 nm). The following compounds may be employed in a similar fashion to prepare the corresponding 2' amino oligonucleotides: 1) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 2) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-deoxyinosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 3) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-N 6 -benzoyl-2'-deoxyadenosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 4) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-N 4 -benzoyl-2'-deoxycytosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 5) 5'-O-di-p-anisylphenylmethyl-2'-N-trifluoroacetyl-2'-amino-2'-N 2 -isobutyryl-2'-deoxyguanosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 6) 5'-O-di-p-anisylphenylmethyl-2'-N-(9-fluorenylmethyloxycarbonyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-dissopropylamino phosphoramidite. 7) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-N,N-diisopropylamino phosphoramidite. 8) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-dimethylamino phosphoramidite. 9) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-morpholino phosphoramidite. 10) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethylmorpholino phosphoramidite. 11) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-p-nitrophenethyl-N,N-dimethylamino phosphoramidite. 12) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyuridine-3'-O-beta-cyanoethyl-N,N-dimethylamino phosphoramidite. 13) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-2'-deoxyinosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 14) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.6 -benzoyl-2'-deoxyadenosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 15) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.4 -benzoyl-2'-deoxycytosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 16) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-trifluoroacetylglycyl)-2'-amino-N.sup.2 -isobutyryl-2'-deoxyguanosine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 17) 5'-O-di-p-anisylphenylmethyl-2'-N-(N-9-fluorenylmethyloxycarbonyl-glycyl)-2'-amino-2'-deoxyuridine-3'-O-methyl-N,N-diisopropylamino phosphoramidite. 5) Synthesis in aqueous solution of oligodeoxyribonucleotides containing one or more fluorescent moieties at internal 2'-positions. As has been described in Section 2, the presence of an aliphatic amino group in an oligonucleotide allows for further reaction of the DNA with a variety of reagents. In the case of fluorescent dyes, enhanced detection sensitivity may be achieved by conjugating more than one dye molecule to an oligonucleotide, thus increasing the amount of fluorescence per oligomer. The ability to incorporate any desired number of amino groups into an oligonucleotide via the 2'-amino-2'-deoxyuridine phosphoramidites can be utilized to achieve this enhancement. The basic procedure for conjugating a fluorescent dye to a 2'-amino oligonucleotide is the same as that described in Example 12. EXAMPLE 15 Conjugation of fluorescein-5-isothiocyanate with 3'>HO-CpApTpGpCpU(2'-NH 2 )pGpT-OH<5' and 3'>HO-CpApTpGpCpU(2'-NHCOCH 2 NH 2 )pGpT-OH<5' ##STR25## The 2'-amino oligonucleotides were synthesized as described in Example 14. Each of the purified amino oligonucleotides (75 ul of a 600-1000 ug/ml solution in water) was diluted with water (105 ul) and 1 M aqueous sodium bicarbonate/sodium carbonate buffer, pH 9 (50 ul) in 1.5 ml Eppendorf tubes. A solution of fluorescein-5-isothiocyanate (FITC) in DMF (20 mg/ml, 20 ul) was added, and the yellow solution mixed well and allowed to stand at room temperature overnight in the dark (about 12-16 hours). Each reaction mixture was then applied to a separate column (10 ml) of Sephadex G-25 packed in water in a 10 ml disposable plastic pipet, and the column was eluted with water. The fast moving yellow band (fluorescent under long wave UV) that eluted with the void volume of the column was collected in each case. The crude dye-DNA conjugates were then lyophilized, dissolved in water, and subjected to RP HPLC using the system described in Example 12. A linear gradient of 10% buffer B/90% buffer A to 30% buffer B/70% buffer A over thirty minutes was used (buffers A and B as described in Example 11), and a flow rate of 1 ml/minute. In the case of the U(2'-NH-FITC)-containing oligonucleotide, two major peaks were observed. The starting 2'-amino oligonucleotide eluted at 18 minutes as expected, while the fluorescent product dye-oligonucleotide conjugate eluted at 26 minutes (UV detection at 260 nm, fluorescent excitation at 240 nm and detection using a 525 nm band-pass filter). The fluorescent product accounted for about 50% of the total amount of amino-containing DNA present in the sample. In the case of the U(2'-NHCOCH2NH-FITC)-containing oligonucleotide, three major peaks were observed. The starting 2'-amino oligonucleotide eluted at 20 minutes as expected. The second major peak at 20.5 minutes was also observed as a contaminant in the chromatogram of the starting 2'-amino oligonucleotide. The fluorescent product dye-oligonucleotide conjugate eluted at 28 minutes. In this case, however, the fluorescent product accounted for at least 90% of the total amount of amino-containing DNA in the sample. The substantially higher degree of conjugation can be attributed to the presence of the glycine moiety on the 2'-amino group. Not surprisingly, moving the reactive amino group away from the sugar ring and thus reducing the steric hindrance to its access- by dye increases the amount of dye-DNA conjugate obtained. Therefore, it is possible to control the degree of reactivity of the amino group by adjusting the length of the spacer, thus controlling its distance from the sugar ring. Both purified fluorescent oligonucleotides had a UV absorbance maximum at 260 nm (characteristic of DNA) and a visible absorbance maximum at 496 nm (characteristic of fluorescein). The above can also be carried out by using Texas Red, tetramethyl rhodamine isothiocyanate eosin isothiocyanate, erythrosin isothiocyanate, rhodamine X isothiocyanate, lissamine rhodamine B sulfonyl chloride, Lucifer Yellow, acridine-9-isothiocyanate, pyrene sulfonyl chloride, 7-diethylamino-4-methylcoumarin isothiocyanate, 4-fluoro-7-nitrobenz-2-oxa-1,3-diazole, and 4-chloro-7-nitrobenz-2-oxa-1,3-diazole. Having fully described the invention, it is intended that it be limited solely by the lawful scope of appended claims.
The invention consists of compounds and methods for the synthesis of oligonucleotides which contain one or more free aliphatic amino groups attached to the sugar moieties of the nucleoside subunits. The synthetic method is versatile and general, permitting amino groups to be selectively placed at any position on oligonucleotides of any composition or length which is attainable by current DNA synthetic methods. Fluorescent dyes or other detectable moieties may be covalently attached to the amino groups to yield the corresponding modified oligonucleotide.
2
BACKGROUND OF THE INVENTION The invention concerns a method and apparatus for controlling the operation of an internal combustion engine, and in particular, to a method and apparatus for controlling the combustion process of an externally ignited internal combustion engine. Different procedures exist to influence the combustion process of externally ignited combustion engines containing at least one combustion chamber with at least one reciprocating or rotating piston. It is an established fact that ignition settings and/or the composition of the combustion charge, i.e., air-fuel ratio of the charge, may be altered in accordance with selected operating parameters, such as, for instance, engines revolutions, outside temperature, barometric pressure, temperature of the cooling water, temperature of the lubricating oil, temperature of the fresh charge and the oxygen content of the exhaust gas. It is also an established fact that knock or detonation sensors can be installed in an internal combustion engine which detect detonation and accordingly alter the ignition setting to elminate the detonation. The aquisition of these parameters and the necessary procedures to alter the ignition setting and/or the composition of the combustion charge do not necessarily guarantee the maintenance of the initial thermal efficiency during long time operation. Rather, on the contrary, due to uncontrolled foreign influences, the initial ignition setting is altered unfavorably during operation. In addition to this situation, if many parameters are sensed and utilized to obtain the ignition setting, the tuning of these parameters to each other can be complicated and time consuming. Furthermore, the existing methods which independently alter the ignition settings cannot take into account all the parameters which really influence the combustion process, i.e., the composition of the actual fuel, the deposits accumulated in the combustion chamber after a certain period of time, the inside temperature of the combustion chamber, and the instantaneous setting of the carburator, etc. OBJECTS AND SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method and apparatus for regulating the combustion process of an internal combustion engine, which will enable high thermal efficiency to be obtained in the engine, without having to sense and process a large number of such parameters and which is able to take into account uncontrolled external influences at the determination of the ignition setting. A further object of the invention is to provide a method and apparatus for governing the optimal ignition timing of extremely diluted and/or lean combustible mixtures of air, fuel, and exhaust gas in an internal combustion engine. Another object of the same invention is to provide a method and apparatus for the anticipated sensing of imminent knock and consequent regulation of the engine combustion process to prevent such undesired knock. A still further object of the invention is to realize in one arrangement all the above mentioned objects in a cost-efficient manner. The invention described herein is used to control the combustion process of an internal combustion engine which includes at least one cylinder having a closed top end and a piston which is translatable within the cylinder between top and bottom positions and which defines, with the closed end of the cylinder, a combustion chamber. During each combustion cycle, a combustion charge, i.e., a combustible gaseous mixture including fuel and air, within the combustion chamber, is progressively ignited, starting at a predetermined ignition initiation location in the combustion chamber, with the flame front expanding outward from the ignition initiation location throughout the cylinder. For example, one or more spark plugs may be used to initiate ignition of the charge at ignition initiation location in the combustion chamber. The invention includes a flame front detector disposed in the combustion chamber at a location F which is spaced from the ignition location to assume that most of the charge will have been ignited by the time the flame front reaches this sensor, at which time the piston is being moved toward its bottom position by the expanding charge. The invention also includes a piston sensor for indicating at least the direction of deviation of the instantaneous piston position, at the moment the flame front sensor, relative to a selected piston position K which defines a K-track defined by the piston from its top position to the K position. With the method and apparatus described herein, it is possible to obtain the most efficient ignition setting, producing optimum, or virtually optimum running conditions of an internal combustion engine, without having to sense and process a large number of parameters influencing the combustion process and the thermal efficiency necessary to produce the required ignition setting. It is sufficient to sense the arrival of the flame front at the predetermined F-location in the combustion chamber and to adjust the K-F coincidence with the arrival of the piston at the end of the K-track. With automatic ignition adjustment in this manner, uncontrolled foreign influences capable of altering the ignition setting can be taken to consideration. The method provides therefore a virtually variable alteration of the ignition setting in such a manner that, the approximate K-F coincidence exists. In this manner, all parameters of the internal combustion and the charge on which the combustion process is dependent, are taken into consideration, including parameters such as the composition of the fuel, the composition of the combustion air, the temperature of the combustion chamber, the influence of the combustion process due to deposits of residues in the combustion chamber and the like. This inventive method may also sense operating conditions indicating the danger of detonation before such detonation occurs, so that detonation or the risk of detonation from the beginning can be counteracted sooner than by the conventional methods known to this day, in such a manner that, if the risk of detonation actually occurs, it can be considerably reduced or even quickly counteracted. Preferably it can be provided for this purpose, that the arrival of the flame front of the flame caused by the spark plug is sensed in an area of the combustion chamber, in which the danger of knock causing self-ignition of the charge is particularly strong or strongest, and, if self ignition occurs, such self ignition occurs before the arrival of the flame front of the flame caused by said spark plug, so that in the occurrence of self-ignition, the flame front sensor placed at the F-location can respond before the arrival of the flame front of the flame caused by the spark plug and by such, generate a shift of the ignition timing point (ITP) which counteracts the risk of detonation during subsequent combustion cycles. It is of particular advantage, if the center (hearth) of self ignition is located, as close as possible to the flame front sensor, so that the flame front sensor (FFS) always detects the knock before the arrival of the flame front of the flame caused by the spark plug. To further assure reliable detection of knock, the flame front sensor is heated up to higher operating temperatures by the charge combustion than are the adjacent wall areas of the combustion chamber, so that this flame front sensor increases slightly the risk of self ignition of the charge and thereby can contribute to initiation of self ignition. Thereby it is also achievable, if the internal combustion engine comprises several cylinders whereby only one cylinder is equipped with the flame front sensor, that the self ignition of the charge starts primarily in this particular cylinder, the other cylinders therefore not requiring flame front sensors. In this case the flame front sensor is acting as a pre-knock sensor for the other cylinders. The internal combustion engine can consist of one or several cylinders, having one or several combustion chambers. If such an engine consists of several cylinders, it is normally sufficient to sense the arrival of the flame front at the F-location and to adjust the K-F coincidence in one combustion chamber only. The influencing variables on which the combustion process is dependent, have virtually identical values in each combustion chamber of an internal combustion engine and small differences between combustion chambers can be neglected. It is nevertheless also possible, in case that each cylinder of an internal combustion engine processes its own ignition system, independent of the other cylinders, to install a flame front sensor in each combustion chamber and to alter the ignition setting in each cylinder independently, according to the inventive system. Or, it is possible to separately check the K-F coincidence of each cylinder or of several groups of cylinders of an internal combustion engine, calculate the average value of the differences and utilize this value to alter the ignition setting of all the cylinders or of one or several groups of cylinders. Preferably, it may be provided for, that the K-F coincidence be exclusively adjusted by altering the ignition setting only and that no other parameters assist hereby. In many cases, it can also be favorable to enable even more improvements to be obtained, or to improve certain operating conditions, to regulate the K-F coincidence in at least one operating range and or upon the occurrence of certain operating conditions or situations, by altering, one or in combination, the composition of the charge, meaning that, then, not only the ignition setting is a regulating variable for the control of the K-F coincidence, but that as an additional correction variable, the modification of the composition of the combustion charge is utilized. This step can be provided for in the whole range of adjustment of the ignition setting, in only one or more selected adjustment ranges, or at one or both limits of the ignition setting adjustment range. For instance, it can be provided for that, in one predetermined ignition adjustment range only the ignition setting be altered to adjust the K-F coincidence, whereas in an adjustment range or ranges bordering one or both extremities of this ignition adjustment range, in addition to, or instead of, altering the ignition setting to adjust the K-F coincidence, the composition of the charge is modified to alter the speed of combustion of the charge in the combustion chamber, for example, by enrichening and or by leaning off the fuel in the air mixture, or by the controlled addition of exhaust gas to the fresh charge. (exhaust gas recirculation). The combustion speed of the charge is generally lower, the leaner the mixture is and is achieved either by increasing the portion of the air and or by adding exhaust gas to the fresh charge. The invention allows the adjustment of the ignition setting of an operating internal combustion engine, exclusively by altering the K-F coincidence, so that existing ignition distributors or other established systems to alter the ignition setting become unnecessary, whereby for the starting of the engine a favorable ignition timing point can be, if required, automatically adjusted. It is nevertheless also possible to continue utilizing existing distributors or other established sytems to obtain a rough setting of the ignition and to supplement this rough setting with a fine setting for regulating the K-F coincidence. It is often favorable to forsee that the regulation of the K-F coincidence is only realized in at least one operating range of the combustion engine and in the other operating ranges the regulation is put out of function, the ignition timing point of the charge in this or these other operating conditions being determined then only by a predetermined ignition timing gap. Thereby it is possible to provide in this or these operating ranges, in which the K-F coincidence is regulated the above-mentioned rough setting of the ignition timing point according to an ignition timing point map which is adjustable, or in several cases also constant--or, in certain cases, to provide in at least one operating range the ignition timing point adjustment only by regulation of the K-F coincidence. The rough adjustment of the ignition timing point according to a predetermined ignition timing point may nevertheless have the advantage that the fine regulation of the K-F coincidence is performed more rapidly. For particular advantage it can be foreseen, that at least in the idle range and the overrunning range of the internal combustion engine, and preferably also in a low part load range adjacent to the idle range, the K-F coincidence regulation is put out of function. It is also often particularly preferable to provide that the regulation of the K-F coincidence is put out of function at mean effective working pressures of the internal combustion engine, which are lower than approximately 1.5 bar. In many cases, it is sufficient if the length of the K-tract, at least in the complete load range of an internal combstion engine stays constant, which means, not adjusted in the load range. This constant value of the K-tract can be also considered of value for the idling range. It is then sufficient to establish this constant for a particular engine directly by the engine constructor. It is also possible, to incorporate provisions for manual adjustment of the K-track, to permit, for instance a repair workshop to adjust the length of this K-track. As the crank angle (rotational angle of the crankshaft) and also the rotational angle of the crankshaft is functionally related to the position of the piston, the K-track can also be indicated in crank or camshaft degrees. Other possibilities exist as well. One could therefore also determine when the piston has arrived at the end of the K-track by means of indicating engine crank--or camshaft angles, or by indicating the angle of any other crank driven component of the engine, so that such measurements need not be made directly on the piston. It is of particular advantage, if the K-track corresponds to relatively large crank angles. Preferably it can be foreseen, that the end of the K-track corresponds, at least at full load, to a crank angle of at least 15°, preferably at least 18°, after the top dead center position of the piston. In many cases it may also be useful to provide an automatic adjustment of the length of the K-track, dependent on at least one parameter of the engine and/or on the charge, preferably dependent on the engine revolutions and or on the position of the power control system, i.e., the carburator throttle valve--or fuel injection control rod position. It can, in many cases, therefore be useful to forsee, to facilitate the starting of an internal combustion engine, that for starting, the K-track length is set to another length than after successful start, so that therefore, in this case two different constant K-lengths are utilized (for the start and for the normal running operation). Or one can provide for the idle range a different length of the K-track than for the load range. It is also possible to provide for the possibility of automatic adjusting of the length of the K-track, continuously or in steps, dependent on at least one parameter of the internal combustion engine, and/or on the charge, preferably dependent on the engine revolutions, and/or on the load, and/or on the selected transmission ratio of the gearbox driven by the crankshaft be used. Also other parameters are conceivable. The adjustment of the length of the K-track (one could speak of the adjustment of the value of the K-track, or even simpler of the adjustment of the K-track) can in many cases be advantageously be utilized to reduce the emissions in one or several operating ranges of the internal combustion engine, where the exhaust gases contain a large pollutant emission, i.e., by retarding the ignition setting more than the setting where it would produce the optimum thermal efficiency for the engine. This is the case, in general, at one or several narrow operation ranges, i.e., in the idling range and/or in a low part load range. In this or these other operating ranges of the internal combustion engine, one can set the K-track to the requirements of possibly the optimum thermal efficiency of the engine. The invention permits high thermal efficiencies to be obtained and allows for high running safety as the ignition setting can no longer be disturbed by uncontrollable foreign effects, and represent a cost efficient solution. Optimum adaption of the system to desired operating conditions can be obtained. The engine can also be operated with very lean fuel--air mixtures, respectively with a fuel-air mixture heavily diluted with exhaust gases, which increases the burning efficiency of the charge. The arrival of the flame front at the F-location can be sensed in different manners. In a preferred embodiment, the arrival is sensed electrically by a sensor, which produce an ion current as the flame front reaches this sensor. Ideally, the flame front sensor will consist of two metallic electrodes connected across an electric voltage source. When the flame front reaches these electrodes, the gap between these electrodes becomes ionnized, resp. ions cross this electrode path and, due to the voltage between the electrodes, an ion current can be measured. Also other methods of sensing the arrival of the flame front are conceivable, i.e., by means of a temperature sensor, which responds nearly without inertia to temperature variations. It can be imagined, that such a temperature flame front sensor can be a temperature-dependent resistance or simply a thermo couple with virtually no inertia. The invention can be applied in several cases only to control the ignition timing in an anti-knock manner, provision being made that the flame front sensor produces only a displacement of the ignition timing point and/or a change in the composition of the charge, if it senses the arrival of the flame front before reaching a predetermined first crankangle, which is smaller than the second crankangles at which the flame front of the flame ignited by the spark plug reaches the flame front sensor, whereby the ignition timing point variation, generated by the flame front sensor, shifts the ignition point towards "later" and whereby under normal conditions the ignition timing point adjustment is done accordingly to a predetermined ignition timing point. The first crankangle can, for instance, be 10° after top dead center of the piston and the flame front sensor is then so positioned, that the flame front of the flame generated by the spark plug reaches the flame front sensor only at greater crank angles, for example 15° or more, after top dead center of the piston. This method of anti-knock control is, for instance, possible in such a manner, that the electric signal indicating the arrival of the flame front at the flame front sensor must pass an AND-gate, which, at each reaching of the first crankangle, is blocked during a larger crankangle, for example 300°, and then is opened again up to the next arrival of the first crankangle, so that only signals caused by self ignited portions of the charge can initiate adjustment of the spark timing, and only towards "later". As long as no trace knock occurs, the ignition timing is adjusted in conventional manner following an ignition timing point map and to this conventional adjustment, as long as the flame front detector senses knock causing self ignition, a shift of the ignition timing point towards "later" is overlayed. This said overlaying is cancelled as knock conditions disappear. The flame front sensor, which senses the arrival of the flame front in the combustion chamber at the F-location can preferably by positioned in the area of the combustion chamber which prevails in the top dead center position of the piston. When greater distances between the flame front sensor and the spark plug are desired or required, a recess in which the flame front sensor is positioned can be forseen in the piston sliding surface. (cylinder wall). Generally, it is especially useful to install the flame front sensor in such a manner, that the flame front only reaches it when at least 70% of the charge is already burnt, preferably when 70-90% of the charge is already burnt. It should preferably be provided for that, the F-track be greater than 1/2 the diameter of the piston sliding surface. Often, it is of advantage to provide that the arrival of the flame front at the F-location takes place only towards the end of the combustion process. The invention will be better understood and further objects and advantages thereof will become more apparent from the ensuing detailed description of the preferred embodiments taken in conjunction with the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows, in schematic presentation, a bottom view of an area of a cylinder head bordering the upper part of a combustion chamber of an externally ignited combustion engine, as well as a schematic diagram of a circuit for regulating the K-F coincidence. FIG. 1a shows an alternative arrangement of the flame-front sensor shown in FIG. 1. FIG. 2 shows a top view of the slotted disc of FIG. 1 connected to the camshaft. FIG. 3 shows a variation of the slotted disc. FIG. 4 is a cross-sectional view of a flame front detector, according to the invention. FIG. 5 is an enlarged view of a portion of FIG. 4. FIG. 6 is a partial, cross-sectional view of another embodiment of the flame front detector. FIG. 7 is a block diagram of another embodiment of a K-F coincidence regulating device. FIG. 7a shows an alternative circuit arrangement to FIG. 7. DESCRIPTION OF PREFERRED EMBODIMENTS FIG. 1 shows a cylinder head 10 of a cylinder having a piston (not shown) which is slidably disposed within the cylinder and defines, with the cylinder head 10, the cylinder combustion chamber. The cylinder head 10, includes an inlet valve 11, an exhaust valve 12 and a spark plug 13. The engine crankshaft (also not shown) related to this piston drives a camshaft 14 which actuates valves 11 and 12. A slotted disc 15 is securely fixed onto the camshaft 14. The disc 15 includes circular arcate slots 16 and 17, concentric to the rotational axis of the slotted disc, but at different radial distances. A short end portion of a flame front sensor 20, arranged in the cylinder head wall, protrudes a short distance into the combustion chamber in a position approximately diametrically opposite the spark plug 13 representing the F-location and contains two closely spaced free ending separate metal electrodes 21, which determine the F-location and are insulted from each other by a ceramic insulator 22 screwed into the cylinder head. This flame front sensor 20 is located near the inlet valve and connected via a resistor 18 to a constant voltage source 24. The resistor 18 is connected to an amplifier 25. The output of the amplifier 25 is connected via a threshold stage 26 to an impulse forming stage 27. Only when the current flowing through the resistor 18 exceeds a predetermined value, will the threshold stage 26 permit the output signal of the amplifier 25 to flow towards the impulse forming stage 27. The impulse forming stage 27 produces an impulse of constant level after each command of the step value stage 26, actuating a switch 29 to commonly turn on and off a first and a second light source 30 and 31, which could be a light-emitting diode, for instance. The light sources 30, 31 are disposed on one side of the disc 15 and two photo sensitive sensors 34, 35 are disposed on the opposite side of the disc 15 so that the light source 30 can illuminate the photo sensitive sensor 34 through the slot 16, and the light source 31 can illuminate the photo sensitive sensor 35 through the slot 17. The slot 16 ends approximately at a geometrical radius line 32 of the disc 15, at which point slot 17 begins in relation to the direction of rotation of disc 15. The photo sensitive sensors 34 and 35 are connected via signal amplifier and forming stages 40 and 41, respectively, to a servomotor 42, for example, a pneumatic or electric servomotor, which is capable of incrementally adjusting a spark distributor 43 for determining the spark timing and delivering ignition voltage to the spark plug 13. The servomotor 42 can alter the ignition setting of the distributor 43 incrementally in small steps, whereby if the sensor 34 is energized, the ignition timing point (ITP) is advanced by a small step, whereas each time when the sensor 35 is energized, the ITP of the ignition distributor 43 is shifted by a small step towards "later", by the servomotor 42. At each signal revolution of the slotted disc 15, corresponding to an operating cycle of this cylinder, such as adjustment of the ignition timing point of the ignition distributor 43 takes place by a predetermined small step, which can correspond to a crank angle (crankshaft rotational angle) of 1 to 2 degrees. In this particular example, the ITP of the spark distributor 43 can already be roughly adjusted to the instantaneous engine speed of the combustion engine by a centrifugal advance mechanism, in which case the servomotor 42 overlays to this centrifugal adjustment a fine adjustment of the ITP to regulate the K-F coincidence. The distributor 43 can supply all cylinders of the internal combustion engine with spark impulses in a known manner. But only the K-F coincidence of one single cylider which comprises the shown cylinder head 10, is directly regulated. If further cylinders are existing, said cylinders do not require flame front sensors 20, as their ignition adjustments are accordingly controlled by said distributor 43. The device shown in FIG. 1, regulates the K-F coincidence in such a way that the ITP of the spark plug 13 is continuously altered via the distributor 43 by the servomotor 42, in such a way that the flame front of the burning charge in the combustion chamber always reaches the flame front sensor 20 approximately when the radius line 32 of the slotted disc 15, passes by the two light sources 30, 31, indicated as dotted lines in FIG. 2. These two light sources 30, 31 are positioned in such a manner, that the passage of the radius line 32 by these two light sources 30, 31, takes place when the piston of the cylinder comprising cylinder head 10, has moved, during the combustion cycle, a predetermined distance (K-track) from its TDC. The ending point K of the K-track can correspond for instance to a crankangle of 18° (related to the top dead center of the piston). Naturally, this is only an example and one has to take various factors into consideration which will alter the K-track, such as the layout of the combustion chamber, the position of the flame front sensor and other influencing variables. To enable the K-track to be adjusted, both light sources 30, 31 are mounted on a support 39, swingable round a swing axis, which is coaxial to the rotation axis of the disc 15, which swing position is adjustable by hand or automatically in accordance with at least one parameter of the combustion engine and/or the charge, preferably in accordance with its power control device (e.g., throttle plate position), the manifold pressure, the mean effective pressure, the engine speed or the like. When the flame front of the burning charge in the combustion chamber arrives at the electrode gap of the flame front sensor 20, the voltage at electrodes 21 produces an ion current of such a value that the amplifier 25 produces an output signal greater than the threshold (minimum perceptible difference) of the threshold value stage, which is then transformed into an impulse by the impulse transformer 27 actuating the electrical, preferably electronic, switch 29, which switches on light sources 30, 31. If at this moment the piston has not yet arrived at the end of the K-track, the slot 17 is still under light source 31, which therefore energize the coordinated sensor 35, thereby a step towards "later" is generated via amplifier 41 and servomotor 42, shifting the ignition timing point of the distributor 43 by one step towards "later". In this particular case the flame front arrived at the flame front sensor too early, so that for regulating the K-F coincidence a small shift of the ITP towards "later" is done. The output signal of amplifier 41 which is also supplied to the switch 29 via a rectifier diode 44 and conductor 46 switches off switch 29 so that light source 30, 31 are switched off, thus preventing any further adjustments of the distributor 43. If during the following operating cycle the same event is repeated, the ITP of distributor 43 is shifted towards "later" by a further step. If, to the contrary, the flame front arrives at the flame front sensor 20, only after slot 16 has arrived under light source 30, then the switching on of the light sources 30, 31, generated by the flame front sensor 20, illuminates only sensor 34 by the light source 30. The sensor 34 then, via amplifier 40 and servomotor 42, triggers a shift of ITP of the distributor 43 by one step towards "earlier". Also the impulse produced by amplifier 40, via the conductor 46' having the diode 44', causes switching off of switch 29 and thereby turns off the light sources 30, 31 in this working cycle. This "K-F coincidence regulator" therefore causes, at each working cycle of the corresponding cylinder, an adjustment of the ITP of the spark distributor 43 by a predetermined small step towards "earlier" or "later". The above-identified K-F coincidence regulator does not include a slack area (dead zone), that is, a small area around the exact K-F coincidence, in which no adjustment of the ITP takes place, if in this area switching on of the switch 29 is triggered. This can be provided, for example, by providing a third slot or hole (perforation) in the slotted disc 15 and coordinating to this a third light source and a third photo sensitive detector, which third detector, upon being illuminated, triggers switching off of switch 29 without an associated shift of distributor 43. Such a disc 15' is shown in FIG. 3. Through the third hole 47 the radius lie 32 passes centrically and the two slots 16, 17 are positioned circumferentially at an angle from one another in the disc 15' in such a manner as to be located offset to the light sources 30, 31 if the third light source triggers the corresponding third photo sensitive detector through hole 47. Therefore, if at the time of the flame front arrival at the flame front detector 20, the hole 47 is positioned adjacent the third light source, switch 29 is immediately switched off, without the servomotor 42 having been triggered. At this operating cycle therefore no shift of the distributor takes place by the flame front sensor 20. However, a shift of the ITP will occur if, upon switch on of switch 29, the light source 30 or 31 excites the sensor 34 or 35, respectively. The aforementioned term "operating cycle" represents either the four strokes of a four stroke engine or the two strokes of a two stroke engine required for the charge to be changed and the combustion to be performed in the cylinder. The distributor 43 can, for example, correspond to a distributor as represented on page 734 of the Taschenbuch fur den Kraftfahrzeugingenieur ("Pocket book for the Passenger Car Engineer"), written by Buschmann and Koessler, 7th Edition, Deutsche Verlagsanstalt, Stuttgart, with the difference, that its distributor housing is not fixed but arranged rotationally around the longitudinal drive axis and is rotatable by means of the servomotor 42 so to regulate the K-F coincidence, so that the predetermined ITP map comprising the parameters of engine speed and manifold pressure controls the rough (coarse) setting and the K-F coincidence regulator controls the fine setting of the ITP of this distributor, according to FIG. 1. With modern electronic timing devices, for instance, digital ignition timing devices, the fine control (adjustment) for the K-F coincidence regulation of the ITP is also applicable without problems, for example, by phase shifting of the signal triggering the ignition coil. In FIGS. 4 and 5 an example of a flame front sensor 20 and its arrangement in the surrounding wall area 52 of the corresponding combustion chamber is shown in longitudinal section. The sensor 20 serves to sense an ion current generated by the arriving flame front in combination with a DC voltage applied to the metal electrodes 50, 51. The central electrode 50 is connected to the DC voltage and the electrode 51 is grounded. Electrode 50 is electrically insulated by an insulating pipe 53 from electrode 51. Both electrodes 50, 51 protrude some millimeters out of the wall 52 into the combustion chamber, so that these electrodes reach relatively high operating temperatures, which somewhat increase the danger of self ignition of the charge, so that the self ignition of the charge, causing knock, can be initiated, by one or both of the electrodes 50, 51. Therefore, in the case of each such self ignition, the induced ion current of sensor 20 appears earlier than it would by being triggered by the arrival of the flame front of the flame ignited by the spark plug 13. Consequently, upon the occurrence of self ignition or knocking, the K-F coincidence regulator shown in FIG. 1 receives a signal from the flame front sensor indicating early ignition, and therefore automatically shifts, by means of servomotor 42, the ITP of the distributor 43 towards "later", so that the ITP is very rapidly shifted towards "later" until this knocking ceases. Afterwards, the ITP is automatically again advanced by the K-F coincidence regulator and if again knock begins, then again automatic retard' of the ITP is realized until the combustion engine again reached operating conditions where the danger of knock does not prevail. Then normal governing of the K-F coincidence takes place until the appearance of an abnormal condition where again danger of knock is present. The flame front sensor 20, shown in FIG. 6, includes a metallic center electrode 50' shaped as a straight pin, which is electrically insulated by an insulating pipe 53 from the casing 54 of the flame front sensor 20 arranged in the wall 52. The electrode 50' is located in a rotationally symmetric recess 55 of approximately 3 to 5 mm diameter of the wall 52, the mass electrode being in this case the wall 52 itself. In the examples of flame front sensors according to FIGS. 4-6, a free end section of the insulating pipe 53 protrudes into the combustion chamber so that this free end section of said insulating pipe 53 can reach self-cleaning temperatures. A value of approximately 12 volts is then generally sufficient for the electrode voltage. Also these flame front sensors 20 are developed in such a manner that the operating temperatures of their electrodes 50, 51, 50', respectively, are so high that they can induce self ignition of the charge whenever it is likely that knock will occur. Preferably it can be provided that the temperature of at least one electrode 50, 51, 50', respectively, reaches values from approximately 400° to 800° C. under full load operation of the internal combustion engine, preferably approximately 600° to 700° C. The double bend of the central electrode 50 of the flame front sensor 20 represented in FIG. 5 increases the distance between the ends of the electrodes 50 and 51 to facilitate the access of the flame into the ion gap formed by the two electrodes 50, 51. The length of the ion gap may be for example 0.6 to 1.0 mm. An electronic K-F coincidence governor is shown in FIG. 7. It cooperates with a rotatable ring gear 60 which is operatively connected to the crankshaft whereby the ring gear 60 is rotated about its axis by the crankshaft so that each revolution of the ring gear 60 corresponds to one combustion cycle of an engine cylinder. A first sensor 63, for example an inductive sensor, is disposed adjacent the circumference of the ring gear 60 so that the passage of each single tooth of the ring gear 60, past the first sensor 63 causes it to trigger one counting impulse, which impulses can be counted in each of two counters 61, 62 in a parallel manner. A metallic pin 64, which is attached to the ring gear 60, cooperates with the further sensors 65, 66, 67 so as to induce, at each passage of the pin 64 in front of the sensors 65-67, a short trigger impulse from these sensors. Sensor 65 is located so that it is excited by the pin 64 and emits a brief pulse always at the moment when the piston of the combustion chamber containing the flame front sensor 20 reaches its top dead center position at the end of its compression stroke. The sensor 65 then starts the parallel counting of the counting impulses generated by sensor 63 by the counters 61, 62. When pin 64 passes sensor 66, sensor 66 emits an impulse which causes the counter 61 to cease counting immediately. The then prevailing content of the counter 61 is a measure for the length of the K-track, that is, the crank angle through which the crankshaft has travelled from the time of reaching the top dead center position of the piston to the end of the counting operation of the counter during the respective combustion cycle. Thus, the angular position of sensor 66 relative to the ring gear 60 describes the length of the K-track, and the length of the K-track is adjustable by shifting the sensor 66. The counting of the counting impulses delivered by sensor 63 to the second counter 62 is terminated at the corresponding combustion cycle by the signal generated by the flame arriving at the flame front sensor 20. The fourth sensor 67 produces a signal upon passage of pin 64 after the termination of counting by the counters 61, 62, which signal triggers the transfer of the counting content of the two counters 61, 62 to a comparator 68 and the two counters 61, 62 are then reset to zero. Thus, at each operating cycle of the combustion engine, the comparator 68 determines the difference of the two counting contents fed into it according to algebraic signal and absolute value and transfers this difference value to an average forming stage 69, which can be, for example a ring counter. The average forming state 69 accumulates and averages the content of a predetermined number of difference values, delivered by comparator 68, according to algebraic sign and absolute value, for example, the average value of the difference values measured consecutively during the last three combustion cycles of the respective cylinder. The measurements delivered by comparator 68 can also eventually be accumulated in the average stage 69 such that they fade with time. The output of the averaging stage 69 is directly a measure for the algebraic signal and dimension of the deviation of the arrival of the flame front at the flame front sensor 20 to the K-F coincidence and is fed directly, or after appropriate further processing, to the servomotor 42 to adjust the ignition timing point to govern the K-F coincidence. Since the output signal delivered from the average former 69 is dependent on the magnitude of the deviation of the K-F coincidence, the ignition timing point of the charge will be adjusted at each time by an increasing value as the average value of several consecutive deviations from the K-F coincidence is increasing. Hereby the task of the average value forming device 69 is to average purely random deviations of the arrival of the flame front at the flame front sensor 20, so to increase the accuracy of the K-F coincidence regulation if, under constant operating conditions, random deviations of the arrival of the flame front at the flame front sensor could appear. If one deletes the average value former 69 from FIG. 7, which also is conceivable, then the ignition timing point can upon every adjustment be shifted by a bigger value, the bigger the deviation of the arrival of the flame front at the flame front sensor 20 to the K-F coincidence is. Such random deviations of the arrival of the flame front at the flame front sensor at constant operation conditions may especially appear when there is an unfavorable design of the combustion chamber. To reduce the influence of such hazardous deviations, other methods can also be foreseen additionally or alone. In many cases it can be preferably provided that an adjustment of the ignition timing point is only realized, if the detected deviation of the arrival of the flame front at the flame front sensor to the K-F coincidence does not change its algebraic sign during a predetermined number of consecutive measurements of the arrival of the flame front at the F-location, for example, during two consecutive measurements. This can be realized, for example, by the following modification of the regulating device shown in FIG. 7. Instead of the average forming stage 69, an AND gate 70 is inserted as shown in FIG. 7a and to the comparator 68 an algebraic sign storage and comparator component 71 is connected, in which the algebraic signs of the last m difference values formed by the comparator 68 are stored and compared, and which opens the AND gate 70 opens only if the stored algebraic signs 71 are same, whereby m may be, for example, 2 or 3. As long as the stored algebraic signs in the component 71 are not identical, no adjustment of the ignition timing point is done by the K-F coincidence regulating device. It can also be provided that the average value former 69 is retained and the AND gate 70 is connected to the output of 69 so that the AND gate 70 prohibits or permits the output of the average value by the component 71. Instead of adjusting the length of the K-track by adjusting the sensor 66 (FIG. 7) or by turning the disc 39 (FIG. 1), it can be provided that the K-track length is adjusted in that the adjusting components contain a time delaying component which delays the arrival of the signal indicating the arrival of the flame front at the flame front sensor. Such a time delay component 73 is shown by dash-dotted lines in FIG. 1. Its time delay is, for example, Dt/n, where Dt is a steady or incrementally variable time span, adjustable by hand or automatically in dependence on at least one operating parameter of the combustion engine, n representing the engine speed. The larger Dt/n, the longer is the K-track. To enable the flame front sensor 20 to detect knock induced by self ignition, immediately upon occurrence of beginning of knock, it can provided in a preferred embodiment, that the flame front sensor 20' is disposed far from the exhaust valve 12, near to the circumferential half of the inlet valve plate of the inlet valve 11 facing away from the exhaust valve 12. Such a disposition of a flame front sensor 20 is shown in FIG. 1a at 20'. Hereby the flame front sensor is located in a relatively "cold" area of the combustion chamber in which normally knock occurs preferentially. The foregoing relates to preferred exemplary embodiments of the invention, it being understood that other embodiments and variants thereof are possible within the spirit and scope of the invention, the latter being defined by the appended claims.
Method and apparatus for controlling the combustion process of an internal combustion engine having at least one cylinder and an ignition device for initiating ignition of a combustible charge, whereby: (1) the moment of ignition of the charge at a position F in the combustion chamber is sensed, the position F being spaced from the ignition device so that the flame front of the flame initiated by the ignition device can only arrive at the position F after a predominant portion of the charge has been burnt; (2) at least the direction of a deviation of the piston moving within the cylinder from a selected piston position K is sensed at the moment of ignition at the position F; and (3) the ignition timing and/or composition of the charge is automatically regulated in accordance with at least the sensed piston deviation to achieve approximate F-K coincidence.
5
CROSS REFERENCE TO RELATED APPLICATION This application claims the benefit of U.S. Provisional Application No. 60/003,265 filed Aug. 11, 1995. BACKGROUND OF THE INVENTION The present invention relates to a carpet extractor and more particularly to a floating powered brush assembly for use with an upright extractor (of the type taught in co-owned U.S. Pat. No. 5,406,673) having powered floor cleaning brushes. Heretofore carpet extractors having powered brushes to assist scrubbing of the surface being cleaned have generally affixed the powered brush and/or brushes to the main body of the machine in such a way that, except for the rotary motion of the brush, the brush assembly did not move relative to the main body. Thus the rotary action of the powered brush tends to lift the liquid suction nozzle upward and away from the surface being cleaned resulting in lost efficiency of the system as a whole. BRIEF DESCRIPTION OF THE INVENTION The herein invention overcomes the above stated disadvantage of prior art extractors by disclosing a novel, free floating, powered, brush assembly and associated fluid supply system whereby the brush assembly is free to float atop the surface being cleaned in such a way that the brush assembly supports none of the extractor's weight nor imparts any forces to the machine that would otherwise tend to lift the liquid recovery suction nozzle upward from the surface being cleaned. The present invention teaches a floating brush support system particularly useful for supporting a multiplicity of laterally disposed cup-like scrubbing brushes rotatable about, generally parallel, vertically aligned, axis of rotation. The brush assembly generally comprises an elongate brush support beam having integrally molded, spaced apart, vertically aligned cylindrical bearings each receiving therein a vertically directed axle shaft of an associated rotary scrubbing brush. The rotary brushes generally comprise a spur gear configuration having tufts of brush bristles retained within each gear tooth and directed axially downward toward the surface being cleaned. The spur gear configurations, of each rotary brush, intermesh with the adjacent rotary brush thereby creating a gear train such that rotating any one rotary brush causes the entire gear train to rotate thereby powering all brushes with one driving brush. The intermeshing of the brush gear teeth and their associated brush bristles assures that no unbrushed area will be present between adjacent brushes. The axial thickness of each gear tooth includes an upper and lower profile. The upper profile provides the tooth involute that engages the tooth involute of the adjacent gear brush. The lower profile is inwardly offset from the upper profile to allow circumferential expansion (or bulging) of the profile upon insertion of the brush bristles that otherwise may cause binding or interference between intermeshing gear teeth. A gear brush guard, affixed to the gear support beam, surrounds the periphery of all brushes and is provided with an internally directed flange at the bottom of the guard sidewall extending inward beyond the outer locus of the gear teeth thereby restricting each gear brush within its associated cylindrical bearing on the support beam. Preferably four outwardly directed tangs, two on either side of the peripheral brush guard, engage vertically disposed guide slots in the brush assembly cavity of the extractor base module thereby permitting the brush assembly to translate or float vertically while retaining the brush assembly therein. To assist and guide the brush assembly as it floats vertically, a vertically directed flange is integrally molded onto the brush support beam, one at each end, which slidingly engage vertically disposed tracks or slots integrally molded into the end walls of the brush assembly cavity. None of the machine's weight is supported by the floating brush assembly. Generous tolerances between all moving parts namely: between the brush axles and cylindrical bearings, between the lower gear tooth surface and the brush guard peripheral flange, and the support beam vertical guide flanges and guide slots are provided such that the brush assembly may float in skewed positions and that the gear brush axle shafts may slightly tilt omnidirectionally from the vertical thereby permitting the scrubbing gear brushes to follow and remain engaged with any unevenness of the surface being scrubbed or to automatically adjust for carpet height The brush assembly further comprises a unique "snap together" structure for ease of assembly on a typical mass production assembly line. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a perspective view of an upright carpet extractor base module incorporating the present invention. FIG. 2 is a left side elevational view of the base module, as seen in FIG. 1, having the forward portion thereof cut away to illustrate the general positioning of the brush assembly therein. FIG. 3 illustrates the forward portion of the base module, illustrated in FIG. 1, having the top cover portion removed. FIG. 4 is an exploded view illustrating the basic subassemblies which form the present invention. FIG. 5 is an exploded view of the brush assembly seen in FIG. 4. FIG. 6 presents a sectional view taken along line 6--6 in FIG. 3 showing the brush assembly in its lowest position. FIG. 6A presents a sectional view taken along line 6--6 in FIG. 3 showing the brush assembly in its uppermost position. FIG. 7 is a bottom view as seen along line 7--7 in FIG. 4. FIG. 8 is a sectional view taken along line 8--8 in FIG. 6. FIG. 9 is a sectional view as taken along line 9--9 in FIG. 3 with the brushes removed. FIG. 10 is a sectional view taken along line 10--10 in FIG. 9. FIG. 11 is a sectional view taken along line 11--11 in FIG. 9. FIG. 12 is a sectional view taken along line 12--12 in FIG. 4 with the brushes shown in phantom. FIG. 13 is a perspective view of one gear brush with all but one of the brush bristle bundles removed. FIG. 14 is a bottom view of the gear brush illustrated in FIG. 13 with all but one of the brush bristle bundles removed. FIG. 15 is a cross-sectional view taken along line 15--15 in FIG. 14 with all but one of the brush bristle bundles removed. FIG. 16 is an elevational view taken along line 16--16 in FIG. 7. FIG. 17 is an elevational view taken along line 17--17 in FIG. 7. DETAILED DESCRIPTION OF THE INVENTION Referring to FIG. 1, the present invention relates to a base module 10 for an upright carpet extractor. The upper portion of a typical upright carpet extractor suitable for use in combination with the herein described base module 10 may be found in co-owned U.S. Pat. No. 5,406,673 issued on Apr. 18, 1995, titled "Tank Carry Handle and Securement Latch", the contents of which are included herein by reference. Base module 10 comprises a lower housing 12 and an upper housing 14 which generally separate along parting line 13. Suction nozzle 16 and suction inlet 18 are part of the upper housing 14 similar to the suction nozzle structure as taught in the above referenced co-owned patent. As principally illustrated in FIGS. 2, 3, and 4, lower housing 12 has suspended therein a floating carpet scrubbing brush assembly 20. FIGS. 3 and 4 illustrate the forward portion of lower housing 12 with the upper housing, including the suction nozzle 16, removed for clarity. The brush assembly may be powered by an air driven turbine 15, or any other suitable motive power means typically used in the industry, through a suitable gear drive train or transmission 54. A suitable air turbine driven gear train is taught in co-owned U.S. Pat. No. 5,443,362 issued on Aug. 22, 1995 and titled "Air Turbine". Turning now to FIGS. 5 and 6, brush assembly 20 comprises brush support beam 22 having five spaced apart, integrally molded, cylindrical bearings 24A, 24B, 24C, 24D and 24E. Rotatingly received within bearings 24 are axial shafts 26A, 26B, 26C, 26D and 26E of gear brushes 25A, 25B, 25C, 25D and 25E. It is to be noted that the axial shafts of brush gears 25C and 25E include extensions 28 and 29, respectfully, for purposes to be described below. During manufacture of brush assembly 20, the gear brush axial shafts 26 are first inserted into the appropriate bearing 24 and with gear brushes 25 in their uppermost position, with gear teeth 78 intermeshed, gear guards 32A and 32B are attached to support beam 22, as described below, thereby forming brush assembly 20, as illustrated in FIG. 4. Once assembled the peripheral lips 33A and 33B, on each gear guard 32A and 32B respectively, extend inwardly beyond the lower portion 84 (see FIG. 13) of gear teeth 78 thereby surrounding the row of rotary brushes and retaining each gear brush within the confines of the surrounding gear guards. Thus each brush may float vertically, with respect to support beam 22, limited in its uppermost travel by abutment of brush 25 with the lower portion of bearing 24 and limited in its lowermost travel by abutment of teeth 78 with lips 33 of gear guards 32. Also by providing a loose fit between the gear brush axial shaft 26 and bearing 24 each brush 25 may also tilt slightly with respect to the vertical axis. Gear guards 32A and 32B are identical in construction so as to be interchangeable on either side of brush support beam 22. To facilitate "snap together" assembly of each gear guard to the brush support beam, each gear guard 32 is provided with three integrally formed, horizontally extending, locking tabs 34, as best seen on gear guard 32B in FIG. 5, extending parallel to and below the top cover plates 36A and 36B of gear guards 32A and 32B. Further each gear guard (32A and 32B) is provided guide and alignment openings 38 for receipt therein (upon assembling the brush assembly) of extended tabs 39 of brush support beam 22. As the gear guards are brought together about brush support beam 22 and its associated gear brushes 25, tangs 34, on both gear guards 32A and 32B, slide under extended tabs 39, of brush support beam 22, engaging slots 41 thereby locking gear guards 32A and 32B to brush support beam 22 as illustrated in FIGS. 11 and 12. It is to be noted that when assembled, extended tangs 39 are sandwiched between the gear guard top cover plate 36A and 36B and its associated tang 34, as seen in FIG. 12, thereby providing lateral stability to the gear guards. Integral to and extending upward from the opposite lateral ends of brush support beam 22 are "T" shaped rails 42 and 43. T-rails 42 and 43 are slidably received within vertical guide slots 46 and 47 integrally molded into lower base module housing 12, as best seen in FIGS. 3, 9, and 10, whereby brush assembly 20 may freely move or float in the vertical direction within the brush assembly cavity 48 of housing 12. During assembly of base module 10, brush assembly 20 is inserted vertically into cavity 48 with T-rails 42 and 43 slidably engaging guide slots 46 and 47 respectfully. As brush assembly 20 is inserted into cavity 48, tabs 51 on gear guards 32A and 32B snap into vertically elongated openings 53 and grooves 57 respectively of housing 12. As illustrated in FIGS. 2, 3, 9, 11, 16, and 17, outwardly projecting tangs 51 from gear guard 32A slidingly engage vertical slots 53 of housing 12 and tangs 51, projecting from gear guard 32B, slidingly engage grooves 57 thereby floatingly retaining brush assembly 20 within cavity 48. Gear brush 25C and 25E (see FIG. 5) are provided with axle shaft extensions 28 and 29, respectively, having a square lateral cross-section. Axle shaft 28 is slidably received within drive gear 52 contained within gear box 54 as illustrated in FIG. 6. Gear 52 is preferably powered by air turbine 15 through an appropriate gear train, such as that disclosed in co-owned U.S. Pat. No. 5,443,362 identified above and incorporated herein by reference. As brush assembly 20 moves vertically, with respect to lower housing 12, axle shaft 28 is slidably received within drive gear 52 as illustrated in FIG. 6A. Gear brush rotation indicator 44 is fixedly attached to shaft extension 29 of gear brush 25E and extends upward through opening 56 in the top 45 of brush cavity 48 of lower housing 12 so as to be visible to the operator through clear lens 19 of upper housing 14 as seen in FIG. 1. Referring to FIGS. 2, 9, 16, and 17, brush assembly 20 floats freely within cavity 48 of lower housing 12. The lower limit of brush assembly 20, as illustrated in FIG. 9, is controlled by tangs 51 which engage the bottom ledge 49 and 50 of slots 53 and grooves 57. The upper travel of brush assembly 20 is limited by abutment of the brush assembly against the top portion 45 of cavity 48. Further, as brush assembly 20 floats vertically within cavity 48 T-rails 42 and 43 slidingly engaging slots 46 and 47 respectively of lower housing 12 thereby maintaining alignment of brush assembly 20 within cavity 48 and transferring the forces applied to brush assembly 20, by movement of extractor 10 forward and rearward, to lower housing 12. T-rails 42 and 43 are configured so as to permit brush assembly 20 to assume a laterally skewed or canted (one end higher than the other) relationship with respect to cavity 48 as it moves vertically. Referring to FIGS. 1 and 2, base module 10 is principally supported upon rear wheels 17 and suction inlet 18 of suction nozzle 16. Thus brush assembly 20, by reason of the above described floating structure, is suspended within cavity 48 of lower housing 12 whereby brush assembly 20 bears none of the extractor weight and permits brushes 25 to "float" atop the surface being cleaned as they rotate. The weight of the extractor is supported by rear wheels 17 and suction inlet 18. With the extractor center of gravity forward of rear wheels 17 and the floating characteristic of brush assembly 20, suction inlet 18 will be in contact with the surface being cleaned thereby assuring maximum recovery of dispensed cleaning solution. The structure described hereinabove is preferably constructed with generous and loose tolerances that permit brush assembly 20 as a unit and the individual gear brushes 25 to separately move in other than vertical straight lines and thereby operate in skewed positions as may be dictated by the unevenness of the surface being cleaned. Cleaning solution supply manifold 60 is positioned above brush assembly 20 and affixed to lower housing 12, as illustrated in FIGS. 3, 6, and 7. Liquid cleaning solution is supplied to nipple 62 on manifold 60 by way of a flexible tube such as, for example, illustrated in co-owned U.S. Pat. No. 5,406,673. Cleaning solution flows throughout manifold channel 64 to discharge orifices 66A, 66B, 66C, 66D and 66E in the bottom thereof as shown in FIGS. 7 and 8. Brush support beam 22 includes a laterally extending trough-like floor 68, as best seen in FIGS. 9 and 12, separated into five zones or troughs 71A, 71B, 71C, 71D, and 71E by walls 72A, 72B, 72C, 72D, 72E, and 72F as best illustrated in FIG. 5. As can be seen in FIGS. 6 and 6A, liquid cleaning solution cascadingly flows, by gravity, from manifold orifice 66A into trough 71A, from orifice 66B into trough 71B, from orifice 66C into trough 71C, from orifice 66D into trough 71D and from orifice 66E into trough 71E. In the configuration as illustrated in FIGS. 6 and 6A, no fluid flows into trough 71C'. The purpose of trough 71C' is to provide symmetry to support beam 22 such that beam 22 requires no specific orientation during assembly. Beam 22 may be positioned as shown in the figures or rotated 180°. When rotated 180° trough 71C' then receives fluid from orifice 66C and supplies brush 25C through conduit 74C' with trough 71C becoming non-functional. Cleaning solution received in troughs 71A, 71B, 71C, 71D, and 71E flows through fluid supply conduits 74A, 74B, 74C, 74D, and 74E, respectively, and into center cups 77A, 77B, 77C, 77D, and 77E of brushes 25A, 25B, 25C, 25D, and 25E as best seen in FIG. 6. Once deposited within brush cup 25, the cleaning solution flows outward toward the surface being cleaned through openings 81A, 81B, 81C, 81D, and 81E in the bottom of brush cups 77A, 77B, 77C, 77D, and 77E, respectively. It is preferred that brush bristles 86 be of a soft texture such that when rotating and in contact with the surface being cleaned the brush bristles bend whereby the bottom of brush cup 77 is in contact with the surface being cleaned. Thus the cleaning solution being dispensed through openings 81 flows directly onto the surface being cleaned. A circumferential rim or edge 88 is provided about the bottom periphery of cup 77 to prevent the centrifuging of cleaning solution radially outward. The preferred operational speed of brushes 25 has been found to be between 500 to 900 RPM for a brush of approximately two inches in diameter. For uniform distribution of cleaning solution on carpeted or other surfaces being cleaned, it is desirable that each brush 25A, 25B, 25C, 25D and 25E receive a steady and equal flow rate of cleaning solution. Therefore, the size of orifices 66A, 66B, 66C, 66D, and 66E are preferably determined by empirical testing. It has been found, for the manifold configuration as illustrated herein, that orifice 66B required a slightly larger diameter than that of the other four which are of equal size. In order to minimize the lead-time required to stop the flow of cleaning solution to the brushes, conduits 74A, 74B, 74C, 74D, and 74E are oversized so as to be more than adequate to convey the flow rate being dispensed by orifices 66 into brush cups 77 thereby assuring that dispensed cleaning solution immediately flows through conduits 74 into brush cups 77 and exits through openings 81 onto the surface being cleaned and does not collect or back-up in troughs 71 A, 71B, 71C, 71D, or 71E. Referring to FIGS. 5, 13, 14, and 15, gear brushes 25C and 25E are identical to brushes 25A, 25B, and 25D in all respects except that brushes 25A, 25B, and 25D do not include key shaft 28 or 29. It is necessary for brush 25C to have extended key shaft 28 as it is the preferred, power driven gear brush which drives the gear brush train. Gear brush 25E includes key shaft 29 so that gear brush rotation indicator 44 may be placed thereon to provide visual verification to the operator that the gear brushes are, in fact, rotating during use. Each gear brush 25 is basically configured as a spur gear preferably having ten teeth 78 which intermesh, as seen in FIGS. 5, 6, and 6A such that when center gear brush 25C rotates all other gear brushes rotate accordingly. The center hub of gear brushes 25 forms a hollow downwardly projecting cup 77 having a multiplicity of openings 81 circumscribing the bottom thereof. Each gear tooth 78 has an upper tooth profile 82 and a lower profile 84 which approximates upper profile 82. However, profile 84 is smaller in size and slightly indented from profile 82, as seen in FIGS. 13, 14, and 15, forming an offset 83. Only profile 82 of gear tooth 78 is intended to drivingly engage the corresponding tooth profile of the adjacent gear brush. Each gear tooth 78 has a blind bore 79, extending to offset 83, into which bristle bundles 86 are compressively inserted. Upon insertion of bristle bundles 86 into blind bores 79 lower profile 84 of tooth 78 may be expected to expand or bulge in the area of bore 79. Thus the offset 83 is sufficiently sized to prevent the bulge, in lower profile 84, from extending beyond the upper profile 82 and thus assuring that the gear teeth of adjacent gear brushes, upon intermeshing, do not bind or otherwise interfere with one another. Alternatively a downwardly extending circular (or any other convenient configuration) boss may be used to receive the bristle bundles and perform the function of alleviating gear binding. The invention has been described with reference to the preferred embodiment having five rotary brushes. However, obvious modifications and alterations (including increasing or decreasing the number of brushes) will occur to others upon a reading and understanding of the specification. It is also to be understood that although the preferred embodiment disclosed hereinabove teaches rotary brushes having intermeshing spur gear configurations it is not to be considered outside the scope of our invention to use other types of brushes, such as a horizontal roll brush, and alternative drive means such as a belt drive etc. It is our intention to include all such modifications, alterations and equivalents in so far as they come within the scope of the appended claims or the equivalents thereof.
Floor care apparatus is disclosed wherein a powered brush assembly having a multiplicity of rotary brushes is suspended within the apparatus such that the brush assembly floats freely upon the surface being cleaned without supporting any of the machine's weight. The rotary brushes are generally configured as spur gears and function in a gear train wherein one brush drives all other gear brushes in the system. Axially projecting brush bristles are embedded in each gear tooth such that there is no unbrushed area between adjacent brushes in the brush line. The portion of the gear tooth wherein the bristles are embedded includes a recessed profile to allow for circumferential expansion of the tooth, upon insertion of the brush bristles, thereby preventing gear tooth interference. The brush assembly is particularly suitable for hot water carpet extractors of the upright design.
0
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The present application is a U.S. Divisional application of co-pending U.S. patent application Ser. No. 15/249,224, entitled “REFRIGERATION SYSTEM INCLUDING MICRO COMPRESSOR-EXPANDER THERMAL UNITS,” filed Aug. 26, 2016 (docket number 3039-001-03); which application claims priority benefit from U.S. Provisional Patent Application No. 62/210,367, entitled “WORK MECHANISMS FOR DIRECTLY-COUPLED MICRO COMPRESSOR-EXPANDER THERMAL UNITS,” filed Aug. 26, 2015 (docket number 3039-001-02); each of which, to the extent not inconsistent with the disclosure herein, is incorporated herein by reference. BACKGROUND [0002] Refrigeration and liquefaction cycles with gas as the working fluid and sometimes also the process gas have been known since about 1900 and are well described in the technical literature. Essentially all of the these cycles operate on the principle of compressing a working gas, transferring the heat of compression to a heat sink, cooling the gas in a recuperative or regenerative heat exchanger, further cooling of the gas via either isenthalpic or isentropic expansion, transferring a thermal load into the working gas from a heat source, warming the lower pressure gas back to near the temperature of the compressor, and repeating the cycle. In cycles such as the Linde cycle, the cooled high-pressure gas is expanded isenthalphically in a Joule-Thomson valve with no work recovery. Cycles with no work recovery generally have low thermodynamic efficiency relative to the minimum work required to pump heat from a colder source to a warmer heat sink. The primary reason for such low efficiency is a fundamental limitation of poor heat transfer during rapid compression of a gas; rather than being isothermal, the process is adiabatic or nearly so via polytropic compression. This inefficiency causes significantly more work input per unit mass flow than the ideal isothermal process. Without recovery of any of this work input during a refrigeration cycle, the ratio of the cooling power to the rate of work input is much lower than the ideal ratio, i.e., low relative thermodynamic efficiency (e.g., a few percent out of 100%). [0003] To improve refrigerator efficiency, gas expanders were invented whereby precooled high-pressure working gas is expanded isentropically from higher pressure to lower pressure with corresponding work production plus larger cooling effect. In refrigeration cycles that recover work of expansion to offset some input work of compression, the thermodynamic efficiency increases. Tagauchi et al. in U.S. Pat. No. 5,737,924 and Saho et al. in U.S. Pat. No. 5,152,147 describe use of regeneration to help recover some of the thermal energy of expansion of a portion of the working gas stream. Kolbinger describes an assembly of two rotary engines to form a compressor-expander with no discussion of recovery of work in U.S. Pat. No. 5,309,716. An electromagnetic apparatus to produce linear motion in a macro-structure device is described by Denne in U.S. Pat. No. 6,462,439, and a micro electro-mechanical system for providing cooling with compression and expansion spaces separated by a regenerator in a Stirling cycle without direct work recovery is described by Tsai et al. in U.S. Pat. No. 6,272,866. An array of refrigeration elements is disclosed by Reid et al., in U.S. Pat. No. 6,332,323. The refrigeration elements are combined to form a highly efficient active gas regenerative refrigerator. Refrigeration elements configured into an appropriate array of dual opposing thermal regenerators in an active regenerative refrigerator simultaneously enable the feature to alternatively provide active heating or cooling to reciprocating heat transfer fluid that flows over the outside surfaces of the refrigeration elements. The active heating or cooling in the opposite ends of small hermetic refrigeration elements can be caused by driving a sealed piston back and forth in each refrigeration element. The drive mechanisms contemplated in the '323 patent are by electromagnetic, pneumatic, or other means, but few details are given. The array of refrigeration elements is configured to enable reciprocating heat transfer fluid motion, as in conventional passive regenerators in regenerative cycle refrigerators such as the Stirling, Gifford McMahon, or pulse-tube cryocoolers, but in active regenerative refrigerator, the heat transfer fluid is separate from the working fluid, and the heat transfer fluid is not compressed or expanded during its cycle, other than as required for flow through the refrigeration element array and external heat exchanger. [0004] A small proof-of-concept active gas regenerative refrigerator was successfully built and initially tested with the support of a NASA Phase I small business innovation research SBIR award (J. A. Barclay, M. A. Barclay, W. Jakobsen, and M. P. Skrzypkowski, NASA SBIR Phase I Final Report, 2004; “Active Gas Regenerative Liquefier”; Contract No. NNJ04JC25C). Approximately 200 identical small stainless steel tubes were assembled into a rectangular array of tubes, each with a micro-regenerator and a common pressure wave means for all tubes in parallel. Initial results from the first lab prototype proved the active end of the tubes did heat and cool upon compression or expansion, respectively, and that the active gas regenerative concept was valid. SUMMARY [0005] Embodiments relate to methods and apparatuses for work input with simultaneous work recovery in a refrigeration cycle by nearly isothermal polytropic compression and synchronous nearly isothermal polytropic expansion of a working gas. Embodiments of the invention relate to a basic thermal unit of an efficient refrigerator and more particularly to active gas regenerative refrigerators utilizing an array of directly coupled micro compressor-expander units (MCEUs) with electromagnetic or pneumatic mechanisms for producing linear reciprocating motion of a piston to cause simultaneous heating or cooling by compression and expansion of a working gas within the basic thermal unit. Embodiments generally relate to fabrication of apparatuses and methods to enable work input into each micro gas compressor region coupled with simultaneous work recovery from the micro gas expander region. The combined effect of a high-performance regenerator array of micro compressor-expander units creates an efficient active gas regenerative refrigeration cycle for transferring heat from a colder thermal source to a hotter thermal sink for numerous refrigeration applications including liquefying natural gas, hydrogen, helium or other gases. [0006] Various embodiments provide work recovery of compression of an equal amount of working gas on one end of a MCEU tube by a common drive piston by simultaneous expansion of an equal amount of working gas on the opposite end of the common drive piston. The net driving force to move the piston alternatively inside the MCEU tube is provided by arrangements of permanent magnets and drive coils, in one embodiment of the invention. [0007] According to an embodiment, the length of thermally active sections at each end of a MCEU remains constant by using radial compression and expansion of a helium (He) working gas. This overcomes limitations of previous designs that used bellows or axial movement of the working gas with changes in the geometry of thermally active regions of the MCEU during its operation. [0008] According to an embodiment, radial motion of helium gas keeps a mass of He working gas constant in each thermally active section during the MCEU cycle. This overcomes one of the disadvantages of the NASA SBIR proof-of-principle prototype referenced above, of having different thermal mass in the thermally active sections at opposite ends of a MCEU by moving more or less working helium gas into or out of each MCEU during compression and expansion steps, respectively. [0009] According to an embodiment, the Biot number of a He working gas and tube walls of a MCEU (e.g. 0.125″ outer diameter Al alloy 2024 T6 tubes with 0.003″ wall) is ˜10 −3 , so tube walls in thermally active sections of the MCEU change temperature almost synchronously with the He working gas during a nominal 1 Hz cycle. The tube walls become part of the active thermal mass of each MCEU during an active gas regenerative refrigeration cycle. [0010] According to an embodiment, a drive piston of a MCEU has two or more sets of small opposing Nd 2 Fe 14 B magnets that create two or more concentrated transverse magnetic flux regions perpendicular to the axis of a center section of the MCEU tube. The MCEU also includes a thin, electrically-energizable coil around the outside of the center section of the MCEU. This arrangement significantly increases the Lorenz force on the drive piston from a magnetic field generated by the coil. [0011] According to an embodiment, a piston of a MCEU has two or more sets of small opposing Nd 2 Fe 14 B magnets that create two or more concentrated transverse magnetic flux regions perpendicular to the axis of a center section of the MCEU tube. The MCEU also includes a thin, annular, cylindrically-shaped permanent magnet array which is closely fitted with low-friction seals inside a hermetic tubular enclosure around the center section of the MCEU. This annular permanent magnet array is pneumatically driven back and forth by pressurized gases such as N 2 or H e , alternatively supplied to drive chambers defined in part by the tubular enclosure, via small tubes from a separate gas-supply subsystem. The transverse flux of the permanent magnets within the drive piston couples strongly with the cylindrically-shaped permanent magnet array. The strong magnetic flux coupling between the opposing magnets in the annular drive array and the magnets of the drive piston cause the drive piston to reciprocally move with the annular permanent magnet array, which simultaneously compresses and expands the working gas at respective ends of the piston during MCEU operation. [0012] According to an embodiment, a hoop stress of thin-walled tubes of a MCEU array during maximum compression of a He working gas is only about ½ of the yield strength of MCEU tube materials such as Al 2024-T6. This enables good dimensional stability and good sealing in the MCEU. [0013] According to an embodiment, a MCEU design enables work recovery from expansion of working gas at one end of the MCEU to offset work input to compress the working gas on an opposite end of the MCEU. [0014] According to an embodiment, a magnetic drive is provided, including a hermetic pneumatic shell containing thin, cylindrical annular permanent magnets around the outer shell wall of a center section of a MCEU tube. The tube contains two or more sets of opposing permanent magnets in an axially moveable compressor/expander piston assembly within the MCEU, which increases the transverse magnetic flux and thereby increases the magnetic coupling between the permanent magnets in the piston and those in the pneumatic drive. [0015] According to an embodiment, the work required for a cycle of a MCEU array is distributed over a wide range of temperatures near the operating temperature of each MCEU of the array, rather than input in a lumped fashion as through a compressor in most conventional gas cycle refrigerators and liquefiers. [0016] According to an embodiment, electronic control of each MCEU of an array is provided, so the performance of an overall active regenerator that includes the array of MCEUs can be fine-tuned during cool-down, to permit compensation for variations in thermal loads from a process stream, to accommodate o-p conversion for hydrogen, and to compensate for performance degradation during long term operation. The hermetic nature of each MCEU provides highly reliable operation. [0017] According to an embodiment, entropy changes required for heat flows in a dual-regenerator design of an active gas regenerative refrigerator (AGRR) come from simultaneous compression and expansion of working gas in each MCEU of an array. Heat flow through the dual regenerators on opposite thermally active ends of the array of MCEUs comes from the coupling of individual MCEUs of the array via a reciprocating flow of heat transfer fluid. The thermodynamic cycle of each MCEU is distinct, consisting of a polytropic compression and associated temperature increase, heat transfer to the heat transfer fluid with a corresponding small temperature and pressure decrease of the compressed working gas inside the MCEU, a polytropic expansion with an associated temperature decrease, and heat transfer from the heat transfer fluid with a corresponding small temperature and pressure increase in the expanded working gas. This combination of events creates a small unique thermodynamic cycle for each MCEU with corresponding heat flows at mean temperatures, T H and T C , and associated work input. [0018] According to an embodiment, there is a recovery of compression work by direct coupling to an expansion at a slightly lower temperature in this cycle. If the heat transfer fluid through the dual regenerators is shut off, the net work input into a MCEU will drop to zero even though the working gas is being compressed and expanded on opposite ends of the MCEU (excluding frictional dissipation in the seal and Joule heating in the drive coils). This feature is difficult to do effectively in conventional gas cycle refrigerators and is one of the reasons that gross efficiencies of conventional gas refrigerators are so low relative to ideal. Turbo-expander units have been built for cryogenic Claude cycle refrigerators but the amount of work recovery is generally relatively small because the gas expansion is done at a temperature substantially different from the gas compression. Intrinsic work recovery to the extent allowed by a thermodynamic refrigeration cycle is one of the reasons that active gas regenerative refrigerators show promise of high efficiency. This is caused by the synchronous force balance in each MCEU. This very desirable feature is enabled by directly coupling the compression of the working gas at one end of each MCEU with the simultaneous expansion of the working gas at the other end of the same MCEU in identical dual regenerators. Accomplishing this coupling allows efficient distributed work input and work recovery from near ambient temperature to cryogenic temperatures as low as ˜4 K. By using this novel concept the net required work input for a given thermal load is reduced substantially no matter what the temperature span of the refrigerator or liquefier is. To the knowledge of the inventors, this input of “distributed net work” is unique among gas refrigerators. [0019] According to an embodiment, the thermal mass of each active end of a MCEU of an array in dual regenerators are similar and provide the desirable feature of thermally-balanced regenerators, even with heat capacity variations of tubing material, piston material, drive mechanism, and working gas as a function of temperature. BRIEF DESCRIPTION OF THE DRAWINGS [0020] FIGS. 1A and 1B illustrate the basic structure of a micro compressor-expander unit (MCEU), according to an embodiment, with a moveable drive piston coupling compression and expansion of a working gas in opposite end sections of the MCEU, with the piston in, respectively, a neutral position and a position at one extreme of movement. [0021] FIGS. 2A and 2B illustrate, respectively, the idealized pressure vs. volume, and pressure vs. temperature cycles of the working gas within one thermally active end section of a MCEU, according to an embodiment. [0022] FIG. 3 illustrates the relative work input in a complete cycle for the working gas in one end section of a MCEU, according to an embodiment. [0023] FIG. 4 illustrates the entropy-temperature diagram for the cycle of the working gas in the thermally active end sections of a MCEU, according to an embodiment. [0024] FIG. 5 shows a calculated P-T diagram for an ideal MCEU gas cycle near 100 K with instantaneous heat transfer during compression/expansion within an active gas regenerative refrigerator (AGRR) cycle, according to an embodiment. [0025] FIG. 6 illustrates details of a piston structure of a MCEU, according to an embodiment, with two sets of opposing permanent magnets, with a magnetic coupler, to create a stronger transverse flux, compared to a single permanent magnet. [0026] FIG. 7 shows key elements of a pneumatically-driven MCEU design, according to an embodiment, with a moveable annular permanent magnet shell around a center section of the MCEU. [0027] FIGS. 8A and 8B are schematic diagrams of an AGRR system showing the system during respective isochoric steps of a refrigeration cycle, according to an embodiment. DETAILED DESCRIPTION [0028] In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here. [0029] During the NASA SBIR project referred to above, several challenging design issues were identified which were beyond the scope of the project. Most of these issues were related to manufacturing individual refrigeration elements, each with means to synchronously drive reciprocating micro pistons in each element when the working helium gas is at sufficiently high pressures (several MPa), and at pressure ratios large enough to cause polytropic temperature changes of between 2 K and 20 K during compression or expansion. The electromagnetic-magnetic drive forces in the initial drive designs were small compared to the pressure forces on the piston from the He gas at the peak pressures in the MCEU cycle. These issues are reduced or overcome by various embodiments of the present invention. [0030] A simple version of a single micro compressor-expander unit (MCEU) tube 100 , according to an embodiment, is illustrated in FIGS. 1A and 1B , including a uniform cylindrical metal tube 102 formed into a hermetic thin shell with good mechanical strength, modest thermal mass, and reasonable thermal conductivity. This MECU has three sections; two “thermally active” end sections 104 , 106 and a thermally static center section 108 . A moveable piston 110 at equilibrium in the center section of the MCEU tube 100 has an electromagnetic or pneumatic drive sufficiently strong to overcome the pressure forces on the piston 110 . A stationary close-fitting, low-friction labyrinth seal 112 keeps the working gas in both thermally active ends 104 , 106 of the MCEU tube 100 during a compression-dwell-expansion-dwell cycle. Working gas in the active sections 104 , 106 of the MCEU tube 100 simultaneously executes the same thermodynamic cycle, but exactly out of phase with the cycle of the working gas at the opposite end of the MCEU tube 100 . The working gas can be any of a number of different gases, including, for example, helium (He). The thermally active sections 104 , 106 in a highly efficient active gas regenerator need high specific area so the tube diameter (od) will be small (specific area for a cylindrical tube is 4/(tube od) or ˜1,200 m 2 /m 3 for a ⅛″ od tube). [0031] In FIG. 1A the piston 110 is in its equilibrium position and the pressure of the working gas is the same in both end sections 104 , 106 of the MCEU tube 100 . In FIG. 1B the piston 110 is in its right-most position, with compressed, hotter helium working gas also on the right end 106 of the MCEU tube 100 , and expanded, colder helium working gas on the left end 104 of the tube 100 (the polytropic temperature changes depend on several MCEU design variables and can be ˜2 K to ˜20 K). According to an embodiment, an enhanced piston design has several components; both ends of the piston 110 that extend into the thermally active sections 104 , 106 of the MCEU tube 100 are made from material with reasonably high mechanical strength, low thermal mass, and poor thermal conductivity. As described in detail below with reference to FIGS. 6 and 7 , the central part of the moveable piston 110 contains several opposing pairs of high-strength, small, cylindrically-shaped, permanent magnets held in a thin tubular structure that moves within a thin tube of material that has a low friction coefficient (e.g. loaded Teflon or Rulon) bonded to the inner wall of the center section 108 of the MCEU tube 100 . The piston's mechanical properties enable a low-leakage, low-friction labyrinth seal 112 as the piston 110 is driven between opposite ends of the MCEU tube 100 by electromagnetic or pneumatic means. [0032] According to an embodiment, the thermally active regions of the MCEU tube 100 enable the execution of an active gas regenerative cycle in the thermally active sections 104 , 106 of the MCEU tube 100 . This cycle executed half a cycle out of phase at opposite active ends of the MCEU tube 100 consists of four steps; i) a polytropic compression with no transverse flow of a separate heat transfer fluid (HTF); ii) an isochoric (constant volume) step with cold-to-hot flow of HTF that causes the temperature and pressure of the compressed He working gas and the shell wall 114 in one end of the MCEU tube 100 to decrease by the temperature increase of the compressed end of the MCEU tube 100 while the HTF is heated; iii) a polytropic expansion with no HTF flow; and iv) an isochoric step with hot-to-cold flow of HTF that causes the temperature and pressure of the expanded He working gas in the same end of the MCEU tube 100 and the shell wall 114 in the thermally active regions 104 , 106 of the MCEU tube 100 to increase while the HTF is cooled. [0033] The resultant force on the piston 110 in each MCEU tube 100 comes from the differential pressures in the opposite end sections of the MCEU tube 100 pushing on the end area of the piston 110 . The cooling power of each MCEU tube 100 , the rejected heat rate, and the net work rate required to move the piston 110 in each polytropic compression step of the MCEU cycle are a function of several design variables such as the mean MCEU operating temperature, temperature span, mean loading pressure of He working gas, diameter and wall thickness of the tube 100 , the pressure ratio and corresponding polytropic temperature changes, etc. For example, in a system configured for liquefying natural gas, the polytropic exponent k changes from ˜1.04 at 290 K to ˜1.1 at 110 K (He alone has a value of 1.66). The inventors' calculations indicate excellent promise for fabrication of small-diameter, tubular, inexpensive MCEUs driven either electromagnetically, at lower temperatures, or pneumatically, at higher temperatures, such as may enable very efficient active gas regenerative refrigerators (AGRRs) and active gas regenerative liquefiers (AGRLs) to be built. [0034] The cylindrical hermetic MCEU tube 100 illustrated in FIGS. 1A and 1B includes many basic elements, according to an embodiment. The detailed MCEU cycle analysis presented below allows calculation of heat flows, work flows, pressures, temperatures, material property changes as a function of temperature, and forces for a wide range of design variables. The further description that follows gives a detailed explanation of the MCEU cycle and work input mechanisms to drive the piston 110 as it simultaneously compresses and expands the working gas. [0035] To better explain the non-obviousness and usefulness of the MCEU, an analysis is provided of a regenerative refrigeration cycle when an array of MCEUs is combined, in accordance with an embodiment of an active gas regenerative refrigerator (AGRR). The working gas cycle in each end section 104 , 106 of a MCEU tube 100 consists of four steps; i) a polytropic compression by moving the piston 110 to the right with no transverse heat transfer fluid (HTF) flow of the AGRR; ii) an isochoric (constant volume) step with cold-to-hot flow of HTF around the MCEUs with thermal energy transfer from the MCEUs to the HTF, thereby decreasing the temperature and pressure of the He working gas in hermetic MCEU tubes 100 as the HTF is heated; iii) a polytropic expansion of the working gas in the MECUs by moving the piston 110 to the left with no HTF flow; and iv) an isochoric step with hot-to-cold flow of HTF that causes the temperature and pressure of the He working gas in the MCEU tubes 100 to increase as the HTF is cooled. It is important to note that the working gas in the other end section of the MCEU tube 100 simultaneously executes exactly the opposite cycle. [0036] The performance of the thermodynamic cycle executed by the working gas at each end 104 , 106 of the MCEU tube 100 is calculated for an ideal gas at constant temperature near room temperature, and then with real gas properties in a MCEU with realistic design specifications for an AGRR operating from near room temperature to cryogenic temperatures applicable for numerous applications. [0037] For the thermodynamic analysis the variables are defined as follows: T w —tube wall temperature T g —working gas temperature m g —mass of working gas in both ends of the tube μ g —molar mass of gas m w —tube wall mass n—number of moles of working gas c v , c p —molar heat capacities of the working gas c w —heat capacity of tube material per unit mass R—universal gas constant, R=8.314 J/(mol K) [0047] Consider a control volume around one thermally active end section 104 , 106 of the MCEU tube 100 including the working gas hermetically contained inside a thin-walled tubular shell. Apply energy conservation to the ideal working gas during the cycle and the shell and assume adiabatic processes, i.e., dQ=0 for control volume which can be expressed as: [0000] m w c w dT w =−dU g −pdV [0048] Assume instantaneous heat transfer from the working gas to the shell wall 114 associated with a very small Biot number which means: [0000] dT w =dT g =dT [0049] The derivation of relationships between p, T and V are: [0000] dU g = nc V  dT ,  n = m g μ g m w  c w  dT = - nc V  dT - pdV  ( m w  c w + nc V )  dT = - pdV [0050] Given the ideal gas equation of state is: [0000] pV=nRT [0000] − pdV=−nRdT+Vdp [0051] After substituting for dT into the first-law equation we have: [0000] ( m w  c w + nc V + nR )  pdV = - ( m w  c w + nc V )  Vd   p ( m w  c w + nc V + nR ) ( m w  c w + nc V )  dV V = - dp p ( m w  c w + nc V + nR ) ( m w  c w + nc V )   ln   ( V ) = - ln   ( p ) + ln   ( const ) pV  ( m w  c w + nc V + nR ) ( m w  c w + nc V ) = const γ = c p c V   c p - c V = R = 8.3144  J mol   K k = ( m w  c w + nc V + nR ) ( m w  c w + nc V ) = m w n  c w + c V + R m w n  c w + c V = m w n  c w + c p m w n  c w + c V = c p a c V a [0052] This equation defines k as the polytropic compression or expansion exponent. In the limit of massless tube walls, it reduces to c p /c v for the working gas as expected. [0000] pV k = const or p 2 - p 1  ( V 1 V 2 ) k and T 2 = T 1  ( V 1 V 2 ) k - 1 [0053] The polytropic exponent, k, and the compression ratios of working gas in the MCEU show the importance of the ratio of thermal mass of the He working gas and the walls of the tube 102 (the drive piston 110 can be selected to minimize its thermal mass), the mean pressure of the He gas in the MCEU, and the geometry of the MCEU design. This derivation also shows that an adiabatic process for the entire control volume at either end 104 , 106 of the MCEU tube 100 means a polytropic process for the working gas during the compression or expansion caused by the moveable piston 110 . [0054] The specific work per mole for the working gas in a non-flow, hermetic MCEU is: [0000] w polytropic , nonflow = - RT 1 k - 1  [ ( p 2 p 1 ) k - 1 k - 1 ] = c V  ( T 1 - T 2 ) [0055] The work of compression for a polytropic process is then: [0000] W polytropic , nonflow = - nRT 1 k - 1  [ ( p 2 p 1 ) k - 1 k - 1 ] [0056] Define [0000] r = V 1 V 2 > 1 , [0000] so the work of compression done on the working gas becomes: [0000] W polytropic = nRT 1 k - 1  [ r k - 1 - 1 ] [0057] If no HTF flows in the regenerator of the AGRR, the temperature T 2 of the helium working gas in the MCEUs does not change after polytropic compression so the working gas upon polytropic expansion returns exactly to T 1 . This is exactly what is expected in an ideal working gas with instantaneous heat transfer, no friction or leakage in the drive piston 110 , no thermal conduction along shell walls 114 , and perfect insulation between the working gas and the drive piston 110 . [0058] Now consider what happens when HTF flows over/around the MCEUs in the respective regenerator arrays to change T 2 to T 3 before the polytropic expansion step occurs. [0000] p 2 = p 1  ( V 1 V 2 ) k , T 2 = T 1  ( V 1 V 2 ) k - 1 , p 3 = p 2  T 3 T 2 , Choose [0059] T 3 = T 1 + T 2 2 = T 1  ( 1 + ( V 1 V 2 ) k - 1 ) 2 [0000] because the temperature approach between the HTF and the MCEU shell at that position in the regenerator of the AGRR decreases from a maximum of T 2 −T 1 to ˜0 during the optimum flow period of the HTF (this average value of T 3 assumes linear temperature chance which is a reasonable choice). [0000] p 3 = p 1  ( V 1 V 2 ) k  T 3 T 2 = p 1  ( V 1 V 2 ) k  ( 1 + ( V 1 V 2 ) k - 1 ) 2  ( V 1 V 2 ) 1 - k = p 1  ( V 1 V 2 + ( V 1 V 2 ) k ) 2 p 4 = p 3  ( V 3 V 4 ) k = p 1  ( V 1 V 2 + ( V 1 V 2 ) k ) 2  ( V 1 V 2 ) - k = p 1  ( V 1 V 2 ) 1 - k + 1 2 [0000] From isochoric cooling/heating: [0000] T 4 = T 1  p 4 p 1 = T 1  ( V 1 V 2 ) 1 - k + 1 2 [0060] Two MCEU cycles, as illustrated in FIGS. 2A and 2B below, are simultaneously executed 180° out of phase by the same mass of working gas at each dual regenerator section at opposite end sections 104 , 106 of the tube 100 . The working gas changes in pressure and temperature as the piston 110 in the MCEU tube 100 is driven to one end or the other end of the MCEU tube 100 . The diagrams described below illustrate the idealized cycle for the working gas in each end 104 , 106 of the MCEU tube 100 , as follows (mass transfer through leaky seals 112 on drive piston 110 neglected): [0061] Calculating the temperature after polytropic expansion as a check: [0000] T 4 = T 3  ( V 3 V 4 ) k - 1 = T 1  ( 1 + ( V 1 V 2 ) k - 1 ) 2  ( V 2 V 1 ) k - 1 = T 1  ( V 1 V 2 ) 1 - k + 1 2   Looks   O . K .  T 1 - T 4 = T 1 - T 1  ( V 1 V 2 ) 1 - k + 1 2 = T 1  1 - ( V 1 V 2 ) 1 - k 2 = T 1  1 - r 1 - k 2 [0062] The resultant work input needed for a complete cycle of the working gas (ideal gas) in a thermally active end section 104 , 106 of the MCEU tube 100 is given by the difference between work of compression from T 1 and the work from expansion from T 3 , a slightly lower temperature: [0000] Δ   W polytropic = W 1 - 2 - W 3 - 4 = nRT 1 k - 1  [ r k - 1 - 1 ] - nRT 4 k - 1  [ r k - 1 - 1 ] Δ   W polytropic = W 1 - 2 - W 3 - 4 = nR  ( T 1 - T 4 ) k - 1  [ r k - 1 - 1 ] Δ   W polytropic = W 1 - 2 - W 4 - 3 = nRT 1 k - 1  ⌊ r k - 1 + r 1 - k - 2 ⌋ 2 x = Δ   W polytropic W 4 - 3 = T 1  ⌊ r k - 1 + r 1 - k - 2 ⌋ 2  1 T 1  [ r 1 - k + 1 ] 2  [ r k - 1 - 1 ] = ⌊ r k - 1 + r 1 - k - 2 ⌋ r k - 1 - r 1 - k x = Δ   W polytropic W 4 - 3 = r k - 1 + r 1 - k - 2 r k - 1 - r 1 - k [0063] FIG. 3 illustrates the relative work input in a complete cycle for the working gas in one end section 104 , 106 of a MCEU tube 100 , according to an embodiment. The curves shown in FIG. 3 indicate that to make an effective MCEU cycle, the design choices must achieve k of ˜1.05 to ˜1.10 with a piston geometry that gives a compression ratio of ˜2. Such values can be obtained with MCEU tube 100 dimensions of 0.125″ o.d. with a wall thickness of 0.003″ with overall length of 8″ and thermally active sections 2″ long with 5.0 MPa (˜750 psia) mean pressure with a piston sized to give a compression ratio of ˜1.2 to ˜2.0 (see FIG. 1B ). If k ˜1 (the isothermal limit), x is close to zero no matter what the compression ratio is, i.e., there is no work recovered because no work is input and there is no cooling. This limit is approached only for very large thermal mass of the MCEU shell 114 , very little working gas in the MECU tube 100 , and/or a small compression ratio. These regions of design space are easy to avoid in fabricating an effective MCEU. [0064] Similarly, the heat and entropy flows for the working gas in the thermally active end sections 104 , 106 of the MCEU tube 100 can be calculated. FIG. 4 illustrates the entropy-temperature diagram for the cycle of the working gas in the thermally active end sections 104 , 106 of a MCEU tube 100 , according to an embodiment. [0065] In FIG. 4 , the path between points 1 and 2 of the entropy-temperature diagram represents a polytropic compression of a working gas (with heat flow from the working gas to a metal shell); the path between points 2 and 3 of the entropy-temperature diagram represents isochoric cooling of the working gas from a separate heat transfer fluid; the path between points 3 and 4 of the entropy-temperature diagram represents polytropic expansion of the working gas (with heat flow from the metal shell to the working gas); and the path between points 4 and 1 of the entropy-temperature diagram represents isochoric heating of the working gas from a separate heat transfer fluid. [0000] dS = C V T  dT + ( ∂ p ∂ T ) V  dV or dS = C p T  dT - ( ∂ V ∂ T ) p  dp [0066] For an ideal gas, the change in entropy is: [0000] S i - S f = ∫ i f  dS = nc V   ln   ( T f T i ) + nR   ln   ( V f V i ) or S i - S f = ∫ i f  dS = nc p   ln   ( T f T i ) - nR   ln   ( p f p i ) [0067] Let's define [0000] Q if = Q f - Q i = ∫ i f  TdS [0068] For the isochoric processes in the working gas (dV=0): [0000] Q 23 =nc V ( T 3 −T 2 )<0, Q 41 =nc V ( T 1 −T 4 )>0 [0069] These equations show that heat (thermal energy) flows out of the selected control volume of the working gas in one end section 104 , 106 of a MCEU tube 100 in the hot-to-cold flow ( 2 to 3 ) of heat transfer fluid through an AGRR comprised of an array of MCEUs and heat flows into the control volume of the working gas in the cold-to-hot flow ( 4 to 1 ) of the HTF in the same AGRR. [0070] For the polytropic processes in the working gas: [0000] Q 12 = nc V  ( T 2 - T 1 ) + ∫ 1 2  TnR  dV V = nc V  ( T 2 - T 1 ) + ∫ 1 2  T 1  V 1 k - 1 V k - 1  nR  dV V Q 12 = nc V  ( T 2 - T 1 ) + nRT 1  V 1 k - 1  ∫ 1 2  dV V k = nc V  ( T 2 - T 1 ) + nRT 1  V 1 k - 1  1 1 - k  ( V 2 1 - k - V 1 1 - k ) Q 12 = nc V  ( T 2 - T 1 ) + nRT 1  1 1 - k  ( ( V 2 V 1 ) 1 - k - 1 ) = nc V  ( T 2 - T 1 ) + nRT 1  1 1 - k  ( r k - 1 - 1 ) < 0 Q 34 = nc V  ( T 4 - T 3 ) + nRT 3  1 1 - k  ( ( V 4 V 3 ) 1 - k - 1 ) = nc V  ( T 4 - T 3 ) + nRT 3  1 1 - k  ( r 1 - k - 1 ) Let Q 12341 = Q 12 + Q 23 + Q 34 + Q 41 [0071] All the nc V terms cancel each other and: [0000] Q 12341 = nRT 1  1 1 - k  ( r k - 1 - 1 ) + nR  T 1  ( 1 + r k - 1 ) 2  1 1 - k  ( r 1 - k - 1 ) Q 12341 = nRT 1 1 - k  [ 2  r k - 1 - 2 + ( 1 + r k - 1 )  ( r 1 - k - 1 ) 2 ] = nRT 1 1 - k  [ r k - 1 + r 1 - k - 2 2 ] [0000] This result shows that Q 12341 =−ΔW polytropic , as it should be. [0072] The inventors have prepared detailed design calculations, according to an embodiment, for a new MCEU with He working gas at up to 5.0 MPa mean pressure at 290 K using ⅛″ diameter Al alloy seamless tubing of type 2024-T6 with 0.003″ wall thickness with pistons 110 ranging in diameter from ⅞ to ⅜ of the i.d. of the MCEU tube 100 . With typical MCEU tube 100 dimensions listed above, using real gas properties for helium working gas at starting pressure of 5.0 MPa at 290 K, and the temperature-dependent heat capacity of 2024-T6 Al alloy tube material, the calculated P-T cycle for an achievable MCEU piston design with He working gas at about 100 K is shown in FIG. 5 . This module could be one of three AGRRs in an efficient AGRL for liquid natural gas (LNG). [0073] FIG. 6 illustrates details of a piston structure of a MCEU tube 600 , according to an embodiment, with one or more sets 602 of opposing permanent magnets 604 , with a magnetic coupler 606 , to create a stronger transverse flux, compared to a single permanent magnet. In one embodiment of the invention, illustrated in FIG. 6 , two small-diameter cylindrical high-field Nd 2 Fe 14 B permanent magnets 604 , which together form one set 602 , are inserted as opposing each other into a cylindrical drive piston assembly 610 within a Rulon sleeve seal (not shown) in the center section 612 of the MCEU tube 600 . The N-S poles of the permanent magnets 604 are aligned as S-N-N-S. This embodiment includes an iron flux coupler 606 to help concentrate the magnetic flux of the radial magnetic field B R created by the opposing permanent magnets 604 . Two or more sets 602 of such opposing permanent magnets 604 are envisioned to increase the Lorenz force applicable on the drive piston 610 . [0074] FIG. 6 also shows a drive mechanism, according to an embodiment. As an example, a thin annular coil 614 with several layers of good electrical conducting or superconducting wire such as AWG 20-30, is assembled surrounding the center section of a hermetic MCEU tube 616 with the piston, seals, and working gas in it (the complete piston and seals are not shown in detail in FIG. 6 , but are shown and described elsewhere). The magnetic field from the energized coil 614 couples tightly to the concentrated magnetic flux from all sets 602 of opposing Nd 2 Fe 14 B magnets 604 within the piston assembly 610 . As the d.c. power supply to each MCEU drive coil 614 charges with appropriate polarity during different steps within the MCEU cycle, the current in the coil 614 creates a Lorenz force on the permanent magnets 604 to thereby move the drive piston 610 inside the MCEU 600 in either axial direction. The Lorenz force in this electromagnetic drive can be adjusted in strength by adjusting the length of the center section 612 of the MCEU tube 600 relative to the thermally active sections 104 , 106 of the MCEU to keep the Joule heating from the drive coils 614 to a small parasitic heat load compared to the cooling power of the MCEU tube 600 (or vice-versa). [0075] In FIG. 7 an embodiment of the invention illustrates another drive mechanism for a MCEU 710 . In this second embodiment of the invention two or more sets of two small-diameter cylindrical high-field Nd 2 Fe 14 B permanent magnets 742 are inserted as opposing each other into a cylindrical drive piston assembly 718 within a Rulon sleeve seal 726 in the center section of the MCEU 710 . A cylindrical soft iron or other high magnetic permeability material 738 is mounted in the seal section 726 of the MCEU 710 to augment coupling of the magnetic flux of the two permanent magnet arrays 734 . Outside the Al tube 714 another cylindrical annular Nd 2 Fe 14 B permanent magnet array 734 is mounted inside a close-fitting, low-friction hermetic tube 730 such that gas at either end of this surrounding tube 730 can change pressure to move the annular magnet array 734 back and forth. The magnetic flux from the opposing permanent magnets 742 in this shell couples tightly to the flux of similar sets of Nd 2 Fe 14 B magnets 742 inside the central MCEU piston 718 . This outer magnet array 734 in its close fitting housing 730 is pneumatically driven, and drives in turn the central piston inside the MCEU 710 , back and forth to alternatively compress or expand its working He gas 722 . One or more cylindrical, thin annular Nd 2 Fe 14 B permanent magnets 734 are assembled inside a close-fitting, low-friction hermetic tube 730 surrounding the center section of the hermetic MCEU tube 710 containing the piston 718 , seals 726 , and working gas 722 . The magnetic flux from annular permanent magnet array 734 couples tightly to the concentrated magnetic flux from all sets of opposing Nd 2 Fe 14 B magnets 742 within the piston assembly 718 . When the outer annular magnet array 734 in its close fitting housing 730 is pneumatically moved back and forth over the center section of the MCEU 710 , it will thereby move the drive piston 718 inside the MCEU 710 . The pneumatic drive in each MCEU 710 is fed by a separate pressurized gas supply (not shown) into either end of the thin hermetic shell 730 around the MCEU 710 . This gas is supplied via a small tube 746 from a common feed gas source with adjustable pressures as necessary to move the annular magnet 734 back and forth. Correspondingly, the gas on the other end of the annular shell 730 around the center section of the MECU 710 will be returned to a common lower pressure vessel from which the suction port of the gas pump 746 will be fed to return higher pressure gas to the supply tank. Two-way valves on the manifolds out of the higher pressure vessel and into the lower pressure vessel of the pneumatic gas drive subsystem (not shown) allow properly-timed connections required to execute MCEU cycles via this pneumatically driven subsystem for an entire array of MCEUs (not shown). [0076] FIGS. 8A and 8B are schematic diagrams of an AGRR system 800 showing the system during respective isochoric steps of a refrigeration cycle, according to an embodiment. The AGRR system 800 includes an array 802 of MCEUs 804 , each having a cylinder 805 and a double-ended drive piston 806 positioned within the cylinder 805 and configured to be driven back and forth to alternately compress and expand equal masses of working gas in respective ends of the MCEU 804 . Each MCEU 804 further includes a seal 807 positioned between the inside of the cylinder 805 and the drive piston 806 . The seal 807 is configured to permit axial movement of the drive piston 806 within the cylinder 805 while preventing movement of the working gas between the ends of the MCEUs 804 . [0077] The drive pistons 806 can be driven by any appropriate mechanism, such as, for example, either of the mechanisms described above with reference to FIGS. 6 and 7 . [0078] First ends 808 of each of the MCEUs 804 are positioned within a first heat transfer chamber 810 , while second ends 812 of each of the MCEUs 804 are positioned within a second heat transfer chamber 814 . The first heat transfer chamber 810 includes first and second fluid ports 816 , 818 and the second heat transfer chamber 814 includes third and fourth fluid ports 820 , 822 . A thermal load 824 is in fluid communication with the first and third fluid ports 816 , 820 , while a heat sink 826 is in fluid communication with the second and fourth fluid ports 818 , 822 . A reversible fluid pump 828 is configured to drive a heat transfer fluid (HTF) through a heat transfer circuit formed by the first and second heat transfer chambers 810 , 814 , the thermal load 824 , and the heat sink 826 . [0079] In operation, during a first operating step, the drive pistons 806 are driven to a first position, defined by an extreme of travel in a first direction, as shown in FIG. 8A , radially compressing the working gas in the first ends 808 of the MCEUs 804 into first annular gaps 830 between radial surfaces of the drive pistons 806 and inner radial surfaces of the first ends 808 , while expanding the working gas in the second ends 812 . This causes the temperature of the working fluid in the first ends 808 to rise, and the temperature of the working fluid in the second ends 812 to drop. During this step, the pump 828 is not in operation. [0080] During a second step, the pump 828 operates to drive the HTF in a first direction D 1 through the fluid circuit, as shown in FIG. 8A , so that fluid heated by the thermal load 824 is carried into the first heat transfer chamber 810 , where it is heated as it flows across the outsides of the first ends 808 of the MCEUs 804 , while cooling the working fluid within the first ends 808 . HTF from the first heat transfer chamber 810 is carried to the heat sink 826 , where the heated fluid is cooled by contact with the heat sink 826 . From the heat sink 826 , the cooled HTF is carried into the second heat transfer chamber 814 , where it is cooled as it flows across the outsides of the second ends 812 of the MCEUs 804 , while warming the working fluid within the second ends 812 . Lastly, cooled HTF is carried from the second heat transfer chamber 814 to the thermal load 824 , where it efficiently chills the thermal load 824 , being heated itself in return. [0081] During a third operational step, the flow of fluid is shut down, and the drive pistons 806 are driven to a second position defined by an extreme of travel in a second direction, opposite the first direction, as shown in FIG. 8B , radially compressing the working gas in the second ends 812 of the MCEUs 804 into second annular gaps 832 between the radial surfaces of the drive pistons 806 and the inner radial surfaces of the second ends 812 , while expanding the working gas in the first ends 808 . This causes the temperature of the working fluid in the second ends 812 to rise, and the temperature of the working fluid in the first ends 808 to drop. [0082] Finally, during a fourth step, the pump 828 operates to drive the HTF in a second direction D 2 through the fluid circuit, as shown in FIG. 8B . Accordingly, HTF is driven from the heat sink 826 to the second heat transfer chamber 814 , from the second heat transfer chamber 814 to the heat sink 826 , from the heat sink 826 to the first heat transfer chamber 810 , and from the first heat transfer chamber 810 to the thermal load 824 . The HTF cools the thermal load 824 while being heated in exchange, cools the second ends 812 of the MCEUs 804 while being heated in exchange, transfers heat to the heat sink 826 , which is configured to remove the heat to a remote location, while being cooled thereby, warms the first ends 808 while being cooled, and back to the thermal load 824 . [0083] The four-step process outlined above is repeated continuously during operation of the device. [0084] The term thermally active section is used here to refer to the outer surface of the portion of a cylinder 805 that is in direct contact, on its inner surface, with a working fluid. Because the MCEUs 804 are configured to form the first and second annular gaps 830 , 832 , the working fluid remains in contact with the inner surfaces of the first and second ends 808 , 812 along a length of the respective cylinders 805 that remains constant throughout the operational cycle. Accordingly, the surface area of the active sections of each of the first and second ends 808 , 812 of the MCEUs 804 also remains unchanged throughout the cycle, even as the respective drive pistons 806 move reciprocally within the cylinders 805 . This means that the ability of the heat transfer fluid outside the MCEUs 804 to exchange heat with the working fluid inside the MCEUs 804 is not affected by the position of the pistons 806 . [0085] This is in contrast to devices in which a piston seal sweeps an inner face of a cylinder as the piston moves, compressing a working fluid into an end of the cylinder. In such a device, the active section is defined by the distance between the piston seal and the end of the cylinder, such that as the piston moves back and forth within the cylinder, the surface area of the active section continually changes, reaching a minimum when the working fluid is at maximum compression. Thus, the heat exchange capacity of the cylinder is at a minimum when the temperature difference across the cylinder wall is at a maximum, which can significantly reduce the heat transfer efficiency of the associated system. [0086] In the embodiment of FIGS. 8A and 8B , the end surfaces of the cylinders 805 lying transverse to the cylinder axes are positioned against the walls of the first and second heat transfer chambers 810 , 814 such that they are not exposed to the HTF as it flows through the chambers 810 , 814 . According to another embodiment, the first and second ends 808 , 812 of each of the MCEUs 804 are positioned within the first and second heat transfer chambers 810 , 814 , respectively, and the HTF flows over and in contact with the transverse end surfaces, such that the active sections of each MCEU 804 are increased by the area of the transverse end surfaces as well. In this embodiment, the array 802 is configured such that when the drive pistons 806 of the MCEUs 804 are in either of their first or second positions, a gap remains between transverse ends of the pistons 806 and the transverse ends of the respective cylinders 805 . Accordingly, working fluid remains in contact with the transverse ends of the cylinders 805 throughout the operational cycle. [0087] The array 802 of MCEUs 804 is represented in FIGS. 8A and 8B by a small number of MCEUs 804 in a single row. It will be understood that in practice, the number of MCEUs 804 in the array can number in the hundreds, or more, and can be arranged in any appropriate configuration, including rows and columns, hexagonal grids, etc. [0088] In the embodiment illustrated in FIGS. 8A and 8B , the AGRR system 800 is configured for use with a gaseous HTF. According to other embodiments, liquid heat transfer fluids may also be employed. It is important to avoid heat transfer fluids that might freeze during operation, which reduces the number of suitable fluids, especially liquids, particularly when the system is to be operated at cryogenic temperatures. Hydrogen and helium are among the fluids that can be employed in most cryogenic applications. According to a preferred embodiment, He gas, at a pressure of around 500 psia, is employed as the heat transfer fluid. [0089] Although in most embodiments, a gaseous HTF is maintained at an elevated pressure of several hundred psia, in some embodiments in which the HTF is not pressurized, ambient air may be used as the HTF, in which case the heat sink 826 can be omitted, so that the air is drawn directly into one or the other heat transfer chamber, then vented back to the atmosphere after exiting the other chamber, or even after passing through the thermal load 824 . [0090] The abstract of the present disclosure is provided as a brief outline of some of the principles of the invention according to one embodiment, and is not intended as a complete or definitive description of any embodiment thereof, nor should it be relied upon to define terms used in the specification or claims. The abstract does not limit the scope of the claims. Elements of the various embodiments described above can be combined, and further modifications can be made, to provide further embodiments without deviating from the spirit and scope of the invention. All of the patents and non-patent publications referred to in this specification and/or listed in the Application Data Sheet are incorporated herein by reference, in their entirety. Aspects of the embodiments can be modified, if necessary to employ concepts of the various patents and publications to provide yet further embodiments. [0091] While various aspects and embodiments have been disclosed herein, other aspects and embodiments are contemplated. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.
An active gas regenerative refrigerator includes a plurality of compressor-expander units, each having a hermetic cylinder with a drive piston configured to be driven reciprocally therein, and a quantity of working fluid in each end of the cylinder. A piston seal in a central portion of the cylinder prevents passage of the working fluid between ends of the cylinder. Movement of the piston to a first extreme results in radial compression of one of the quantities of working fluid in a cylindrical gap formed between one end of the piston and an inner surface of the cylinder, while the other quantity is expanded in the opposite end of the cylinder. The piston includes a plurality of magnets arranged in pairs, with magnets of each pair positioned with like-poles facing each other. A piston drive is configured to couple with transverse magnetic flux regions formed by the magnets.
5
FIELD OF THE INVENTION [0001] The present invention relates to a method and apparatus for communicating data over a data network. In particular, it relates to an access device or sub-system such as a Digital Subscriber Line Access Multiplexer (DSLAM) or similar access node terminating a digital subscriber line, a method of operating such an access device and an access network including one or more such access devices. BACKGROUND TO THE INVENTION [0002] ITU recommendation G992.1 specifies how the maximum bandwidth which can be supported over a particular ADSL connection between a particular Remote ADSL Transceiver Unit (ATU-R) and a particular Central office or network operator ADSL Transceiver Unit (ATU-C) may be determined at the time of initiation of the ADSL connection (see G992.1 Chapter 10) and may even be periodically re-negotiated during a connection (see G992.1 Appendix II); the maximum bandwidth in fact depends upon various factors which will differ from line to line and from time to time depending on things such as the amount of electromagnetic noise present in the environment of the ATU-R, etc. [0003] However, despite this, it is common in most practical implementations of ADSL for a network operator to offer an end user a fixed bandwidth (commonly offered values being 500 kb (kilo bits/second), 1 Mb (Mega bits/second) and 2 Mb). In such circumstances, the initiation process happens in the standard way to establish the maximum bandwidth available over the connection, but instead of then setting up the connection at that maximum setting, it is simply checked whether or not this maximum is at least equal to the contractually agreed bandwidth, and if so, then the connection is made at this agreed amount (rather than the maximum available) but otherwise the connection is just not made at all. [0004] Because an access network is likely to contain a large number of DSLAMs they have generally been designed to operate as autonomously as possible. As such, although they will generally store some useful data about each digital subscriber line (hereinafter referred to simply as a “line”) to which it is connected such as the theoretical maximum rate at which the line could have been connected last time an ADSL connection was set up over the line, each DSLAM operates according to a server client model where each DSLAM operates as a server and only reacts to requests issued to it from a client. Thus in current DSLAMs, in order to access information about an individual line a requesting device generally needs to issue a request to the DSLAM and await a response. SUMMARY OF THE INVENTION [0005] According to a first aspect of the present invention, there is provided an access device including a plurality of digital subscriber line modems for terminating a plurality of corresponding digital subscriber lines and connecting them to an access network, the access device being operable to monitor one or more of the digital subscriber lines and to generate and transmit a message to another device in dependence upon the results of monitoring the one or more digital subscriber lines. [0006] According to a second aspect of the present invention, there is provided a method of operating an access device including a plurality of digital subscriber line modems for terminating a plurality of corresponding digital subscriber lines and connecting them to an access network, the method comprising: monitoring one or more of the digital subscriber lines; and generating and transmitting a message to another device in communication with the multiplexer in dependence upon the results of the monitoring step. [0007] In the case that the access device is a DSLAM, this means that the DSLAM no longer acts purely in a server role. That is to say, instead of responding only when requested to do so by another device, the DSLAM can generate and transmit messages purely as a result of its own internal processes. Preferably, the DSLAM monitors events to do with the establishment of Digital Subscriber Line (DSL) connections over the DSL's and determines if one or more certain predetermined conditions or sets of conditions arise. [0008] Preferably, for example, the DSLAM monitors any lines which are operating in a rate adaptive mode (i.e. where the lines connect up at a data rate which depends on the actual circumstances present within the system at the time the connection is made—e.g. at the maximum possible speed achievable (for a given noise margin and mode of operation (i.e. fixed or interleaved) rather than at a fixed pre-agreed rate) and whenever there is a change in the rate at which a particular line has connected up (but most preferably only when the change exceeds a minimum threshold), the DSLAM (or, in an alternative embodiment, a management device acting as an intermediary between the DSLAM and a central management device associated with the access network) automatically generates a message indicating the new rate at which the line is connected and transmits this to a management device associated with the access network which can then use the information to make any necessary corresponding changes to other components within the access network, such as a corresponding Broadband Remote Access Server (BRAS). [0009] In certain embodiments, each DSLAM may transmit the messages which it generates to a device such as an element manager or a data collector which interfaces between, or aggregates messages received from, a subset of the total number of DSLAMs operating within the access network and then forwards the (possibly aggregated) messages to a centralised management function (which may be distributed over a number of separate hardware devices) for further processing of the messages and subsequent control of other devices within the access network (and possibly beyond the access network, e.g. to an associated service provider etc.). [0010] The term Digital Subscriber Line Access Multiplexer (DSLAM) is a well known term in the art and the term is used throughout this specification to refer to such devices, but is also intended to include any device housing one or more units (e.g. ATU-C's) which terminate (at the network end of a twisted copper pair line) an XDSL connection (XDSL refers to any of the standards for transmitting much more than 64 kb of data over a copper line, by using frequencies greater than those required for transmitting analogue voice signals, such standards including ADSL SDSL, HDSL and VDSL—further including any further similar standards not yet developed), since subsequent devices might not be known as DSLAMs even though they perform a similar function (i.e. of terminating a number of digital subscriber lines and aggregating them into a higher bandwidth transmission medium of an access network). By comparison with the Technical Report of the DSL Forum TR-059, the term DSLAM as we intend it to be used is more closely aligned to the term “Access Node” used in that document. The term “Access Device or Subsystem” is also intended to be understood in this way. [0011] Further aspects of the invention include processor implementable instructions for causing a processor controlled device to carry out the method of the first aspect of the present invention and carrier means carrying such processor implementable instructions. BRIEF DESCRIPTION OF THE FIGURES [0012] In order that the present invention may be better understood, embodiments thereof will now be described, by way of example only, with reference to the accompanying drawings in which: [0013] FIG. 1 is a schematic block diagram illustrating a telecommunications network incorporating a plurality of DSLAMs according to a first aspect of the present invention; [0014] FIG. 2 is a schematic block diagram illustrating an alternative telecommunications network similar to that of FIG. 1 , but further including a plurality of element manager devices which interface between a subset of the DSLAMs and a management device which ultimately receives messages from the DSLAMs; [0015] FIG. 3 is a schematic block diagram illustrating one of the DSLAMs of FIG. 1 in more detail; and [0016] FIG. 4 is a flow diagram illustrating the steps carried out by the DSLAM of FIG. 3 to generate messages to send to the management device of the network of FIG. 1 . DETAILED DESCRIPTION OF EMBODIMENTS [0017] Referring to FIG. 1 , a first embodiment of the present invention is illustrated in overview. Copper pair loops 19 connect a number of sets of customer premises equipment 10 a , 10 b . . . 10 i . . . 10 n to a smaller number of DSLAMs 20 a . . . 20 i , . . . 20 l . Each DSLAM is typically located within a local exchange (also known as a central office in the US) each of which may house one or more DSLAMs. Each DSLAM 20 separates normal voice traffic and data traffic and sends the voice traffic to the Public Switched Telephone Network (PSTN) 70 . The data traffic is passed on through an Access Network 30 (which will typically be an ATM network as is assumed in this embodiment) toga Broadband Remote Access Server (BRAS) 40 at which several IP traffic flows from (and to) multiple Service Providers (SP's) 62 , 64 , 66 are aggregated (and disaggregated) via an IP network 50 (which may, of course, itself be provided on top of an ATM network). Note that although only a single BRAS is shown, in practice a large access network will include a large number of BRAS's. Within each set of customer premises equipment 10 , there is typically an ADSL splitter filter 18 , a telephone 12 , an ADSL modem 16 and a computer 14 . [0018] In addition to the above mentioned items, in the present embodiment, there is also a management device 100 which communicates between the DSLAMs 20 and the BRAS (or BRAS's) 40 . In the present embodiment, the management device communicates with individual BRAS's via one or more further interface devices 39 each of which communicates directly with one or more BRAS's in order to set user profiles, etc. A detailed understanding of the operation of the management device, the interface device(s) and the BRAS(s) is not required in order to understand the present invention, however, for completeness an overview of their operation is set out below. For a more detailed discussion, the reader is referred to co-pending European patent application No. 05254769.2 the contents of which are incorporated herein by reference. Thus, in overview, the management device 100 obtains information from each DSLAM 20 about the rate at which each Digital Subscriber Line (DSL) connects to the DSLAM (as is discussed in greater detail below, in the present embodiment this is done by each DSLAM generating and transmitting to the management device 100 a message indicating the new line rate each time a line connects up at a speed which differs from the speed at which the line last connected up—or synchronised as this process is commonly termed). [0019] In the present embodiment, the management device then processes this information to assess a consistent connection speed achieved by each such DSL. If it determines that this consistent rate has increased as a result of recent higher rate connections, it instructs the BRAS to allow higher through flows of traffic for that DSL. On the other hand, if it detects that a particular connection speed is below the stored consistent value, it reduces the consistent value to the current connection rate and immediately informs the BRAS of the new consistent value rate so that the BRAS does not allow more traffic to flow to the DSL than the DSL is currently able to cope with. [0020] The exact algorithm used by the management device to calculate the consistent rate in the present embodiment is not pertinent to the present invention and therefore is not described. However, it should be noted that the intention of the algorithm is to arrange that the user will receive data at the highest rate which his/her DSL is consistently able to obtain without requiring the BRAS to be reconfigured every time the DSL is connected. At the same time the algorithm seeks to ensure that if the DSL connects at a rate which is below that at which the BRAS is currently configured to allow data through, then the BRAS is quickly reconfigured to avoid overloading the DSLAM. The reason for wanting to avoid having to contact the BRAS each time a DSL connects to the DSLAM is because with current systems it is not generally possible to reconfigure the BRAS without a significant delay (e.g. of a few minutes). Furthermore, there is a limit to the rate at which a BRAS can process reconfiguration requests. These restrictions are sometimes referred to by saying that the BRAS needs to be provisioned, and drawing a distinction between systems which are switched (e.g. ATM Switched Virtual Circuits) and systems which are provisioned. Current systems allow for quite quick provisioning (often a matter of minutes rather than days or weeks) but there is still a significant difference between such quick provisioning and realtime switching. [0021] FIG. 2 shows an alternative embodiment to that of FIG. 1 which is very similar and common reference numerals have been used to describe common elements. The main difference is simply that in FIG. 2 , instead of the DSLAMs communicating notification messages directly to the management device 100 , an element manager device 25 (which connects to a plurality of DSLAMs) acts as an interface between the DSLAMs and the management device. Note that in a large access network, there may be many DSLAMs and several element managers, each of which may connect to a sub-set of the DSLAMs. Furthermore, additional levels of hierarchy could be imposed where a number of element managers communicate with an element manager manager which then interfaces to the management device, etc. [0022] The embodiment of FIG. 2 can be operated in at least two slightly different ways in order to generate and transmit notifications to the management device 100 . Firstly, each DSLAM can perform monitoring and determine whenever a condition or set of conditions has arisen which requires a notification to be passed to the management device 100 in which case the DSLAM can generate the notification and send it to the element manager 25 (using, for example the well known SNMP protocol as illustrated in FIG. 2 ) whereupon the element manager 25 then simply forwards on the notification message to the management device (e.g. using a Remote Procedure Call (a well known Java based protocol) as illustrated in FIG. 2 ). Alternatively, each DSLAM can simply forward on a notification to the element manager each time a DSL synchronises (again for example using SNMP) and the element manager can process this information to determine if a notifiable event has occurred (e.g. such as the synchronisation line rate for a particular line having changed). Then if the element manager determines that such an event has occurred, it can generate and transmit (again using, for example an RPC) a suitable notification message to the management device 100 . In this latter method of operation, a group of DSLAMs and their corresponding element manager form an access sub-system within the meaning of the term as used in the appended claims. [0023] Referring now to FIG. 3 , this shows a DSLAM of FIG. 1 (or FIG. 2 ) in slightly more detail. Each incoming DSL line terminated by the DSLAM enters the DSLAM at one of a plurality of input ports in an interface module 209 , which connects these to a plurality of modems, in this case a plurality of ADSL Terminating Units—Central office side (ATU-C's) 210 a - n. The ATU-C's are connected to an ATM switch for forwarding on the data (in the form of ATM cells in the present embodiment) to an ATM switch 230 which switches the resulting cells onto the ATM access network 30 . Within the DSLAM, there is a control unit 220 which includes a processor unit 222 and a data store 224 . The control unit 220 performs various control functions including ensuring that each time a connection is made over a particular DSL that it complies with a stored profile for that line. As is well known within the field of xDSL, each line is set up according to a DSL profile which specifies various parameters necessary for establishing an xDSL connection. [0024] In the present embodiment, the control unit 220 additionally performs the function of monitoring each DSL, determining if it has re-synchronised at a rate which differs from the rate at which it previously synchronised (or re-synchronised) and, if so, generating a notification message to send to the management device 100 (or to an element manager or other intermediate device in alternative embodiments including such devices). The steps carried out in performing this additional function are described below with reference to the flow diagram of FIG. 4 . [0025] Thus, upon initiation of the method illustrated in FIG. 4 when a DSL line connected to the DSLAM is provisioned for monitoring by this new function (e.g. because the end user has opted to move his broadband connection service to a new rate adapted service), the first time it synchronises (step 10 ), the line rate achieved is stored (step S 20 ). The control unit then waits until the next time that the line tries to re-synchronise (step S 30 ) whereupon it determines (step S 40 ) whether the new line rate at which the line has synchronised is the same as that at which it previously synchronised (note that for modems operating in accordance with the ADSL 1 standard, the line rate can only change in steps of 32 Kb (Kilo bits per second), thus only changes of 32 Kb or greater will be detected; in ADSL 2 this reduces to 4 Kb or so) and if so it waits (step S 50 ) until a new re-synchronisation attempt is made whereupon the method loops back to the re-synchronisation step S 30 . If at step S 40 it is determined that the line rate at which the line has re-synchronised is different to that which it has stored (corresponding to the rate at which the line previously re-synchronised), then the control unit generates a notification message in the form of a Simple Network Message Protocol (SNMP) trap which it transmits directly (or indirectly in alternative embodiments) to the management device 100 (step S 60 ). The control unit then stores the new line rate for future comparisons (at step S 70 ) before proceeding to step S 50 to await a new request to resynchronise the line. Naturally, this function is performed in parallel in respect of each line which is terminated by the DSLAM. [0026] The notification message includes a unique identification of the line to which it relates, a date and time stamp indicating when the line resynchronised and the new line rate (specifying both the new upstream rate and the new downstream rate—note that a change in either of these will, in the present embodiment, trigger a notification to be sent, though in alternative embodiments a change in only, say, the downstream rate could trigger such a notification). [0027] It will be understood by a person skilled in the art that a number of different methods may be used to transmit the messages between the DSLAMs, element managers and the management device 100 . In the embodiment of FIG. 1 an SNMP message is sent directly from the DSLAMs to the management device 100 . However many other possibilities exist. For example, in the embodiment of FIG. 2 an SNMP message could be sent from the DSLAMs to the element manager which could then forward on the message using a CORBA interface or by means of a JAVA based Remote Procedure Call. Naturally, many other possibilities will occur to a person skilled in the art of data networking. VARIATIONS [0028] In alternative embodiments, instead of generating and sending notifications of changes of line rate equal to the granularity of the xDSL standard used, notifications could only be sent if the change is above a specified magnitude of change threshold (which could vary in dependence on the absolute value of the line rate). In this way, the number of notifications generated and sent could be reduced. Preferably, the threshold could be set to equal the threshold used for the purposes of reprovisioning the BRAS by the management device 100 , which, in the present embodiment, is done in steps of 500 Kb. [0029] Instead of, or in addition to, sending notifications of a change of line rate, a notification could be sent each time a line re-synchronises. This could be useful for identifying lines which are frequently going down, perhaps because the provisioning is incorrect and needs to be changed (e.g. to force the line to connect at a lower rate rather than at the maximum achievable rate). [0030] Instead of, or in addition to, sending notifications of a change of line rate, the DSLAM or an element manager or other interface type device could monitor whether a particular line has had to re-synchronise more than a certain given number of times within a certain given period such as, for example, more than 10 times within an hour and send a notification to the management device whenever this condition is detected as occurring.
A Digital Subscriber Line Access Multiplexer (DSLAM) is modified to monitor when a line synchronizes (i.e. sets up a DSL connection) and to automatically generate a notification to be sent to a management device of the access network if the rate has changed from the last time the line synchronized.
8
INCORPORATION BY REFERENCE [0001] The present application is a divisional of U.S. patent application Ser. No. 11/128,852, filed May 13, 2005, which claims priority under 35 U.S.C. §119 to Korean Patent Application No. 2004-74872 filed on Sep. 18, 2004. The contents of both applications are incorporated herein by reference in their entirety. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates, in general, to a printed circuit board (PCB) and a method of fabricating the same and, more particularly, to a PCB and a method of fabricating the same, in which a contact portion is formed on an internal layer of the multi-layered PCB, a groove is formed so as to expose the contact portion of the internal layer, and a chip package is mounted on the PCB while being flip-chip bonded to the exposed contact portion of the internal layer. [0004] 2. Description of the Prior Art [0005] A semiconductor package is exemplified by a resin seal package, a tape carrier package (TCP), a glass seal package, and a metal seal package. Furthermore, the semiconductor package is classified into a TH-type, in which a hole is formed through a PCB and a pin is inserted into the hole, and a surface mounting technology (SMT) type, in which it is mounted on a surface of a PCB, according to a mounting method thereof. [0006] The TH-type is the typical integrated circuit (IC) package which has been used for the longest time, and representative examples include a dual inline package (DIP), in which a plurality of pins protrude from both sides of the package in a straight line, and a pin grid array (PGA), in which pins are arranged on the underside of a large hexahedron. [0007] The SMT-type is a package having a structure in which, when a packaged chip is electrically connected to a substrate, the electric connection is achieved on the substrate unlike the TH-type, in which the pin is inserted into the hole and soldered. [0008] Compared to the TH-type, the SMT-type is advantageous in that, assuming that chips having the same size are employed, the mounting area is reduced because of the small size, it is thin and lightweight, and operation speed improves with an increase in frequency because of a low parasitic capacitance or inductance. [0009] Other advantages are that it is unnecessary to form a hole, a soldering region and a pitch can be reduced, it is possible to achieve highly dense wiring and mounting, and the cost of fabricating a PCB can be reduced. However, the SMT-type is disadvantageous in that it is difficult to inspect the appearance of a soldered part. [0010] Representative examples of the SMT-type package include a quad flat package (QFP), a plastic leaded chip carrier (PLCC), a ceramic leaded chip carrier (CLCC), and a ball grid array (BGA). [0011] Meanwhile, there are some limits with respect to the size and thickness of a PCB in the course of mounting many parts on the PCB. Recently, demand for slim mobile devices which are handy to carry is growing, and thus, it is necessary to arrange integrated and passive components in a space having a restricted area and height on a surface of the PCB. [0012] A thin chip may be fabricated to satisfy such a necessity. In this case, however, handling problems and signal interference problems between layers may occur. [0013] In other words, multiple layers of integrated circuit chips are integrated in one conventional integrated circuit chip package. At this time, the integrated circuit chip must be very thin in order to insert many layers of chips into a package having a restricted thickness. However, since the integrated circuit chip is very thin, it is difficult to handle the chip and signal interference problems between the integrated circuit chips occur. [0014] Meanwhile, a technology of embedding an integrated circuit chip in a PCB has been suggested to compensate for insufficient space. [0015] With respect to the above technology, Japanese Pat. Laid-Open Publication No. 11-274734 discloses an electronic circuit device which is provided with a circuit substrate that acts as a core, electronic parts mounted on the circuit substrate, an insulating layer formed on the circuit substrate, and a circuit formed on the insulating layer. [0016] FIG. 1 is a sectional view of a conventional PCB having a chip mounted thereon. [0017] Referring to FIG. 1 , in the conventional PCB having the chip mounted thereon, a circuit substrate 10 is used as a core, and circuit patterns 12 , 18 are formed on upper and lower sides of the circuit substrate. [0018] A through hole 13 is formed through the circuit substrate 10 to connect external and internal circuits to each other. A chip 16 is flip-chip bonded to the circuit substrate 10 and thus mounted on it. A welding bump 17 formed on a pad of the integrated circuit chip 16 is connected to a land 18 on the circuit substrate 10 . [0019] Additionally, a plurality of insulating layers 22 is laminated on the circuit substrate 10 , and a circuit pattern 25 is formed on each of the insulating layers 22 . [0020] At this stage, an integrated circuit chip 29 is mounted on an external surface of the outermost layer 22 of the insulating layers 22 , and connected to a wire pattern on the surface of the outermost insulating layer 22 . [0021] However, in the conventional technology of embedding the integrated circuit chip in the PCB, it is difficult to form a passage for emitting heat, and thus, it is hard to apply the technology to an integrated circuit chip which generates a lot of heat. [0022] Furthermore, since it is necessary to control occurrence of dust during the fabrication of the PCB to be the same level as that during the fabrication of a semiconductor, undesirably, clean room facilities must be newly installed or the level of dust must be tightly controlled. SUMMARY OF THE INVENTION [0023] Therefore, the present invention has been made keeping in mind the above disadvantages occurring in the prior arts, and an object of the present invention is to provide a PCB and a method of fabricating the same. In the method, a contact portion, on which a chip package is to be mounted, is formed in the PCB, the lamination of layers is conducted so that the contact portion formed on an internal layer of a substrate is exposed, and the chip package is flip-chip bonded to the contact portion of the internal layer, thereby mounting the thick chip package in a space having a restricted height on a surface of the substrate. [0024] The above object can be accomplished by providing a PCB having a chip package mounted thereon, which comprises a substrate having a plurality of electric contact portions formed on an upper side thereof and acting as a core. The chip package is mounted on the substrate and has bumps connected to the electric contact portions. An insulating layer is laminated on the substrate and has a hole in which the chip package is to be mounted. [0025] Furthermore, the present invention provides a method of fabricating a PCB having a chip package mounted thereon. The method includes the steps of forming a first etching resistor to form an electric contact portion on an upper side of a first circuit layer on one side of a substrate; applying a first photosensitive substance on the first circuit layer of the substrate to form a first circuit pattern on the first circuit layer, and removing the first photosensitive substance; laminating an insulating layer and a second circuit layer on the substrate, and forming a hole through a portion of the insulating layer, in which the chip package is to be mounted; applying a second photosensitive substance to form a second circuit pattern on the second circuit layer, and forming the electric contact portion on the exposed first circuit layer of the substrate, on which the first etching resistor is formed; and mounting the chip package so that the chip package is connected to the electric contact portion formed on an exposed internal layer of the substrate. [0026] Furthermore, the present invention provides a method of fabricating a PCB having a chip package mounted thereon. The method includes the steps of laminating an insulating layer and a first circuit layer on an upper side of a second circuit layer on one side of a substrate, on which a first circuit pattern is formed; removing portions of the insulating layer and the first circuit layer laminated on the substrate, which have a position corresponding to an area in which the chip package is to be mounted; applying a photosensitive substance on internal and external layers so that the photosensitive substance adheres closely to the internal and external layers, and forming a second circuit pattern on the photosensitive substance to form an electric contact portion and to form a third circuit pattern on the external layer; conducting an etching process using the second circuit pattern, formed on the photosensitive substance, to form the third circuit pattern on the external layer and to form the electric contact portion on the internal layer; and mounting the chip package so that the chip package is connected to the electric contact portion formed on the exposed second circuit layer of the substrate. [0027] Furthermore, the present invention provides a method of fabricating a PCB having a chip package mounted thereon. The method includes the steps of forming a first circuit pattern, which includes an electric contact portion, to be connected to the chip package, on a first circuit layer of a substrate; laminating an insulating layer and a second circuit layer on an upper side of the first circuit layer on one side of the substrate, on which the first circuit pattern is formed; removing portions of the insulating layer and the second circuit layer laminated on the substrate, which have a position corresponding to an area in which the chip package is to be mounted; and mounting the chip package so that the chip package is connected to the electric contact portion formed on the exposed first circuit layer of the substrate. [0028] Furthermore, the present invention provides a method of fabricating a PCB having a chip package mounted thereon. The method includes the steps of forming a first circuit pattern, which includes an electric contact portion, to be connected to the chip package, on a first circuit layer of a substrate; surrounding the electric contact portion using an etching resistor; laminating an insulating layer, through which a hole is formed so as to mount the chip package therein while the chip package being connected to the electric contact portion, and laminating a second circuit layer on the insulating layer; laminating a photosensitive substance on the second circuit layer, forming a second circuit pattern, of which a portion, having a position corresponding to the hole, is removed, on the photosensitive substance, and etching the resulting substrate to form a third circuit pattern on the second circuit layer; and mounting the chip package so that the chip package is connected to the electric contact portion formed on the exposed first circuit layer of the substrate. BRIEF DESCRIPTION OF THE DRAWINGS [0029] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: [0030] FIG. 1 is a sectional view of a conventional PCB having a chip mounted thereon; [0031] FIG. 2 is a sectional view of a PCB having a chip package mounted thereon according to an embodiment of the present invention; [0032] FIGS. 3 a to 3 p are sectional views illustrating the fabrication of the PCB having the chip package mounted thereon according to an embodiment of the present invention; [0033] FIGS. 4 a to 4 q are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to a further embodiment of the present invention; [0034] FIGS. 5 a to 5 k are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to another embodiment of the present invention; [0035] FIGS. 6 a to 6 l are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to a further embodiment of the present invention; [0036] FIGS. 7 a to 7 l are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to another embodiment of the present invention; [0037] FIGS. 8 a to 8 m are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to a further embodiment of the present invention; and [0038] FIGS. 9 a to 9 d are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0039] Hereinafter, a detailed description will be given of the present invention with reference to FIGS. 2 to 9 d. [0040] FIG. 2 is a sectional view of a PCB having a chip package mounted thereon according to an embodiment of the present invention. [0041] Referring to FIG. 2 , the PCB having the chip package mounted thereon according to an embodiment of the present invention comprises a copper clad laminate 210 acting as a core, a plurality of insulating layers 231 , 233 laminated on the copper clad laminate 210 , a plurality of circuit layers 232 , 234 , solder resist films 240 , 241 applied on the external circuit layers 232 , 234 and an exposed internal circuit layer 212 , a chip package 250 , and a conductive material 242 interposed between bumps 251 of the chip package 250 and contact portions of the internal circuit layer 212 . [0042] The copper clad laminate 210 is made of an insulating material, and comprises an insulating layer 211 having a predetermined thickness, and copper foil layers 212 , 213 positioned on both sides of the insulating layer 211 and having circuit patterns. [0043] In this respect, the contact portions, to which the bumps 251 of the chip package 250 are capable of being flip-chip bonded, are formed on the copper foil layer 212 on one side of the insulating layer 211 . The contact portions are electrically connected to other portions 213 through holes 214 . [0044] Additionally, a groove, which corresponds in size to the chip package 250 , is formed on the insulating layer 231 laminated on an upper side of the copper clad laminate 211 so that the chip package 250 is flip-chip bonded to the contact portions formed in the internal circuit layer 212 . Furthermore, the contact portions of the internal circuit layer 212 are exposed. [0045] The chip package 250 is flip-chip bonded through the groove to the contact portions using the bumps 251 attached thereto, thereby being mounted on the PCB. [0046] At this stage, the electric conductive material 242 may be applied so as to improve the adhesion strength between the bumps 251 of the chip package 250 and the contact portions. [0047] Furthermore, the solder resist may be applied on the external circuit layers 232 and the exposed internal circuit layer 212 . [0048] As well, as shown in FIG. 2 , a side wall connection is feasible by use of a lead frame, and thus, it is possible to assure many channels for signal connection. [0049] FIGS. 3 a to 3 p are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to an embodiment of the present invention. [0050] Referring to FIG. 3 a , a circuit substrate 310 acting as a core is provided. The circuit substrate 310 is made of an insulating material, and comprises an insulating layer 311 , having a predetermined thickness, and copper foil layers 312 , 313 positioned on upper and lower sides of the insulating layer 311 . Furthermore, a plurality of through holes 314 is formed through the circuit substrate 310 to connect circuits on both sides of the circuit substrate to each other. [0051] With reference to FIGS. 3 b and 3 c , photosensitive substances 321 , 322 are applied on the copper foil layers 312 , 313 of the circuit substrate 310 . Subsequently, the upper photosensitive substance 321 is selectively removed through exposure and development processes to expose a portion of the copper foil layer 312 which is not to be removed, thereby forming a portion on which the chip package is to be mounted. Such a photolithography process may be classified into a photographic process and a screen printing process. Employing an art work film having a circuit pattern printed thereon, the photographic process is divided into a dry film (D/F) process using a dry film as a photosensitive material, and a photosensitive liquid process using photosensitive liquid. [0052] Referring to FIG. 3 d , an etching resistor 323 , which is capable of being used as a resistor during a copper etching process using gold or nickel, is applied on the exposed portion of the copper foil layer so as to prevent the copper foil layer from being etched when the copper etching process is conducted using gold or nickel, thereby providing an electric connection to the chip package to be mounted. At this time, it is preferable to form the etching resistor 323 through a plating process. [0053] Referring to FIG. 3 e , the photosensitive substances 321 , 322 are removed from both sides of the copper foil layers 312 , 313 using a stripping process, and photosensitive substances 324 , 325 are further applied to form a circuit as shown in FIG. 3 f. [0054] At this time, a portion of the photosensitive substances 324 , 325 corresponding in position to an area in which the chip package is to be mounted is not etched. However, the remaining portion, under which the copper foil layer is to be etched, is exposed and developed to expose a portion of the copper foil layer to be etched, as shown in FIG. 3 g. [0055] As shown in FIG. 3 h , after a circuit pattern of the copper foil is formed using circuit patterns of the photosensitive substances 324 , 325 as an etching resist, the photosensitive substances 324 , 325 as the etching resist are stripped to complete the formation of the circuit pattern of the copper foil. At this time, the etching resistor 323 must not be removed. [0056] Next, after an etching process is conducted as shown in FIG. 3 i to form a circuit on an internal layer, the photosensitive substances 324 , 325 are removed through a stripping process, and a plurality of insulating layers 331 , 333 and circuit layers 332 , 334 are further laminated. [0057] As shown in FIG. 3 j , in order to remove a portion of the insulating layer 331 , corresponding in position to an area in which the chip package is to be mounted, the copper foil positioned on that portion of the insulating layer 331 is removed through a process using a laser or a plasma. [0058] Subsequently, after a portion of the copper foil, corresponding in position to an area in which the chip package is to be mounted, is removed as shown in FIG. 3 k , a portion of the insulating layer 331 , also corresponding in position to the area in which the chip package is to be mounted, is removed through a process, using a laser or a plasma, capable of removing the insulating layer 331 . At this time, if necessary, it is preferable to control the removal of the insulating layer so as to prevent the resulting substrate from being excessively removed. Additionally, it is preferable that a material of the insulating layer, which is to be removed, be different from that of the insulating layer, which must not be removed, so as to prevent the insulating layer, which must not be removed, from being etched. [0059] As shown in FIG. 31 , photosensitive materials 335 , 336 are applied to form circuits on the outermost layers 332 , 334 . [0060] As shown in FIG. 3 m , the photosensitive materials 335 , 336 are exposed and developed to form circuit patterns thereon. At this time, a portion of the photosensitive materials 335 , 336 , corresponding in position to an area in which the chip package is to be mounted, is removed so that an exposed copper foil portion of the internal layer 312 , corresponding in position to an area in which the chip package is to be mounted, is removed by a copper etching process. [0061] As shown in FIG. 3 n , wire patterns are formed on the external circuit layers 332 , 334 and the exposed internal copper foil layer 312 using the circuit patterns of the photosensitive materials 335 , 336 and the etching resistor 323 as an etching resist. In other words, circuits are formed on a surface of the resulting substrate and the copper foils 312 , 332 , 334 of the internal layer through the etching process. [0062] As shown in FIG. 3 o , after the photosensitive materials 335 , 336 are completely removed through a stripping process, the chip package is mounted on the surface of the internal layer of the substrate. In the case where the etching resistor 323 formed on the internal layer must be removed, the removal may be conducted through an etching resistor stripping process as shown in FIG. 3 p . However, if the etching resistor is formed by gold plating, it is preferable that the etching resistor be not removed. [0063] FIGS. 4 a to 4 q are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to another embodiment of the present invention. [0064] Referring to FIG. 4 a , a circuit substrate 410 acting as a core is provided. The circuit substrate 410 is made of an insulating material, and comprises an insulating layer 411 , having a predetermined thickness, and copper foil layers 412 , 413 positioned on upper and lower sides of the insulating layer 411 . Furthermore, a plurality of through holes 414 is formed through the circuit substrate 410 to connect circuits on both sides of the circuit substrate to each other. [0065] With reference to FIGS. 4 b and 4 c , photosensitive substances 421 , 422 are applied on the copper foil layers 412 , 413 of the circuit substrate 410 . Subsequently, the photosensitive substances 421 , 422 are selectively removed through exposure and development processes to expose a portion of the upper copper foil layer 412 , which is not to be removed, thereby forming a portion on which the chip package is to be mounted. [0066] Referring to FIG. 4 d , an etching resistor 423 , which is capable of being used as a resistor during a copper etching process using gold or nickel, is applied on the exposed portion of the copper foil layer so as to prevent the copper foil layer from being etched when the copper etching process is conducted using gold or nickel, thereby providing an electric connection to the chip package to be mounted. At this time, it is preferable to form the etching resistor 423 through a plating process. [0067] Referring to FIG. 4 e , the photosensitive substances 421 , 422 are removed from both sides of the copper foil layers 412 , 413 using a stripping process, and photosensitive substances 424 , 425 are further applied to form a circuit as shown in FIG. 4 f. [0068] At this stage, a portion of the photosensitive substances 424 , 425 , corresponding in position to an area in which the chip package is to be mounted, is not etched. However, the remaining portion, under which the copper foil layer is to be etched, is exposed and developed to expose a portion of the copper foil layer to be etched, as shown in FIG. 4 g. [0069] As shown in FIG. 4 h , after a circuit pattern of the copper foil is formed using circuit patterns of the photosensitive substances 424 , 425 as an etching resist, the photosensitive substances 424 , 425 as the etching resist are stripped to complete the formation of the circuit pattern of the copper foil. [0070] Next, after an etching process is conducted as shown in FIG. 4 i to form a circuit on an internal layer, the photosensitive substances 424 , 425 are removed through a stripping process, and a plurality of insulating layers 431 , 433 and circuit layers 432 , 434 are further formed. [0071] As shown in FIG. 4 j , in order to remove a portion of the insulating layer 431 corresponding in position to an area in which the chip package is to be mounted, a portion of the copper foil, which is positioned on such portion of the insulating layer 431 , is removed through a process using a laser or a plasma. [0072] Subsequently, after a portion of the copper foil, corresponding in position to an area in which the chip package is to be mounted, is removed as shown in FIG. 4 k , a portion of the insulating layer 431 , corresponding in position to an area in which the chip package is to be mounted, is removed through a process, using a laser or a plasma, capable of removing the insulating layer 431 . At this stage, if necessary, it is preferable to control the removal of the insulating layer so as to prevent the resulting substrate from being excessively removed. Additionally, it is preferable that the material of the insulating layer, which is to be removed, be different from that of the insulating layer, which must not be removed, so as to prevent the insulating layer, which must not be removed, from being etched. [0073] As shown in FIG. 41 , photosensitive materials 435 , 436 are applied to form circuits on the outermost layers 432 , 434 . [0074] As shown in FIG. 4 m , the photosensitive materials 435 , 436 are exposed and developed to form circuit patterns thereon. At this stage, a portion of the photosensitive materials 435 , 436 , corresponding in position to an area in which the chip package is to be mounted, is not removed. [0075] As shown in FIG. 4 n , etching resistors 437 , 438 are applied on the circuit patterns formed on the photosensitive materials 435 , 436 using exposure and development processes. At this stage, it is preferable that the application of the etching resistors 437 , 438 be conducted by a plating process. [0076] As shown in FIG. 4 o , the photosensitive materials 435 , 436 are removed so as to form wire patterns on the copper foil using the circuit patterns of the etching resistors 437 , 438 as an etching resist. [0077] As shown in FIG. 4 p , after the photosensitive materials 435 , 436 are removed through a stripping process, circuits are formed on a surface of the resulting substrate and the copper foils 412 , 413 , 432 , 434 of the internal layer through an etching process employing the etching resistors 437 , 438 as the etching resist. [0078] As shown in FIG. 4 q , after the etching resistors 437 , 438 are completely removed through a stripping process, the chip package is mounted on the surface of the internal layer of the substrate. In case that the etching resistor 423 formed on the internal layer must be removed as shown in FIG. 4 q , the removal may be conducted through an etching resistor stripping process. However, if the etching resistor is formed by a gold plating, it is preferable that the etching resistor not be removed. [0079] FIGS. 5 a to 5 k are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to another embodiment of the present invention. [0080] Referring to FIG. 5 a , a circuit substrate 510 acting as a core is provided. The circuit substrate 510 is made of an insulating material, and comprises an insulating layer 511 , having a predetermined thickness, and copper foil layers 512 , 513 positioned on upper and lower sides of the insulating layer 511 . Furthermore, a plurality of through holes 514 is formed through the circuit substrate 510 to connect circuits on both sides of the circuit substrate to each other. [0081] With reference to FIGS. 5 b and 5 c , photosensitive substances 521 , 522 are applied on the copper foil layers 512 , 513 of the circuit substrate 510 . Subsequently, circuit patterns are formed on a portion of the photosensitive substances 521 , 522 , corresponding in position to an area in which the chip package is not mounted, through a photolithography process, and another circuit patterns are formed on the copper foil layers 512 , 513 using the photosensitive substances 521 , 522 as an etching resist. [0082] As shown in FIG. 5 d , the photosensitive substances 521 , 522 are removed through a stripping process, and a plurality of insulating layers 531 , 533 and circuit layers 532 , 534 are further formed as shown in FIG. 5 e. [0083] As shown in FIG. 5 f , in order to remove a portion of the insulating layer 531 , corresponding in position to an area in which the chip package is to be mounted, photosensitive substances 535 , 536 are applied on the outermost layers 532 , 534 . [0084] As shown in FIG. 5 g , in order to remove a portion of the insulating layer 531 , corresponding in position to an area in which the chip package is to be mounted, the photosensitive substance 535 is exposed and developed to be removed at a portion thereof, corresponding in position to the area in which the chip package is to be mounted. Subsequently, an etching process is conducted to remove a portion of the copper foil layer 532 of the outermost layer, corresponding in position to the area in which the chip package is to be mounted. [0085] After the function of the photosensitive substance 531 is completed, the photosensitive substance is removed by a stripping process as shown in FIG. 5 h . Subsequently, a portion of the insulating layer 531 , corresponding in position to an area in which the chip package is to be mounted, is removed through a process, using a laser or a plasma, capable of removing the insulating layer 531 . Furthermore, photosensitive materials 537 , 538 are applied on a surface of the resulting substrate to form circuits on external layers. [0086] As shown in FIG. 5 i , circuits are formed on the photosensitive materials 537 , 538 through exposure and development processes. At this time, in the exposure process, a portion of the photosensitive materials 537 , 538 , corresponding in position to an area in which the copper foil must not be removed, may be hardened using radiation that travels very straight, such as UV radiation, X-rays, or a laser. [0087] As well, as shown in FIG. 5 j , the copper foil 532 on a surface of the resulting substrate, and the copper foil 512 of the internal layer, on which the chip package is to be mounted, are simultaneously etched through an etching process employing the photosensitive materials 537 , 538 as an etching resist. [0088] As shown in FIG. 5 k , after the photosensitive materials are completely removed through a stripping process, the chip package is mounted on a surface of the internal layer of the substrate. [0089] FIGS. 6 a to 6 l are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to another embodiment of the present invention. [0090] Referring to FIG. 6 a , a circuit substrate 610 acting as a core is provided. The circuit substrate 610 is made of an insulating material, and comprises an insulating layer 611 , having a predetermined thickness, and copper foil layers 612 , 613 positioned on upper and lower sides of the insulating layer 611 . Furthermore, a plurality of through holes 614 is formed through the circuit substrate 610 to connect circuits on both sides of the circuit substrate to each other. [0091] With reference to FIGS. 6 b to 6 d , photosensitive substances 621 , 622 are applied on the copper foil layers 612 , 613 of the circuit substrate 610 . Subsequently, circuit patterns are formed on the photosensitive substances 621 , 622 through a photolithography process, and other circuit patterns are then formed on the copper foil layers 612 , 613 using the photosensitive substances 621 , 622 as an etching resist. Thereby, the circuit patterns are formed on a portion of the internal layers 612 , 613 , corresponding in position to an area in which the chip package is to be mounted, and another portion of the internal layers. [0092] As shown in FIG. 6 e , the photosensitive substances 621 , 622 are removed through a stripping process, and a plurality of insulating layers 631 , 633 and circuit layers 632 , 634 is further formed as shown in FIG. 6 f. [0093] As shown in FIG. 6 g , in order to remove a portion of the insulating layer 631 , corresponding in position to an area in which the chip package is to be mounted, photosensitive substances 635 , 636 are applied on the outermost layers 632 , 634 . [0094] As shown in FIG. 6 h , in order to remove a portion of the insulating layer 631 , corresponding in position to an area in which the chip package is to be mounted, the photosensitive substance 635 is exposed and developed to be removed at a portion thereof, corresponding in position to the area in which the chip package is to be mounted. Subsequently, an etching process is conducted to remove a portion of the copper foil layer 632 of the outermost layer, corresponding in position to the area in which the chip package is to be mounted. [0095] After the function of the photosensitive substance 635 is completed, the photosensitive substance is removed through a stripping process as shown in FIG. 6 i . Subsequently, as shown in FIG. 6 j , a portion of the insulating layer 631 , corresponding in position to an area in which the chip package is to be mounted, is removed through a process capable of removing the insulating layer 631 using a laser or a plasma. [0096] As shown in FIG. 6 k , photosensitive materials 637 , 638 are applied on a surface of the resulting substrate, and exposure and development processes are then conducted to form circuit patterns on external layers. Since the circuit pattern is already formed on the internal layer 612 , on which the chip package is to be mounted, the circuit patterns are formed on a portion of the external layers, on which the chip package is not to be mounted. At this time, in the exposure process, a portion of the photosensitive materials 637 , 638 , corresponding in position to an area in which the copper foil must not be removed, may be hardened using radiation that travels very straight, such as UV radiation, X-rays, or a laser. [0097] As shown in FIG. 6 l , after the copper foil 632 on a surface of the resulting substrate is etched through an etching process employing the photosensitive materials 637 , 638 as an etching resist, and the photosensitive materials are completely removed through a stripping process, the chip package is mounted on a surface of the internal layer of the substrate. [0098] FIGS. 7 a to 7 l are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to another embodiment of the present invention. [0099] Referring to FIG. 7 a , a circuit substrate 710 acting as a core is provided. The circuit substrate 710 is made of an insulating material, and comprises an insulating layer 711 , having a predetermined thickness, and copper foil layers 712 , 713 positioned on upper and lower sides of the insulating layer 711 . Furthermore, a plurality of through holes 714 is formed through the circuit substrate 710 to connect circuits on both sides of the circuit substrate to each other. [0100] With reference to FIGS. 7 b to 7 d , photosensitive substances 721 , 722 are applied on the copper foil layers 712 , 713 of the circuit substrate 710 . Subsequently, circuit patterns are formed on the photosensitive substances 721 , 722 through a photolithography process, and other circuit patterns are then formed on the copper foil layers 712 , 713 using the photosensitive substances 721 , 722 as an etching resist. Thereby, the circuit patterns are formed on a portion of the internal layers 712 , 713 , corresponding in position to an area in which the chip package is to be mounted, and another portion of the internal layers. [0101] As shown in FIG. 7 e , the photosensitive substances 721 , 722 are removed through a stripping process. [0102] As shown in FIG. 7 f , photosensitive substances 723 , 724 are applied to achieve the selective application of an etching resistor 725 . [0103] As shown in FIG. 7 g , the photosensitive substance 723 is exposed and developed to expose a portion on which the etching resistor 725 is to be applied. [0104] As shown in FIG. 7 h , after the etching resistor 725 is applied, the photosensitive substances 723 , 724 are removed through a stripping process. At this stage, it is preferable that the application of the etching resistor 725 be conducted using a plating process. [0105] As shown in FIG. 7 i , a plurality of insulating layers 726 , 728 and circuit layers 727 , 729 are further formed. In this regard, a portion of the insulating layer 726 , in which the chip package is to be mounted, is already removed, and a portion of the copper foil layer 727 , corresponding in position to that portion of the insulating layer, remains. Accordingly, it is unnecessary to etch that portion of the insulating layer 726 to mount the chip package in the insulating layer. [0106] As shown in FIG. 7 j , photosensitive substances 730 , 731 are applied on the outermost layers 727 , 729 to form a circuit pattern on the outermost layer 727 . [0107] As shown in FIG. 7 k , the photosensitive substance 730 is exposed and developed to be removed at a portion thereof, which corresponds in position to the circuit pattern of the outermost layer 727 , so as to form the circuit pattern on the outermost layer 727 . At this stage, a portion of the photosensitive substance 730 , corresponding in position to an area in which the chip package is to be mounted, is completely removed. [0108] Furthermore, an etching process is conducted using the photosensitive substance 730 as an etching resist to remove a portion of the copper foil layer 727 of the outermost layer, corresponding in position to the circuit pattern of the photosensitive substance 730 . [0109] After the function of the photosensitive substance 730 is completed, the photosensitive substance is removed through a stripping process as shown in FIG. 7 l . Thereby, it is possible to mount the chip package on a surface of the internal layer of the substrate. [0110] FIGS. 8 a to 8 m are sectional views illustrating the fabrication of a PCB having a chip package mounted thereon according to another embodiment of the present invention. [0111] Referring to FIG. 8 a , a circuit substrate 810 acting as a core is provided. The circuit substrate 810 is made of an insulating material, and comprises an insulating layer 811 , having a predetermined thickness, and copper foil layers 812 , 813 positioned on upper and lower sides of the insulating layer 811 . Furthermore, a plurality of through holes 814 is formed through the circuit substrate 810 to connect circuits on both sides of the circuit substrate to each other. [0112] With reference to FIGS. 8 b to 8 d , photosensitive substances 821 , 822 are applied on the copper foil layers 812 , 813 of the circuit substrate 810 . Subsequently, circuit patterns are formed on the photosensitive substances 821 , 822 through a photolithography process, and other circuit patterns are then formed on the copper foil layers 812 , 813 using the photosensitive substances 821 , 822 as an etching resist. Thereby, the circuit patterns are formed on a portion of the internal layers 812 , 813 , corresponding in position to an area in which the chip package is to be mounted, and another portion of the internal layers. [0113] As shown in FIG. 8 e , the photosensitive substances 821 , 822 are removed through a stripping process. [0114] As shown in FIG. 8 f , photosensitive substances 823 , 824 are applied to achieve the selective application of an etching resistor 825 . [0115] As shown in FIG. 8 g , the photosensitive substance 823 is exposed and developed to expose a portion on which the etching resistor 825 is to be applied. [0116] As shown in FIG. 8 h , after the etching resistor 825 is applied, the photosensitive substances 823 , 824 are removed through a stripping process. At this stage, it is preferable that the application of the etching resistor 825 be conducted using a plating process. [0117] As shown in FIG. 8 i , a plurality of insulating layers 826 , 827 is further laminated. In this regard, a portion of the insulating layer 826 , in which the chip package is to be mounted, is already removed. Accordingly, it is unnecessary to etch that portion of the insulating layer 826 to mount the chip package in the insulating layer. [0118] As shown in FIG. 8 j , electroless and electrolytic copper plating processes are conducted to form plating layers 828 , 829 . [0119] As shown in FIG. 8 k , photosensitive substances 830 , 831 are applied on the outermost layers 828 , 829 to form circuit patterns on the plating layers 828 , 829 . [0120] As shown in FIG. 81 , the photosensitive substance 830 is exposed and developed to be removed at a portion thereof, which corresponds in position to the circuit patterns of the plating layers, so as to form the circuit patterns on the plating layers 828 , 829 . At this time, a portion of the photosensitive substance 830 , corresponding in position to an area in which the chip package is to be mounted, is completely removed. [0121] Furthermore, an etching process is conducted using the photosensitive substance 830 as an etching resist to remove a portion of the copper foil layer 828 of the outermost layer, corresponding in position to the circuit pattern of the photosensitive substance 830 . [0122] After the function of the photosensitive substance 830 is completed, the photosensitive substance is removed through a stripping process as shown in FIG. 8 m . Thereby, it is possible to mount the chip package on a surface of the internal layer of the substrate. [0123] Meanwhile, a process of FIGS. 9 a to 9 d may be further conducted in all the above embodiments of the present invention. [0124] FIGS. 9 a to 9 c are sectional views illustrating the fabrication of a PCB having an integrated circuit chip mounted thereon according to yet another embodiment of the present invention. [0125] Referring to FIG. 9 a , a solder resist ink 940 is applied to an entire side of a PCB from which a portion of an insulating layer 931 , in which a chip package is to be mounted, is removed according to the procedures of the preceding embodiments. [0126] With reference to FIG. 9 b , a solder resist layer 940 , formed by the solder resist ink applied to the PCB, is removed at a portion thereof, which corresponds in position to solders 951 of the chip package or shown in FIG. 9 d. [0127] As shown in FIG. 9 c , an electric conductive material or a nonconductive material 942 may be applied on a copper foil layer 912 partially exposed by removing a portion of the solder resist layer 940 of the PCB so as to prevent oxidation of the copper foil layer and to improve adhesion strength between parts to be mounted on the PCB and the copper foil layer. At this stage, it is preferable that the application of the material be conducted through gold plating. [0128] As shown in FIG. 9 d , the chip package 950 is mounted using a flip chip on the PCB. [0129] The fabrication of a PCB of the present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. [0130] As described above, the present invention is advantageous in that since a finished chip package is mounted on a PCB, the required degree of cleanliness is reduced, eliminating the necessity for additional devices and costs. [0131] Another advantage of the present invention is that since it is possible to position a chip closer to an electric power source layer, the occurrence of noise caused by interference can be reduced. [0132] Still another advantage of the present invention is that connection is feasible through side walls of the package as well as through the bottom of the package because of the use of a lead frame, and thus, it is possible to provide many channels for signal connection.
Disclosed is a printed circuit board (PCB) and a method of fabricating the same. A contact portion is formed on an internal layer of the multi-layered PCB. A groove is formed so as to expose the contact portion of the internal layer. A chip package is mounted on the PCB while being flip-chip bonded to the exposed contact portion of the internal layer.
8
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to a clutch mechanism for an automatic washer and specifically to a device for providing a drive connection to a wash basket during selected portions of a wash cycle. 2. Description of the Prior Art In the drive of an automatic washer, the agitator is driven selectably in a back and forth oscillating agitating motion or in a single direction spinning motion depending upon the particular portion of the wash cycle: the wash, rinse or centrifuge steps. Additionally, the wash basket is selectibly held fixed or caused to spin relative to a wash tub depending upon the particular portion of the wash cycle. Various locking or clutching mechanisms have been disclosed in the prior art which engage or lock an agitator or wash basket to a drive. The description of several references are provided. U.S. Pat. No. 2,167,086 discloses a clutching mechanism which includes a pair of plates which engage corresponding projections. A basket is permitted to be raised or lowered relative to the agitator and a drive shaft connected to the agitator by means of a lever. One plate is raised to engage projections on the bottom of the wash basket and to raise the basket relative to the agitator. The basket is then fixed relative to a wash tub and disengaged from the agitator drive. When the plate is lowered, the basket is lowered and a second set of projections engages a second plate attached to the agitator drive shaft. The first plate is lowered further until it is completely disengaged from the basket. At that time, the wash basket is coupled to the agitator drive for spinning. The agitator is never disengaged from its drive. U.S. Pat. No. 2,219,680 discloses another agitator which is fixedly mounted on a drive shaft. There is included a ring with inwardly extending lugs mounted inside the agitator. A complementary ring with outwardly extending lugs for engaging the inwardly extending lugs is mounted concentrically on the wash basket. During the washing step when only agitation is desired, the agitator is permitted to oscillate, without causing the basket to move, in an arc limited by the space between the two sets of lugs. During the spin step, when it is desired to spin the basket, a continuous rotation of the agitator causes the two sets of lugs to engage and accordingly, the basket to rotate with the agitator. U.S. Pat. No. 2,268,204 discloses a washing machine with a wash tub supported on a spring which deflects vertically downward whenever the tub is sufficiently filled with washing liquid. When it is deflected, a conical member located about a central shaft engages a seat. The arrangement serves to stabilize the tub during washing and at the beginning of the spin step. The drive mechanism which oscillates the agitator is located within the central shaft. Thus, the agitator and basket are driven separately. U.S. Pat. No. 2,665,576 discloses yet another washing machine wherein the agitator is driven by a shaft located within a shaft which separately drives the basket. Gearing devices are used to separately drive the agitator or basket shafts in oscillatory or continuous motion, respectively. It is desirable to provide an automatic washer with means for clutching the basket and agitator drives such that both the agitator and basket are spun together in a spin step while the agitator alone is oscillated or agitated in a wash or rinse step. The art has provided some ways for undertaking this function but all are relatively cumbersome, complicated or expensive. SUMMARY OF THE INVENTION The present invention provides a device which locks a basket to an agitator, which is fixedly mounted on a drive shaft, in response to the level of wash liquid in the basket. Thus, the basket may be driven by the agitator whenever the wash liquid level is such that the basket and agitator are locked together. When the wash liquid is high, as during a washing step, the basket is disengaged or unlocked from the agitator. When the wash liquid is low, as during a spinning step, the basket is locked to the agitator. There is also provided a similar device which locks the wash basket to a wash tub surrounding the basket in response to the wash liquid level in the tub. When the wash liquid level is high, as during a washing step, the basket is locked to the tub to prevent movement of the basket. When the wash liquid level is low, as during a spinning step, the basket is unlocked from the tub to permit the basket to spin to extract liquid from the contents of the basket. The two locking devices are similar in construction and concept but they operate oppositely in response to the wash liquid level. The device which locks the agitator to the basket comprises a deep inverted pocket mounted on the skirt of the agitator and a ring of shallow pockets mounted on the inside of the floor of the basket. Similarly, the device which locks the tub to the basket comprises a deep pocket located in the floor of the tub and a ring of shallow pockets mounted on the bottom side of the floor of the basket. Both devices comprise hollow or light weight articles which float in water. In operation, when the wash liquid in the basket is high, the basket is locked to the tub and the agitator is not locked to the basket. The flotation device of the device for locking the agitator to the basket floats completely without the deep inverted pocket located on the agitator skirt. The flotation device of the device for locking the basket to the tub floats partially within a shallow pocket of the ring located underneath the basket and partially within the deep pocket located on the tub floor. When the wash liquid level is low, the basket is not locked to the tub and the basket is locked to the agitator. The flotation device of the device for locking the basket to the agitator rests partially within a shallow pocket of the ring located inside the basket and protrudes partially into the deep pocket mounted on the agitator skirt. The flotation device of the device for locking the basket to the tub rests completely within the deep pocket located on the tub floor. This arrangement eliminates the need for cumbersome or complex clutching arrangements for drives for the basket and agitator. With the present invention, there need only be provided a single drive shaft coupled to a reversible motor. When the washer is in a wash step, the motor will drive the shaft in an oscillatory fashion. The wash liquid level will be high and the wash basket will not be locked to the agitator. Thus only the agitator will be driven during a washing step. However, when the washer is in a spinning step, or just about ready to go into a spinning step, the wash liquid level will be low and the agitator will be locked to the basket. The basket will be unlocked from the tub and thus, the agitator and basket will be driven together. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of an automatic washing machine, partially cut away, embodying the principles of the present invention. FIG. 2 is a side sectional view through the interior of the washing machine of FIG. 1 and showing the basket locked to the tub. FIG. 3 is a sectional view, partially cut away, of the agitator, wash basket and wash tub of the washer of FIG. 1 wherein the locking rings are shown taken generally along the line III--III of FIG. 2. FIG. 4 is a partial side sectional view of the agitator, wash basket and wash tub of the washer of FIG. 1 showing a flotation device clutching mechanism embodying the principles of the invention with the basket locked to the agitator. FIG. 5 is a partial sectional view taken generally along the line V--V of FIG. 4. FIG. 6 is a partial sectional view taken generally along the line VI--VI of FIG. 4. FIG. 7 is a side elevational view of a locking ring of the washer of FIG. 1. FIG. 8 is a side elevational view of a pocket used in the washer of FIG. 1. FIG. 9 is a sectional view of a flotation device used in a clutch embodying the principles of the invention. FIG. 10 is a plan view of the flotation device of FIG. 9. DESCRIPTION OF THE PREFERRED EMBODIMENT In FIG. 1 there is shown an automatic washer generally at 10 having an outer cabinet 12 to surround and enclose a wash load receptacle. The wash load receptacle comprises an imperforate wash tub 14 and a concentrically mounted inner perforate wash basket 16. A vertical axis agitator 18 is concentrically located within the wash basket 16 and is driven by means of an agitator drive shaft 20, not shown, which extends through the floor of the wash tub 14 and the floor of the wash basket 16. The shaft 20 is driven by a reversible motor 22 as described below. The washer cabinet 12 has a top openable lid 24 and has a console 26 at the rear edge of the top of the washer which includes a plurality of control dials 28 that permit a user to select a series of automatic washing, rinsing and spinning steps. The interior of the washer is shown in greater detail in FIG. 2 where it is seen that the agitator 18 is connected to the shaft 20 by appropriate fastening means which may include a threaded end 30 on the shaft 20 and a corresponding threaded hole 32 in the agitator 18. The shaft 20 extends downwardly into a spin tube 34 and is secured to a drive pulley 36. The pulley 36 is connected by means of a drive belt 38 to a drive pulley 40 mounted on a drive shaft 42 of the reversible motor 22. This type of drive arrangement has many advantages, such as being able to quickly change pulley diameters to cause the machine to run at different speeds, for example, when switching between 60 cycle current and 50 cycle current. The spin tube 34 is mounted on top of brake means 50 such that it is free to rotate thereon. Thus the tube 34 act as a bearing extension so that anything attached to it may also freely rotate about the agitator shaft. The brake 50 is used to stop the agitator shaft from spinning or oscillating at the end of a step or whenever the lid 24 is opened for safety purposes. There is also provided a pump 52 which is used to extract wash liquid from the tub 14. Because the basket 16 is perforate, the pump 52 necessarily extracts wash liquid from the basket 16. The wash liquid is extracted generally, at the end of a wash step, at the end of a rinse step and during a spin step. During a spin step, as is well known in the art, the basket 16 is spun at a high rate of rotation to cause it to act as a centrifuge to extract wash liquid from articles contained therein. The pump 52 is connected to a drain hole, not shown, in the tub 14. The wash tub 14 is shown as being supported by lugs 60 which are secured to lugs 62 on base plate 64 by bolts 66. The wash tub 14 is also secured about center post 67, which surrounds spin tube 34, by sealing means 68. Sealing means 68 comprises two annular rings, 70 and 72 which clamp together about the center hole 74 of the wash tub 14. The wash basket 16 is supported on spin tube 34 by wedge means 80. Wedge means 80 comprises an annular wedge 82 and an annular wedge nut 84. The annular wedge 82 has an annular ring 86 which protrudes inwardly and which hooks onto the end of the spin tube 34. Thus the wedge 82 hangs from the spin tube 34. The wash basket 16 further comprises a central tube 88 with inwardly bent end 90. Because of the shape of the end 90 the wash basket is placed on the wedge 82 such that it too hangs form the spin tube 34. The wedge nut 84 further comprises wedged portion 92 in addition to its inner threaded portion 94. As wedge nut 84 is tightened, the wedged portion 92 is driven into the space between the wedge 82 and the tube end 90 forcing the end 90 downward to fit tightly onto the wedge nut 84 and the wedge 82. Thus the wash basket 16 is made to fit tightly onto spin tube 34 yet is permitted to rotate freely on spin tube 34 about agitator shaft 20. During a normal wash step, the agitator 18 is oscillated about its vertical axis by the reversible motor 22 such that the lower vanes operate as pumping arms to cause a toroidal flow of wash liquid downwardly along the agitator body 100 and outwardly along the skirt 102 and upwardly along the wall 104 of the wash basket. The toroidal flow increases turnover of clothes and the like within the wash basket to enhance washability. Referring now to FIGS. 1-4, the clutching mechanism of the preferred embodiment will be described. There is provided on the agitator skirt 102 a tall or deep inverted pocket 110. Such pocket may be formed concurrently with the agitator 18 such that they comprise an integral article. Alternatively, the pocket 110 may be formed separately from the agitator 18 and secured thereon by means well known in the art. Preferably, both the agitator 18 and the pocket 110 are made of plastic material, however any suitable material may be used withtout departing from the spirit of the invention. The pocket 110 preferably comprises a hollow cylindrical shape with closed top end 112 having an air vent 113 therein. As such, the pocket looks like an inverted cup. An open bottom end 114 of the pocket 110 is angled as is shown most clearly in FIGS. 2, 4 and 8 to match the contour of the agitator skirt through which it extends. There is also provided a ring 120 of short or shallow pockets 122 located on an inside floor 123 of the basket 16 concentrically about agitator shaft 20. The ring 120 is located and sized such that the shallow pockets 122 may be vertically aligned with the deep pocket 110. As is shown in FIGS. 2, 4 and 7, the shallow pockets have angled open top ends 124 and closed bottom ends 126 formed by the basket bottom wall or floor. Placed within the deep pocket 110 is a flotation device 130 which will float in the wash liquid. Whenever the level of wash liquid in the basket 16 is below the height of the ring 120, the flotation device 130 will not float and will rest in one of the shallow pockets 122 of the ring 120. As is shown in FIGS. 4 and 5, the flotation device 130 is much longer than the shallow pockets 122 and therefore, it protrudes into the agitator's deep pocket 110. As such, the flotation device 130 acts like a pin to lock the agitator 18 to the basket 16. However, when the level of wash liquid in the basket 16 is above the level of the ring, the flotation device 130 will float up into the agitator's deep pocket 110. As is shown in FIG. 2, the entire flotation device 130 fits within the deep pocket 110. Hence, when the basket 16 is sufficiently full of wash liquid, the flotation device 130 will disengage from the ring 120 and no longer act as a pin to lock the basket 16 to the agitator 18. It is apparent then that when the basket 16 is sufficiently full of wash liquid, the agitator 18 is permitted to oscillate free of the basket. Conversely, when the basket 16 is sufficiently empty of wash liquid, the basket is locked to the agitator and both will rotate together. As discussed earlier, in FIGS. 2, 4 and 8 it is shown that the open end 114 of pocket 110 and open ends 124 of pockets 122 have angled edges. The open end 114 is aligned with the open ends 124 such that the pocket 110 and any given pocket 122 would form a cylinder. This angling of the open ends provides the best locking capability for a flotation device 130 used in connection with the angled profile agitator skirts used extensively in the industry. As is shown in FIG. 9, the flotation device 130 comprises two cylindrical-conical portions 132 and 134. The conical portions are included to permit the flotation device 130 to more easily penetrate a pocket which may only be partially exposed due to partial alignment between the deep pocket 110 and any given shallow pocket 122. The flotation device 130 is preferably made of a plastic or like material. But, any material which will produce a rigid device which will float in water might be usable. With the use of plastic material, the two cylindrical-conical halves may be formed separately and then sealed together by means well known in the art, such as by spin welding or gluing to produce the device of FIGS. 9 and 10. Moreover, the flotation devices may be of solid construction so long as the specific gravity of the device is less than that of the wash liquid. When the flotation device 130 is in locked position, the conical shape causes it to stand vertically due to the angled profile of the floor of the basket 16. Thus, the angling of the open ends 114 and 124 is provided to cut across as much of the cylindrical surface area of the flotation device 130 as possible so that the greatest amount of the device 130 is located in both the deeper pocket 110 and any given shallower pocket 122. This assures locking. There is also shown in the embodiment of FIGS. 1-4 and 6 another locking mechanism designated generally 150, which is similar to the one described above. The inclusion of this mechanism is optional as it serves merely to lock the basket 16 to the tub 14 but not to any drive means. The mechanism 150 comprises a ring 160 which is similar to the ring 120. However ring 160 is larger in diameter and because of the larger diameter it contains a larger number of shallow pockets 162, that the number of shallow pockets 122. As is shown clearly in FIGS. 2 and 4, the ring 160 is located underneath the basket 16 with open ends 164 of the pockets 162 facing the tub 14. The mechanism 150 further comprises a deep pocket 170 located in the floor of tub 14. An open end 172 of the deep pocket 170 faces the underside of the basket 16 in vertical alignment with a pocket 162. Disposed within the deep pocket 170 is a flotation device 180 which may be exactly the same as flotation device 130. However, in mechanism 150, the flotation device 180 serves to lock the basket to the tub when the wash liquid level is high. It is appreciated from FIGS. 2, 4 and 6, that when there is no wash liquid in the tub 14 above the level of the ring 160, the flotation device 180 does not float and instead rests within deep pocket 170. However, when tub 14 is sufficiently full of wash liquid, the flotation device 180 will float upwards until it engages one of the shallow pockets 162 on ring 160 to lock the tub 14 to the basket 16. Thus, when the washer is in a wash step and full of wash liquid, the basket 16 will be locked to tub 14 and will be prevented from moving in response to agitation of wash liquid. Conversely, when the washer is in a spin step, the basket 16 will not be locked to tub 14 and will be free to spin. Two arrangements may be employed to permit the flotation device 180 to rest within the deeper pocket 170 when the wash liquid is extracted from the wash tub 14. In the first arrangement, shown in the drawings, no drain is provided to permit accumulated liquid to drain from the pocket 170. However, the flotation device 180 is of such specific gravity that it barely floats in the remaining liquid and will be contained within the pocket 170. Thus, the mechanism 150 will unlock when the wash liquid is extracted from the wash tub. Alternatively, a drain line, not shown in the drawings, may be provided to allow fluid communication between the bottom of the pocket 170 and a portion 200 of the wash tub 14 which is below the open end 172 of the pocket 170. Such a drain line would permit all or most of the wash liquid to drain from the pocket 170 and, therefore, allow the flotation device 180 to rest completely within the pocket 170. Additionally, there is no need to utilize a valve with the drain line because it will not be draining when the wash liquid level is at or above the bottom of the pocket 170. It can be appreciated by those in the art that removal of the mechanism 150 from the washer is optional because the basket 16 may be hindered from movement due to agitation of the wash liquid simply by inertia. Mechanism 150 offers a means to ensure prevention of such movement only. It can also be appreciated that a washing machine embodying the principles of the instant invention could comprise the mechanism 150 only, the agitator and tub being driven by alternate means known in the art. Although changes and modifications of the present invention may be apparent to those skilled in the art, it should be understood that such changes and modifications are included within the patent as may reasonably and properly be included within the scope of the present contribution to the art.
The present invention concerns a spin basket clutching device which includes a flotation device which locks the spin basket to an agitator in response to the level of wash liquid in the basket. During a wash step, the basket will be full of liquid and the flotation device floats within an inverted pocket located on the agitator skirt. During a spin step, the basket will be empty of liquid and the flotation device will drop partially out of the inverted pocket and rest partially within a pocket on the spin basket, thus locking the agitator to the spin basket for concurrent rotation. Also disclosed is a device which responds oppositely to the level of wash liquid in the wash tub locking the spin basket to the wash tub to prevent rotation of the basket during agitation of the wash liquid by the agitator during the wash step and unlocking the basket from the tub in a low liquid level step such as spin.
3
BACKGROUND OF THE INVENTION 1. Filed of the Invention This invention relates to automobile wheels. More particularly, it relates to the wheels to be used temporarily in case of damage to a pneumatic tire, or else in case of driving under difficult conditions, such as in mud or snow. 2. Background of the Invention At present, when one of the pneumatic tires mounted on the wheels of a vehicle has suffered a puncture, it is necessary to remove the wheel concerned and replace it with a reserve wheel, commonly called a spare wheel. Another possibility known in the art consists of mounting a spare wheel beside the deflated pneumatic tire, without removing the latter. An illustration of this is found in patent GB 967 397. Hereinafter, such a spare wheel will be called an "auxiliary wheel," and the wheel normally mounted on the vehicle, with which the auxiliary wheel will be paired in case of damage to the pneumatic tire mounted on the main wheel, will be called a "main wheel." These auxiliary wheels have not found practical application, although they are very appealing in theory since the installation operations are simplified relative to the replacement of one wheel by another. The unresolved difficulty in the art consists in reconciling two contradictory requirements. It is necessary that the means of fastening the auxiliary wheel to the main wheel make possible an extremely simple handling for the driver, so that the use of such an auxiliary wheel will confer a major advancement relative to the standard use of a spare wheel. It also is necessary that the means of fastening be solid enough to hold the auxiliary wheel absolutely parallel to the main wheel, so that the use of such an auxiliary wheel can be made with a sufficient level of reliability. Further, the weight and the overall dimensions of such an auxiliary wheel should compare favorably with those of a spare wheel, in particular with a temporary use type spare wheel as is found on some vehicles. It also is necessary that the mounting of the auxiliary wheel on the main wheel does not involve for the latter a substantial increase in weight, a large increase in cost or a deterioration of aesthetic appearance. SUMMARY OF THE INVENTION It is an object of the present invention to provide an auxiliary wheel fastenable to a main wheel so as to provide a spare traveling device. It is a further object of the invention to provide an auxiliary wheel fastenable to a main wheel such that the auxiliary wheel is absolutely parallel to the main wheel. It is a further object of the invention to provide an auxiliary wheel having a weight and overall dimensions which compare favorably with those of a spare wheel. It is a further object of the invention to provide an auxiliary wheel which can be mounted on a main wheel without a substantial increase in the weight and the cost of the main wheel, or in a deterioration of the aesthetic appearance of the main wheel. The above, and other, objects are achieved according to the present invention by an auxiliary wheel to be paired with a main wheel of a vehicle, in which the auxiliary wheel comprises a disk having a wheel rim, and a tire mounted on the wheel rim. Pivot means are formed on the disk at a position eccentric to the center of the tire for pivoting the auxiliary wheel relative to the main wheel. Guide means are formed on the disk and define an arc of a circle centered on the pivot means for guiding the pivoting of the auxiliary wheel during pairing of the auxiliary wheel with the main wheel. BRIEF DESCRIPTION OF THE DRAWINGS A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein: FIG. 1 is an elevation view of the auxiliary wheel; FIG. 2 is a section along II--II in FIG. 1; FIG. 3 shows the modification provided in the disk of the main wheel; FIGS. 4 and 5 illustrate the mounting of the auxiliary wheel; FIG. 6 shows a detail of the pairing means; and FIG. 7 shows a variant embodiment of the flexible ring encircling the auxiliary wheel. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIGS. 1 and 2 illustrate the structure of auxiliary wheel 1. The latter comprises a flat disk 10 supporting the pairing means. Disk 10 is as hollow as possible in an effort to lighten it and also facilitate installation, wide recess 100 making it possible to clearly see the main wheel during the mounting. Auxiliary wheel 1 also comprises a wheel rim 11 supporting a tire, here consisting of a solid rubber tire 12, but which could also be a pneumatic tire. The outside diameter of auxiliary wheel 1 corresponds approximately to the diameter of main wheel 2 when pneumatic tire 24 is inflated to the nominal pressure. The means for pairing auxiliary wheel 1 with the main wheel essentially comprises a pivot, and guide means placed in an arc of a circle center on the pivot. These guide means should constitute an arcuate slot which prevents the auxiliary wheel from separating from the main wheel, while making possible the rotation of auxiliary wheel 1 around the pivot defining an axis of rotation perpendicular to disk 10 of auxiliary wheel 1 and to disk 20 of main wheel 2 during the pairing. Disk 10 therefore has a hole 30 cooperating with a bolt 31 to define the pivot, and a slot 40 placed in an arc of a circle centered on hole 30. The slot comprises guide means whose edges form guide surfaces extending along an arc centered on the hole 30. A circular housing or recess 41, whose role will be explained later, is also provided in the disk 10. The pairing of auxiliary wheel 1 with main wheel 2 necessitates some adaptations of the latter, shown more particularly in FIG. 3. The pairing means according to the invention requires, on disk 20 of main wheel 2, only an extremely simple modification which is modest and not very costly. It comprises providing at least two, and preferably four, threaded holes 15 distributed on the periphery of disk 20 at equal distances from one another and at equal distances from the center of main wheel 2. Preferably, the threaded holes 15 are placed as far as possible from the center of main wheel 2. The axes of these holes are parallel to the axis of rotation of main wheel 2. For wheels made of sheet metal, the threaded holes may be placed at the vertex 21 of the boss between wheel rim 22 and zone 23 for holding main wheel 2 at the hub of the vehicle, as seen in FIG. 3. The mounting of auxiliary wheel 1 will now be explained in relation to FIGS. 4 and 5, which illustrate some characteristics of the spare traveling device resulting from associating auxiliary wheel 1 and main wheel 2, by the pairing means described. The addition of auxiliary wheel 1 to main wheel 2 modifies the offset of the point of contact of the vehicle with the ground. The offset is an important parameter which has a great influence on the behavior of the vehicle, i.e., on its handling. It therefore is important to make this offset supplement, due to the keeping in place of the main wheel, as small as possible. These considerations dictate the form of the meridian section of auxiliary wheel 1, as it appears in FIG. 5, in relation to the meridian section of main wheel 2. Disk 10 of auxiliary wheel 1 is substantially flat and is connected to wheel rim 11 at the axially inside end of the latter. The ideal main wheel 2 is that where flange 220 of main wheel rim 22 is axially at the same level as boss 21 of disk 20, as shown in FIGS. 3 and 5. The disk 10 of auxiliary wheel 1 is in contact with disk 20 of main wheel 2, at the position of boss 21, which makes possible a good holding by locking the holding elements (pivot and guide means) when auxiliary wheel 1 is centered on main wheel 2. If the boss 21 is offset axially toward the inside, then, as disk 10 of auxiliary wheel 1 should remain approximately flat to make possible a sufficient eccentricity and/or a connection to main wheel 2 at sufficiently separated points, it is necessary to provide reinforcements, in the form of washers for example, making possible the final locking without excessively deforming disk 10 of the auxiliary wheel. If the boss 21 is offset axially toward the outside, then the mechanical connection poses no problem, but by maintaining the same auxiliary wheel 1, the offset is increased. The mounting is made in the way illustrated more particularly in FIG. 4. On main wheel 2, the one of the threaded holes 15 is sought which is in the portion of disk 20 located in the left upper quarter, i.e., at a position between 9 and 12 o'clock. A bolt 31 is inserted through hole 30 in disk 10 of the auxiliary wheel to form the pivot means. The bolt 31 comprises a head 310 intended to hold disk 10 axially relative to disk 20 and a threaded portion 311. Threaded portion 311 is screwed into tapped hole 15 selected as explained above. Bolt 31 is then tightened sufficiently so that disks 10 and 20 are held parallel to one another. The pneumatic tire 24 is assumed to be deflated during the mounting of auxiliary wheel 1, as FIG. 4 shows. It is noted that the mounting would be carried out in the same way regardless of the state of inflation of pneumatic tire 24 because the wall of the latter projects from the wheel rim. It can be considered possible to also provide such pairing as an emergency repair device to improve the adherence on icy roads, for example. During the tightening of bolt 31, auxiliary wheel 1 will necessarily be eccentric relative to main wheel 2, all the more so as it will most often be necessary to mount auxiliary wheel 1 so as to overlie walls 240 of a deflated pneumatic tire 24. Then, threaded end 515 of a rod 51 is screwed into the one of the tapped holes 15 which are seen behind slot 40. This rod 51 cooperates with the slot to define the guide means and comprises a head 510, a stop 511, and a spring 512 which tends to hold a washer 513 away from stop 511. In a first step, rod 51 is screwed into the tapped hole 15 behind slot 40 until washer 513 rests firmly on disk 10 of auxiliary wheel 1, on both sides of slot 40. The guide means for auxiliary wheel 1 relative to main wheel 2 are thus provided. A movement of the vehicle, either forward or backward, then causes the centering of auxiliary wheel 1 relative to main wheel 2 by a rotation of auxiliary wheel 1 around bolt 31 constituting a pivot, by the action of the weight of the vehicle as soon as tire 12 comes into contact with the ground. For example, a vehicle movement causing the main wheel to rotate in a clockwise direction (as seen in FIG. 4) will cause the bolt 31 to move upward and to the right. This causes the weight of the vehicle to be shifted to the auxiliary wheel 1 as the bolt 31 pivots on a pivot arm centered on the point of contact of the auxiliary wheel with the ground. Eventually, the bolt 31 reaches a "top dead center" position (i.e., vertically above the point of contact of the auxiliary wheel with the ground), after which the weight of the vehicle causes the rotation of the main wheel to accelerate such that the centers of the main and auxiliary wheels become concentric. During this time the rod 51 moves along the slot 40 until it enters the housing 41. FIG. 5 shows the position of the spare traveling device after such a rotation. Preferably, locking means which prevent any return to an eccentric position of auxiliary wheel 1 relative to main wheel 2 are provided. The role of housing 41 is to receive washer 513 and comprise the locking means when the concentricity of wheels 1 and 2 is achieved. To finish the mounting, it is sufficient to finish the screwing of rod 51 into the hole 15 until stop 511 comes into contact with washer 513, thus immobilizing the auxiliary wheel relative to disk 20. To reduce as much as possible the alterations of the behavior of the vehicle due to the increase of the offset, many recesses 120 have been provided in the tire 12, conferring therein a great flexibility in the peripheral direction. A number of substantially radial incisions also can be provided. FIG. 7 illustrates other measures that can be taken to correct any pull of the vehicle due to the increased offset. For example, tire 12 may be modified so that its tread is deformed into a section of a cone expanding in one direction or in the other (i.e., so that one axial side of the tread has a larger diameter), according to the engine or brake torque applied in use, to compensate for the undesired pull. This result can be obtained by placing two elastic rubber tires 12i, 12e side by side on the wheel rim 11, a first one 12i of said tires to be placed beside main wheel 2 having incisions 120i inclined circumferentially backward relative to the direction of advance f, and the other tire 12e having incisions inclined circumferentially in the other direction 120e. FIG. 7 shows a 180° segment of the tire 12i being cut away to show the incisions in the tire 12e. The invention therefore makes possible a spare traveling device by mounting the auxiliary wheel with a main wheel which remains in place on the vehicle. According to the invention, a guide slot separated from the pivot assures, contrary to what has been conventionally thought, an excellent mechanical connection of the auxiliary wheel to the main wheel, while making possible an extremely light design. Actually, the support points of the auxiliary wheel on the main wheel can be separated from one another and perform their guiding operation even during the mounting by relative rotation, i.e., while the wheels are still eccentric. This device can be used instead of the conventional spare wheel or also can be used during such circumstances as, for example, those which require the use of chains to drive on a snowy road. In this case, such a device is mounted on each of the wheels of an axle and the tread of tire 12 is provided with a suitable pattern and/or provided with suitable elements, such as, for example, studs. Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that with the scope of the appended claims, the invention may be practice otherwise than as specifically described herein.
An auxiliary wheel is to be paired with a main wheel of a vehicle, while the main wheel remains on the vehicle. The auxiliary wheel includes a disk having a wheel rim, as well as a tire mounted on the wheel rim. In order to securely mount the auxiliary wheel on the main wheel, a bolt is insertable through a hole in the disk of the auxiliary wheel, the hole being eccentric with respect to the rotational center of the auxiliary wheel. An arcuate guide slot is formed in the auxiliary wheel disk, the guide slot forming an arc of a circle centered on the hole. A threaded rod fits into the slot and can be threaded into the main wheel, and tightened when the centers of the main and auxiliary wheels become concentric after mounting.
1
TECHNICAL FIELD [0001] The invention relates to a fluorescent lamp for stimulating previtamin D3 production. More specifically, to a low-pressure mercury discharge lamp for producing ultraviolet light in a spectrum and with intensity appropriate for stimulating D3 previtamin production in human skin. BACKGROUND OF THE INVENTION [0002] Vitamin D is a fat-soluble vitamin that is found in food and can also be made in the human body after exposure to ultraviolet (UV) rays from the sun. Sunshine is a significant source of vitamin D because UV rays from sunlight trigger vitamin D synthesis in the skin. [0003] Vitamin D exists in several forms (D1 to D5), each with a different level of activity. The natural form of vitamin D produced in skin when exposed to sunlight is cholecalciferol (D3). It is the result of a reaction between 7-dehydrocholesterol (7-DHC) and UVB ultraviolet light with wavelengths from 290 to 315 nm. This UV spectrum can be found in natural sunlight when the sun is high enough above the horizon for UVB to penetrate the atmosphere. Cholecalciferol is hydroxylated in the liver to 25-hydroxycholecalciferol (25(OH)D 3 or calcidiol) and stored until it is needed. Measuring the blood's calcidiol level is the only way to determine vitamin D deficiency; levels should be between 40 and 60 ng/mL (100 to 150 nMol/L) for optimal health. Calcidiol is further hydroxylated to 1,25-dihydroxy-cholecalciferol (1,25(OH)2D 3 or calcitriol in the kidneys and in tissues. It is the most potent steroid hormone derived from cholecalciferol and has significant anti-cancer activity. Calcitriol, also referred to as active vitamin D, functions as a hormone because it sends a message to the intestines to increase the absorption of calcium and phosphorus that may be used in the bones. Without vitamin D, bones can become thin, brittle, or misshapen. Vitamin D sufficiency prevents rickets in children and osteomalacia in adults, which are both skeletal diseases that weaken bones. Vitamin D deficiency also contributes to osteoporosis by reducing calcium absorption. Vitamin D malnutrition may possibly be linked to chronic diseases such as cancer (breast, ovarian, colon, prostate, lung, skin and probably a dozen more types), chronic pain, weakness, chronic fatigue, autoimmune diseases like multiple sclerosis and Type 1 diabetes, high blood pressure, mental illnesses (depression, seasonal affective disorder and possibly schizophrenia) heart disease, rheumatoid arthritis, psoriasis, tuberculosis, periodontal disease and inflammatory bowel disease. [0004] According to current studies one needs about 4,000 units of cholecalciferol a day to meet the body's need for vitamin D. Four thousand units of cholecalciferol are equal to 100 micrograms, or 0.1 milligrams. These studies have also shown that 15 to 20 minutes daily exposure to sunlight with an impart angle above 50 degrees can contribute to sufficient previtamin D3 production in the skin. [0005] Season, geographic latitude, part of the day, cloud coverage, smog, and sunscreen affect UV ray exposure and vitamin D synthesis. Insufficient exposure to sunlight causes vitamin D deficiency, which hinders calcium absorption in bones and weakens the immune system. In order to compensate for vitamin D deficiency, vitamin D preparates can be taken in prescribed amounts. As vitamin D is a highly potent vitamin, there is a danger of toxication if it is taken in overdoses. [0006] On the other hand, natural sunlight may be replaced by artificial sun tanning lamps emitting ultraviolet light. When considering the effects of UV radiation on human health and the environment, the range of UV wavelengths is often subdivided into UVA (400-315 nm), also called Long Wave or “blacklight”; UVB (315-280 nm), also called Medium Wave; and UVC (<280 nm), also called Short Wave or “germicidal”. [0007] Conventional sun tanning lamps such as disclosed in U.S. Pat. No. 4,194,125 emit ultraviolet radiation primarily or exclusively in the UVA range and emit no radiation in the UVC range. The usual UVB/UVA emission power ratio is 0.02 to 0.08. [0008] U.S. Pat. No. 5,557,112 discloses a fluorescent lamp having multiple zones with different ultraviolet radiation characteristics along its length with a first fluorescent coating for producing a first UV radiation and a second fluorescent coating for producing a second UV radiation, which is different from the first UV radiation. Generally, the UVB intensity and UVB/UVA ratio is increased in one longitudinal area. In the example of the suggested lamp, the UVB/UVA ratio of the higher intensity coating is 0.066 and radiation levels are 2.1 (UVA) and 0.14 (UVB) microwatts/cm 2 . The UVB/UVA ratio of the lower intensity coating is 0.052, and the radiation levels are 2.10 (UVA) and 0.12 (UVB) microwatts/cm 2 . [0009] U.S. Pat. No. 4,967,090 offers a fluorescent lamp and system for providing cosmetic tanning with an adjustable UVB/UVA ratio. This adjustment is achieved by two phosphor coatings with different UVB/UVA ratio and an axial rotation of the lamp. The proposed lamp includes a first ultraviolet-emitting phosphor disposed on a portion of the circumference of the interior of an ultraviolet-transmitting glass envelope. A second ultraviolet-emitting phosphor is disposed on the remaining portion the lamp envelope. In one embodiment, the proportions of UVB to UVA from the same light source are about 1.6% and 4.2%. [0010] In the prior art tanning lamps the erythemal effect limits the irradiation doses. The tanning effect is achieved by both the UVA and the UVB radiation. UVB radiation must however be limited because of its high erythemal effect. The UVB part of the radiation provides a contribution to vitamin D3 synthesis, however it is not effective enough. [0011] Recently a few UVB lamps have been suggested for medical purposes, such as for the treatment of psoriasis. One group of these lamps provides wide band UVB radiation, while another group may be used for generating narrow band UVB radiation. An example for a wide band UVB is TL/12 and an example for a narrow band UVB is TL/01 available from Philips. These special UVB lamps have no radiation in the UVA and UVC spectral range. The input electric power of the lamps is 100 W and the output radiation level is relatively high, therefore extreme care should be taken in order to avoid overexposure to UVB which may cause sunburn effect (erythema) or may even contribute to developing skin cancer. [0012] Therefore it is an objective of the present invention to provide a fluorescent lamp, preferably a low pressure mercury discharge lamp, that emits an optimized radiation which induces significantly more efficiently the photosynthesis of previtamin D3 in human skin, without exceeding the erythemal effect caused by related prior art products. DISCLOSURE OF THE INVENTION [0013] The objectives of the invention may be accomplished by using a fluorescent lamp, preferably a low-pressure mercury discharge lamp, for stimulating previtamin D3 production. The lamp has a discharge tube with a discharge gas filling. The inside wall of the discharge tube is covered with a phosphor coating for converting short wave UV radiation of the ionized discharge gas into longer wave UV radiation. The discharge tube is closed at both ends and provided with electrodes that are held and lead through a base cap at both ends. The base caps of the lamp have contact pins on them for connecting the lamp to an electrical power supply. [0014] According to the improvement of the invention, the UV light-radiating coating of the discharge tube is comprised of [0015] a first phosphor for emitting light waves in the UVB spectrum and [0016] a second phosphor for emitting light waves in the visible light spectrum and for suppressing the emitted light in the UVB spectrum. [0017] The suggested lamp will emit no light in the UVC spectrum, it mainly provides radiation in the UVB spectrum and there may be some radiation in the UVA spectrum, however with less power than in the UVB spectrum. In consequence, this lamp will not provide light waves that cause a useful tanning effect, however it will provide light waves that contribute very effectively the production of previtamin D3 in human skin. [0018] The lamp provides a light emission spectrum with a maximum in the range of 310 nm<λ<330 nm, preferably within the range of 315 nm<λ<325 nm. The selected spectral range provides for an effective stimulation of the previtamin D3 production, while the erythemal effect is minimized. [0019] Also, the maximum of the emission spectrum of the lamp is less than 0.05 W/m 2 , preferably less than 0.04 W/m 2 and even more preferably less than 0.03 W/m 2 . The suggested power range makes it possible to select longer exposure times without negative effects as well as to determine the necessary dosage more precisely. SHORT DESCRIPTION OF THE DRAWINGS [0020] The invention will be described in more detail below on the basis of and in connection with exemplary embodiments shown in the drawings, in which [0021] FIG. 1 is a side view of a fluorescent lamp with base caps on both ends also provided with two pairs of contact pins, [0022] FIG. 2 is a cross sectional view of an embodiment of the lamp shown in FIG. 1 , [0023] FIG. 3 is a cross sectional view of another embodiment of the lamp shown in FIG. 1 , [0024] FIG. 4 is an action spectrum diagram of 7-DHC to previtamin D3 conversion in human skin, [0025] FIG. 5 is a sensitivity diagram of the human skin as a function of the wavelength of the irradiating light, [0026] FIG. 6 is a power spectrum diagram of a conventional mercury vapor sun-tanning lamp combined with the diagram of FIG. 5 , [0027] FIG. 7 is the same diagram as shown in FIG. 6 completed with a power spectrum diagram of a lamp according to the invention, [0028] FIG. 8 is an enlarged view of FIG. 7 , with a range of 290 nm to 330 nm, [0029] FIG. 9 is a power spectrum diagram of the lamps of FIG. 8 weighted with the vitamin D3 sensitivity diagram, [0030] FIG. 10 is a transmission diagram of the glass of the discharge tube of a conventional lamp and the lamp according to the invention. DESCRIPTION OF PREFERRED EMBODIMENTS [0031] FIG. 1 shows a lamp comprised of a sealed hollow discharge tube 10 made of glass, which contains a quantity of mercury and an inert gas such as argon, krypton or the like. At each end of the glass tube 10 there is an electrode comprised of an oxide-coated tungsten coil and lead-in wires (not shown). Suitable bases 11 and 12 are fixed to the ends of discharge tube 10 and carry contact pins 13 , 14 and 15 , 16 . [0032] The lamp shown in FIG. 1 may be of any standard size, for example 6′ of type T12 for use in connection with a sun bed or a smaller sized personal tanning apparatus or of any special size to be used in a special apparatus in order to achieve the desired stimulation of the synthesis of previtamin D3. Although the shown lamp is sealed and has electrodes on both ends of a straight discharge tube, it will be apparent to those skilled in the art that any other form, size, and construction of a fluorescent lamp may be used just as well for the purposes of the invention. [0033] In a fluorescent lamp usually a suitable phosphor coating is used on the inner surface of the discharge tube which will absorb the shorter wave UV radiation (mainly UVC radiation) generated by the arc discharge within the lamp and re-emit this energy at a different, more useful longer wave UV spectrum. [0034] According to the invention a mixture of at least two phosphors is used for creating a suspension which is used for covering the inside surface of the discharge tube. This coating is then burned to provide the required mechanical strength. As it is apparent to those skilled in the art, further layers may be applied in addition to the phosphor layer. Such layers may for example include a protective, a reflective layer and other layers. The two component phosphor layer provides a light emission mainly in the UVB spectrum and a visible spectrum. One phosphor of the mixture is responsible for the UVB radiation and the other phosphor provides for a visible light emission and a suppression of the UVB radiation. Different phosphors may be used as a UVB phosphor. One such phosphor may be a cerium-activated magnesium barium aluminate ((Mg,Ba)Al 11 O 19 :e) phosphor. It might be of further advantage if the second phosphor is a phosphor for emitting visible yellow light. On one hand, it improves the aesthetic effect of the lamp in use. On the other hand, it has been found especially suitable for suppressing the light emission power in the UVB range. Different phosphors may be used for providing visible yellow light. One such phosphor may be cerium-activated yttrium aluminate (Y 3 Al 5 O 12 :Ce) phosphor. The saturated yellow color of the Y 3 Al 5 O 12 :Ce phosphor has the additional benefit of resulting in a nice aesthetic appearance that gives the impression that the client has been sunbathing. [0035] Regarding another aspect of the invention, the proportion of the second phosphor to the first phosphor is selected to be in the range of 30 wt % and 50 wt %. On one side, a lower proportion (below 30 wt %) of the yellow phosphor would not provide sufficient visible light and suppression in the UVB spectrum. On the other hand, however, a higher proportion (above 50 wt %) of the yellow phosphor would result in two much energy of the visible light and an undesired level of suppression in the UVB spectrum. [0036] In order to achieve a uniform effect, the two phosphors 20 in a suspension may be distributed uniformly on the inner surface of the envelope of the discharge tube 10 as shown if FIG. 2 , where the discharge tube 10 has a uniform phosphor layer 20 on the inside surface. [0037] According to another embodiment, as shown in FIG. 3 , the discharge tube 10 has a first phosphor layer 21 on a part of the inside surface of the discharge tube 10 and a second phosphor layer 22 on the remaining part of the inside surface of the discharge tube 10 . Such an embodiment may be advantageous if different effects along the surface of the lamp should be achieved. To this effect, any pattern may be used for an uneven distribution along the inner surface of the discharge tube to provide for the desired uneven effect. [0038] According to one aspect of the invention, the two phosphors may have an uneven distribution along the longitudinal direction of the discharge tube. This would enable to provide different power spectral distribution characteristics of the lamp along the longitudinal direction, and therefore different exposure of different parts of the human body. In another aspect of the invention, the two phosphors may have an uneven distribution along the circumferential direction of the discharge tube. This would provide a lamp with different power spectral distribution characteristics of the lamp along the circumferential direction. Such a lamp could be used for example as a combination of a conventional sun tanning lamp and a lamp for stimulating the synthesis of previtamind D. As it may be apparent to those skilled in the art, different additional phosphors and layers may be applied in order to achieve different additional effects. [0039] In FIG. 4 , the action spectrum of 7-DHC (7-dehydrocholesterol) to previtamin D3 conversion in human skin can be seen in terms of the reciprocal dose (cm2/J) depending on the wavelength of the light. This diagram represents the relative sensitivity of human skin and was published by MacLaughlin J. A., Anderson R. R., Holick M. F. in Spectral character of sunlight modulates photosynthesis of previtamin D3 and its photo isomers in human skin. (Science 216(4549):1001-1003, 1982). The photosynthesis of previtamin D3 from 7-dehydrocholesterol in human skin was determined after exposure to narrow-band radiation. The optimum wavelengths for the production of previtamin D3 were determined to be between 295 and 300 nanometers. [0040] According to a CIE (International Commission on Illumination) technical report (CIE 174:2006) the action spectrum for the production of previtamin D3 in human skin has a maximum at about 300 nm and no significant action can be found above 330 nm. According to the relative sensitivity diagram shown in FIG. 5 , a spectrum between 250 nm and 320 nm may be used for stimulating previtamin D3 synthesis. There is, however, another effect caused by UV radiation in human skin that has to be taken into consideration. If human skin is exposed to shorter wave UV light, especially UVB and UVC, there may be an undesired sunburn effect. The relative sensitivity of skin to develop sunburn effect, or erythema, is shown in a second diagram with a broken line in FIG. 5 . As it can be seen clearly, the relative sensitivity to erythema is very high in the range of λ<300 nm. The highest sensitivity is determined to be 100% or 1 . This sensitivity drops very rapidly from 10 0 to 10 −3 in the range of 300 nm<λ<330 nm and drops less rapidly from 10 −3 to 10 −4 in the range of λ<330 nm. Conventional sun tanning lamps emit light in the UVA range and practically no or very few light in the UVB range causing minimal erythemal effect. [0041] FIG. 6 shows the emission power spectrum of a conventional sun-tanning lamp HL such as those produced by Philips under the trade name Swift 100R (also known as Dr Holick UV-System Vitamin D3 Sunlamp) and the relative sensitivity diagrams (previtamin D3 and erythema action spectra) of the skin. All irradiance data is measured at 25 cm distance from the middle of the lamp, according to IEC 61228. It consumes 100 Wrms electric power and emits 17.7 W/m 2 total UVA radiation and 0.33 W/m 2 total UVB radiation. The total radiation weighted by the previtamin D3 action spectrum is 44.6 mW/m 2 . The total radiation weighted by the erythema action spectrum is 58 mW/m 2 , which results in approximately 8 minutes exposure, depending on the sun bed or sun booth in which they are applied, to reach a minimum erythemal dose (one MED) when exposed to one lamp. A significant part of the total erythema is obtained from the UVA part of the lamp spectrum, instead of the UVB range, in an approximate 25:75 ratio. This lamp has a power spectrum substantially in the UVA range with two local peaks at 311 nm and 365 nm due to the mercury arc. The maximum emission power (irradiance) of about 0.42 W/m 2 can be observed at a wavelength of 365 nm. The irradiance values for the power spectrum diagram can be seen on the right side in the range of 0 to 0.5 W/m 2 . The relative sensitivity values are shown on the left side. This prior art sun-tanning lamp has a good tanning effect in the UVA range of 330 nm<λ<370 nm with little erythemal effect, and also contributes to vitamin D synthesis in the UVB range of 300 nm<λ<330 nm, especially at the 311 nm peak of the mercury arc. The UVB range however poses a high risk of erythema which further limits the allowable exposure time. [0042] The lamp also has a certain stimulating effect for previtamin D3 production but because of the high erythemal effect no sufficient exposure time may be selected in order to achieve an effective previtamin D3 synthesis. [0043] FIGS. 7 and 8 show the power spectrum diagram of a lamp DL according to the invention in comparison with a conventional lamp HL shown in FIG. 6 and with the relative sensitivity diagrams of the skin. FIG. 7 shows the same diagrams as already seen in FIG. 6 with a new power spectrum diagram of a lamp DL according to the invention. FIG. 8 shows these diagrams in an enlarged view with a smaller spectral and irradiance range. As best seen in FIG. 7 , the lamp according to the invention provides a light emission spectrum mainly in the range from 290 nm to 330 nm, preferably in the range of 315 nm and 325 nm with a maximum at about 325 nm. The proposed lamp has no significant emission in the range below 290 nm and above 340 nm. The selected spectral range provides for an effective stimulation of the previtamin D3 production, while the erythemal effect is minimized. [0044] The maximum of the emission spectrum of the lamp according to the invention is less than 0.05 W/m 2 , preferably less than 0.04 W/m 2 and even more preferably less than 0.03 W/m 2 . As shown in FIG. 8 in connection with an exemplary embodiment of the invention, the maximum power (0.025 W/m 2 ) of irradiance of the new lamp is significantly lower than the peak power (0.06 W/m 2 ) of the prior art lamp in the UVB range. On the other hand, the new lamp has a higher output power in the range of 290 nm<λ<310 nm which results in a better stimulating effect for producing previtamin D3. The suggested power range makes it possible to select longer exposure times without negative effects and to determine the necessary dosage more precisely. As it can be seen best in FIG. 8 , the lamp DL has a significantly higher emission in the range of 295 nm to 310 nm resulting in a better stimulating effect for the production of previtamind D3. [0045] The effectiveness of the stimulation of the previtamin D3 synthesis is best seen in FIG. 9 , which shows the power spectra of the lamp according to the invention and the conventional sun tanning lamp weighted with the previtamin D3 action spectrum (relative sensitivity of the skin). The weighted diagram of the lamp according to the invention peaks at about 305 nm and as it can be clearly seen, in most of the active range of the power spectrum of the lamp according to the invention, the output power is higher than that of the conventional lamp HL. In consequence, the suggested lamp DL has a significantly better previtamin D3 efficacy at the same or lower erythemal effect. [0046] In FIG. 10 , the transparency diagrams of two different glasses are shown in a comparable way. As seen on the figure, both of the glasses are transparent to light with a wavelength of λ>350 nm and opaque to light with a wavelength of λ<280 nm that is for the UVC spectrum. Both of the glasses have a similar transparency diagram, which is offset along the x axis by about 10 nm. The 50% transparency of the first glass OG is at λ=305 nm and the 50% transparency of the second glass CG is at λ=315 nm. Since the first glass is transparent for shorter waves, it is also referred to as “open glass”; the second glass, which is not transparent to these shorter waves, is also referred to as “closed glass” in the sun tanning industry. [0047] In order to further reduce the intensity of the emitted UVB spectrum of the lamp according to the invention, it might be advantageous to use a “closed glass” instead of an “open glass”. The discharge tube therefore may be made of a glass material which has a 10% transparency for the light waves with a wavelength of λ>295 nm. According to a further aspect, the glass material of the discharge tube may have a 50% transparency for the light waves with a wavelength of λ>310 nm, preferably of λ>315 nm. In order to achieve the so called “closed” characteristic of the glass, additives such as Fe, Ce or Ti may be added to the glass material resulting in a slightly different transparency curve which makes it necessary to reoptimize the phosphor blend. [0048] In the example shown in FIG. 10 , the first glass OG was a glass LT 101 (open glass) available from LightTech, Budapest. The second glass CG was a glass LT 103 (closed glass) available from LightTech, Budapest. [0049] In order to further decrease the emitted light power, the input electric power of the lamp may be selected in a low wattage range of about 40 W so that the lamp can be driven at lower arc current, preferably with a 40 W electromagnetic ballast. This has the additional benefit of consuming 60% less electric power, which enables a less expensive usage of the device during its functional lifetime. Lower wattage electromagnetic ballast cannot operate 6 ′ lamps stably due to the high arc voltage. A specially designed electronic ballast would be able to operate a 6′ T12 lamp in a stable way, but such ballast is not favored due to its high cost compared to an electromagnetic ballast. [0050] The following table provides a comparison of a prior art lamp and an example according to the invention. For the purposes of a comparative test sample we used a 6′ long discharge tube made of a closed glass without a reflecting layer, with a short mount for holding the electrodes, with a phosphor blend of 65 wt % UVB phosphor of the type NP807-32, 35 wt % yellow phosphor of the type NP204 both available from Nichia (Tokushima), an inert gas filling of 50 wt % krypton and 50 wt % argon at a cold filling pressure of about 2 mbar. The low wattage (40 W) power supply and the electromagnetic ballast provided a cathode current of about 1 A. [0000] TABLE 1 Dr. Holick Vitamind Example according to D3 Sunlamp the invention Lamp power (W) 100 40 Total UVA (W/m 2 ) 17.7 0.8 Total UVB (W/m 2 ) 0.33 0.26 Erythema (mW/m 2 ) 58.1 49.3 Erythema A (mW/m 2 ) 14.9 1.1 Erythema B (mW/m 2 ) 43.2 48.2 Previtamin D3 (mW/m 2 ) 44.6 57.4 Previtamin D3 efficacy 0.47 1.49 (mW/m2/W) [0051] The lamp according to the invention has a high efficiency in converting electric power to previtamin D3 production when compared to the prior art lamp by Dr. Holick. Both the total UVA and total UVB radiation of the tested example are lower than that of the prior art lamp, but it has as high as 58 mW/m 2 previtamin D3 weighted irradiance even when operated with a low power 40 W conventional electromagnetic ballast, while its erythema is 49 mW/m 2 , resulting in 8.5 min MED for one lamp. This means that using this lamp the client gets 30% higher previtamin D3 dose during the same exposure session, without an increased risk of sunburn. In addition, the previtamin D3 efficacy (calculated as dividing the previtamin D3 weighted irradiance with the lamp wattage, similar to the “lumen per watt efficacy” of general lighting lamps) is three times higher than that of the prior art lamp. (See FIG. 9 for spectral comparison and Table 1 for data.) [0052] The fluorescent lamp according to the invention has a significantly higher vitamin D3 efficacy, because it induces more previtamin D3 production in human skin during the same exposure time, without causing more skin burn.
The invention relates to a fluorescent lamp, preferably a low pressure mercury discharge lamp for stimulating previtamin D3 production. The lamp has a discharge tube with a discharge gas filling. The inside wall of the discharge tube is covered with a phosphor coating for converting short wave UV radiation of the ionized discharge gas into longer wave UV radiation. The discharge tube is closed at both ends and provided with electrodes which are held and lead through a base cap at both ends. The base caps of the lamp are provided with contact pins for connecting the lamp to an electrical power supply. According to the improvement of the invention the UV light radiating coating of the discharge tube comprises a first phosphor for emitting light waves in the UVB spectrum and a second phosphor for emitting light waves in the visible light spectrum and for suppressing the emitted light in the UVB spectrum.
2
BACKGROUND OF THE INVENTION One of the major problems facing today's society and future generations is the production of air pollution by a variety of combustion systems, such as boilers, furnaces, engines, incinerators and other combustion sources. Air pollutants produced by combustion include particulate emissions, such as fine particles of fly ash from pulverized coal firing, and gas-phase (non-particulate) species, such as oxides of sulfur (SO x , principally SO 2 and SO 3 ), carbon monoxide, volatile hydrocarbons, volatile metals (i.e., mercury—Hg), and oxides of nitrogen (mainly NO and NO 2 ). Both NO and NO 2 are commonly referred to as “NO x ” because they interconvert, the NO initially formed at higher temperature being readily converted to NO 2 at lower temperatures. The nitrogen oxides are the subject of growing concern because of their toxicity and their role as precursors in acid rain and photochemical smog processes. One other major problem facing society is the ever expanding consumption of and dependence on energy, including specifically fossil fuels. One area of great promise for better, more efficient and environmentally conscious energy usage is in the utilization of waste fuels for energy production. Large quantities of agricultural and other biomass resources are available throughout the world. Biomass is a renewable source of energy, but a lot of this material is being land filled, burned in the open fields, or plowed under and, thus, are not utilized as an energy feedstock. Utilization of biomass for energy production eliminates costs for its disposal, provides a renewable energy resource and decreases CO2 emissions. Currently, due to slagging and fouling of boilers' heat transfer surfaces, biomass boilers cannot use a variety of bio-feedstocks with high alkali content. Accordingly, two key needs are 1) decreasing NOx emissions from combustion sources and 2) increasing utilization of low-grade waste fuels for energy production. There are several commercial technologies that are available to control NOx emissions from stationary combustion sources. Combustion modifications such as Low NOx Burners (LNB) and overfire air (OFA) injection provide only modest NOx control, on the level of 30-50%. However, their capital costs are low and, since no reagents are required, their operating costs are near zero. For deeper NOx control, Selective Catalytic Reduction (SCR), reburning, Advanced Reburning (AR) or Selective Non-Catalytic Reduction (SNCR) can be added to LNB and OFA, or they can be installed as stand alone systems. Currently, SCR is the commercial technology with the highest NOx control efficiency. With SCR, NOx is reduced by reactions with N-agents (ammonia, urea, etc.) on the surface of a catalyst. The SCR systems are typically positioned at a temperature of about 700° F. SCR can relatively easily achieve 80% NOx reduction. However, SCR is far from an ideal solution for NOx control. There are several important considerations, including cost. SCR requires a catalyst in the exhaust stream. Catalysts and related installation and system modifications are expensive. In general, SCR catalyst life is limited. Catalyst deactivation, due to a number of mechanisms, typically limits catalyst life to about four years for coal-fired applications. In addition, catalysts are toxic and pose disposal problems. Reburning is a method for controlling nitrogen oxides that involves combustion of a fuel in two stages. FIG. 1 may be referred to in this discussion concerning reburning techniques. As shown in the reburning system 100 of FIG. 1, in the main combustion zone 102 80-90% of the fuel is burned with normal amount of air (about 10-15% excess). This corresponds to an Air/Fuel Stoichiometric Ratio (SR) about 1.10-1.15. The combustion process forms a definite amount of NOx. Then, in the second stage, the rest of the fuel (reburning fuel) is added at temperatures of about 2300-3000° F. into the secondary combustion zone 104 , called the reburning zone, to generate a fuel-rich environment. Test results indicate that in a specific range of conditions (equivalence ratio in the reburning zone, temperature and residence time in the reburning zone) the NOx and N2O concentrations can typically be reduced by 50-60%. In the third stage 106 the OFA is injected at a lower temperature to complete combustion. Typically the OFA is injected at 1800° F.-2800° F. to achieve essentially complete combustion. The flow diagram section, b, of FIG. 1 illustrates the main reactions in the reburning zone process. Adding the reburning fuel leads to its rapid oxidation by the excess oxygen to form CO and hydrogen. The reburning fuel provides a fuel-rich mixture with certain concentrations of carbon containing radicals 108 , e.g., CH3, CH2, CH, C, and HCCO, which can react with NO. The carbon containing radicals (CHi) formed in the reburning zone are capable of reducing NO concentrations by converting it to various intermediate species with C—N bonds, 110 . These species are reduced in reactions with different radicals into NHi species 112 , e.g., NH2, NH, and N, which react with NO to form N2 114 . N2O is reduced mainly via reaction with H atoms: N2O+H→N2+OH. The OFA added on the last stage of the process oxidizes existing CO, H2, HCN, and NH3. Typically, reburning fuel is injected at flue gas temperatures of 2300-3000° F. The efficiency of NOx reduction in reburning increases with an increase in injection temperature. This is because at higher temperatures oxidation of the reburning fuel occurs faster, resulting in higher concentrations of carbon containing radicals involved in NOx reduction. Efficiency of NOx reduction also increases with an increase in the amount of the reburning fuel at reburning fuel heat inputs of up to 20-25%. Larger amounts of reburning fuel practically do not increase and sometimes even slightly decrease the efficiency of NOx reduction. Conventional reburning typically requires 15% to 20% reburning fuel heat input to achieve 40%-60% NOx reduction. In so-called Fuel-Lean Reburning (FLR) the amount of the reburning fuel is controlled to maintain an overall fuel-lean stoichiometry in the upper furnace. Therefore, no additional OFA is required for completing burnout. FLR has shown the potential to achieve about 25-35% reduction in NOx emissions using 7-8% natural gas heat input or less. Greater levels of NOx control can be achieved using Advanced Reburning (AR) techniques. AR is a synergistic combination of basic reburning and N-agent (ammonia or urea) injection. Initial AR studies focused on N-agent injection into the burnout zone (AR-Lean). It was found that AR-Lean incorporates the chain branching reaction of CO oxidation which promotes the reaction between NO and ammonia. When CO reacts with oxygen, it initiates many free radicals. Experiments and modeling studies have demonstrated that the de-NOx temperature window can be substantially broadened and NO removal efficiency increased, if both CO and the O2 concentrations are controlled to fairly low values (CO at the order of 1000 ppm and O2 at less than 0.5 percent). At the point of air addition, CO and O2 are both at low values because of the close approach to SR=1.0, yielding about 85% NO reduction. Injection of small amounts of alkali promoter species, such as sodium carbonate, along with ammonia into the reburning zone (AR-Rich) can further improve upon the AR process. These AR improvements are capable of achieving greater than 90% NOx control. Waste fuels can be very effective for reburning. Tests with several feedstocks (yard waste, furniture manufacturing sawdust, walnut shells, willow wood, waste coal fines and others) demonstrate that advanced waste reburning technologies can achieve higher NOx reduction even than that achieved with natural gas. Efficiency of NOx reduction for most waste fuels increase with an increase in the amount of the reburning fuel. In one technique, biomass pyrolysis gas serves as the reburning fuel. Pyrolysis-based units produce gas, char and tar. Using a reburning technique, pyrolysis products are injected in a combustor as reburning fuel at different temperatures of pyrolysis and various air/fuel stoichiometric ratios in the combustor's reburning zone. Maximum NOx control performance of 87% has been achieved with biomass gas combined with the tar formed at pyrolysis temperature of 1650° F. At a stoichiometric ratio of 0.8, biomass gas has exceeded the performance of natural gas, which was about 75%. A number of efforts have been made to utilize waste fuels for energy production. One driving force to make fuel-flexible power technologies less costly than conventional fuel power technologies is the low or negative cost associated with opportunity fuels. Another reason is the societal goals, energy conservation, environmental conservancy and care, and others. Large quantities of opportunity fuels including urban wood waste, agricultural residues, forest waste, municipal solid waste, and sewage sludge are land filled and, accordingly, their beneficial uses are unrealized. These feedstocks are low-grade waste fuels. There are several technologies that are available to produce energy from waste fuels. Direct combustion involves the burning of fuel with excess air, producing hot flue gases that are used to produce steam in the heat exchange sections of boilers. The steam is used to produce electricity in steam turbine generators. Direct combustion of waste fuels has proven inefficient because of poor combustion characteristics generally associated with waste fuels. When compared to fossil fuels, waste fuels have a heterogeneous composition, sometimes high ash and/or moisture content, low heating value, substantial chlorine content, and trace heavy metal content. Because of that, existing biomass boilers are limited in efficiency and suffer undesirable consequences of fuel ash fouling. Combustion of these fuels requires expensive solids handling equipment, corrosion protection, high excess air, scrubbers, filters, and other air pollution control systems. Co-firing refers to the practice of introducing biomass or waste fuels in the main combustion zone of fossil fuel fired boilers as a supplementary energy source. Co-firing has been evaluated for a variety of boiler technologies including pulverized coal combustors, fluidized bed units, and stokers. Because waste fuel comprises only a fraction of fossil fuel, negative impact of waste fuel on boiler performance is reduced in co-firing. As an alternative for direct waste combustion, gasification can be applied to a variety of waste products, providing a cleaner gaseous fuel. The gasification process takes solid waste products and improves its combustion characteristics, handleability, and simultaneously may reduce pollutant emissions. Gasifiers can frequently handle high fouling fuels without excessive slagging/fouling due to the lower temperatures at which they can operate in comparison with direct combustion units. Waste fuel gasification generally involves heating fuel in an oxygen-starved environment to produce a medium or low calorific gas. This “biogas” is then used as fuel in a combined cycle power generation plant that includes a gas turbine topping cycle and a steam turbine bottoming cycle, or can be used for co-firing in coal and biomass fired boilers. SUMMARY OF THE INVENTION The present invention is related to processes for removing emissions of nitrogen oxides in combustion systems. More specifically, the present invention provides methods for decreasing nitrogen oxides emissions from stationary combustion sources and for utilizing low-grade biomass and other waste fuels without slagging and fouling problems. The present invention represents an improvement over prior techniques in that it presents methods and systems that effectively and efficiently reduce NOx while utilizing gasified fuels, including biomass and low-grade waste fuels. In general, the present invention unconventionally achieves these improvements by gasifying solid fuels and injecting produced gas into a reburning zone of a boiler at relatively low temperatures and in relatively small amounts. If the gas is fed into a reburning zone of a boiler, the gas cleaning requirement is eliminated or substantially reduced, as tars are burned in the flame and alkali species may be present at much lower levels than is the case with direct combustion applications. Importantly, there are key differences between the present invention and prior techniques, including, for instance: 1) conditions in a gasifier are such that gasification products with optimum concentrations of nitrogen (N)- and alkali (Na and K)-containing species are produced; 2) specific flue gas temperature of the boiler at which the gaseous products are injected is selected, and 3) reaction time in the post-combustion or reburning zone for effective interaction of the N- and alkali-containing species in the gasification products with NOx in flue gas is provided. In addition, the present invention improves over prior techniques by realizing a very high efficiency of NOx removal by gasification products. Generally, propane and natural gas have been thought to be the most effective reburning fuels with coal being slightly less effective. Also, the efficiency of syngas, with CO and H2 being its major components, is much less than that of propane and natural gas. Implementation of the present invention yields the surprising result that efficiency of syngas, such as from waste gasification, under optimized conditions can be higher than that of propane and natural gas, as shown in the examples set forth in the detailed description hereinbelow. Moreover, the invention achieves efficiencies of 70% NOx reduction and higher at 6%-8% reburning fuel heat inputs. This result is quite remarkable and unexpected since in Fuel-Lean Reburning only 25-35% reduction in NOx emissions is obtained using 7-8% natural gas heat input. Particular embodiments of the invention provides a method of decreasing emissions of nitrogen oxides (NOx) in combustion systems in combination with utilization of at least one low grade solid fuel. The inventive method comprising the steps of: causing the combustion of a main fuel in a combustion system, thereby resulting in the generation of a combustion flue gas in a post combustion zone, the combustion flue gas comprising nitrogen oxides; gasifying at least one solid fuel in a gasifier causing the generation of a gaseous product containing solid particles, the gaseous product comprising one or more of the group consisting of carbon monoxide, hydrogen, hydrocarbons, water, carbon dioxide, ammonia and other reduced N-containing species, and small amounts of alkali-containing compounds; and injecting the gaseous product into the post combustion zone of the combustion system to create a reaction zone in which nitrogen oxides are reduced to molecular nitrogen by introducing the gaseous product into the post combustion zone at a temperature designed to promote reaction of NO with one or more of the group comprising syngas components, CO, H2, hydrocarbons, ammonia, and N- and alkali-containing compounds. In another embodiment, the invention provides a combustion system for causing the combustion of fuel, the combustion of fuel resulting in the generation of post-combustion flue gas, including NOx, the combustion system comprising: a primary combustion zone in which the combustion of a main fuel occurs, the combustion of the main fuel generating flue gas, which exit the combustion zone; a post-combustion zone for receiving the flue gas; and a gasifier receiving biomass or waste fuel and producing a gaseous product at least in part therefrom and delivering the gaseous product into the post-combustion zone for reacting with the flue gas to reduce NOx emissions, the gaseous product being introduced into the post combustion zone at a temperature designed to promote reaction of NO with one or more of the group comprising syngas components, CO, H2, hydrocarbons, ammonia, and N- and alkali-containing compounds. It is therefore an object of the present invention to provide methods for eliminating or at least dramatically reducing nitrogen oxides from combustion flue gas before they are emitted to the atmosphere. It is an object of the invention to introduce gaseous products into a post combustion zone at such a temperature so as to promote the reaction of ammonia and alkali-containing compounds with NO contained in flue gas to reduce NOx emissions. It is another object of the present invention to decrease the concentration of nitrogen oxides formed in combustion by injection gasification products of different fuels into a post combustion or reburning zone of a combustion system. It is another object of the present invention to utilize biomass and low-grade waste fuels with high fuel-N and alkali content for production of syngas. Additional objects and advantages of the present invention will be apparent to those skilled in the art upon reading the description and claims and examining the figures, or may be learned by the practice of the invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram illustrating (a) the reburning process, in corresponding view of (b) the main reaction paths in the reburning zone; FIG. 2 is a schematic diagram illustrating a reburning and gasification arrangement incorporating the present invention; FIG. 3 is a cross-sectional schematic diagram illustrating a waste fuel gasifier in combination with a boiler for realizing the NOx reduction benefits of the present invention; FIG. 4 is a schematic view of a fluidized bed gasifier for use in a system incorporating the present invention; FIG. 5 is a schematic view of a solid fuels test facility for use with a continuous emissions monitoring system in determining the efficacy of and in setting operating conditions for the present invention; FIG. 6 is a graph illustrating the composition of combustible gases as a function of waste fuel feed rate for almond shell gasification products from a HFBG; FIG. 7 is a bar graph comparing synthesis gas composition of various waste fuels at a stoichiometric ratio of 0.3; FIG. 8 is a graph comparing reburning performance of gasified waste fuels at NOi=300 ppm; FIG. 9 is a graph illustrating the exemplary correlation for NOx reduction and fuel-N at 20% reburning heat input; FIG. 10 is a graph illustrating the exemplary correlation between Fuel-N and sodium content of waste fuel and NOx reduction at 8% reburning heat input; FIG. 11 is a graph comparing the NOx reduction efficacy in the example of waste paper reburning at 2350° F. and 2150° F.; FIG. 12 is a graph comparing the NOx reduction efficacy for examples of almond shells reburning at 2150° F. and 1830° F.; FIG. 13 is a graph comparing the NOx reduction efficacy of modeling predictions vs. experimental data for LPG reburning; FIG. 14 is a graph comparing the NOx reduction efficacy of modeling predictions vs. experimental data for the example of reburning with almond shells gasification products; FIG. 15 is a graph comparing the NOx reduction efficacy of modeling predictions vs. experimental data for the example of wood P gasification products; FIG. 16 is a graph comparing the NOx reduction efficacy of modeling predictions vs. experimental data for the example of reburning with waste paper gasification products; FIG. 17 is a graph comparing the predicted effects of Na and NH3 on NOx reduction for the example of almond shells reburning at 2150° F.; and FIG. 18 is a graph illustrating the predicted temperature dependence of the efficiency of NOx reduction in reburning with almond shells gasification products. DETAILED DESCRIPTION OF THE INVENTION The present invention discloses a method for decreasing concentration of NOx in flue gas of combustion systems. According to the present invention, the NOx concentration can be reduced by combining direct gasification of solid fuels, including biomass and low-grade waste fuels, with reburning under specific conditions. As will be appreciated by consideration of the following description as well as the accompanying figures, the present invention may be embodied in different forms. The embodiments described herein represent a demonstration of modes for carrying out the invention. Nevertheless, many embodiments, or variations of them, other than those specifically detailed herein, may be used to carry out the inventive concepts described in the claims appended hereto. The invention can be applied to various combustion facilities, e.g., power plants, boilers, furnaces, incinerators, engines, and any combinations thereof, and utilizes solid fuels including coal, biomass and waste fuels. FIG. 2 demonstrates an exemplary embodiment 200 for integrating waste fuel gasification with reburning in a pilot-scale combustor, such as for testing the efficacy of this approach. In this example, waste fuel gasification was conducted in a Hybrid Fluidized Bed Gasifier (HFBG) 202 . The HFBG includes an auxiliary combustor 204 fired by natural gas burner 206 . The fluidized bed 210 is separated from the burner by a distributor plate 208 . The waste fuel 212 is fed directly into to the bed from a side port. The syngas is transported via a metal duct 214 to the Solid Fuels Test Facility (SFTF) 216 that simulates, and in practice may be replaced with, for example, a stoker-boiler. The primary fuel for the SFTF is, in one example, natural gas, but may be other fuels such as other fossil fuels or biomass/waste fuels. The syngas is injected into the SFTF reburning zone 218 . Overfire air 220 is injected upstream of the reburning fuel injection to complete combustion. As shown by experimental and modeling results presented in the next section, conditions in the gasifier 202 can be optimized to produce syngas 222 with certain concentrations of N- and alkali-containing species. Fuel-N from waste fuel is released in the gasifier mostly in the form of NH3. Sodium and potassium from waste fuel are released into the gas phase or carried to the reburning zone of the combustor with fly ash. Injection of syngas into the SFTF reburning zone under certain process conditions will result in a significant decrease in NOx concentration in flue gas. When conditions in the reburning zone of a boiler are optimized, the presence of NH3 and sodium in biogas will result in an increase in NOx reduction in comparison with traditional (basic) reburning. Additional NOx reduction under optimized conditions of the present invention will occur at relatively low reburning fuel injection temperatures as required for effective reactions between NOx and syngas components, such as CO, H2, hydrocarbons, ammonia, and N- and alkali-containing compounds. Prior teachings stand for the proposition that reburning efficiency increases with an increase in the amount of the reburning fuel and in the temperature of flue gas at the injection point of the reburning fuel. One unexpected finding associated with the present invention is that the efficiency of NOx reduction increases with a decrease in the post combustion or reburning fuel injection temperature. In one example, the efficiency was optimized with the flue gas temperature in the range of 1200-2200° F. at the location of the reburning fuel injection. Another surprising finding associated with the present invention is that maximum NOx reduction may be achieved at 5%-15% reburning heat input rather than at 20%-25% as suggested in prior teachings. In one set of conditions used to exemplify the operational efficacy of the embodiment of FIG. 2, the reburning fuel, i.e. the gaseous product from HFBG 202 , is injected in the range of flue gas temperatures of 1800° F.-2200° F. This is quite distinct when compared with prior teachings, wherein typical reburning applications call for OFA to be injected in the temperature range of 2300° F.-3000° F. A variety of test conditions in the embodiment of FIG. 2 yield that CO concentrations in flue gas at the SFTF exit fall below 10 ppm. It is possible to achieve such low CO concentrations in combustion products at OFA injection temperatures of 1700-1900° F. because reburning fuel was a gas. Significant NOx reduction for fuels with high fuel-N content may be achieved at 5-15% reburning fuel heat input with maximum NOx reduction at 7-10% reburning fuel heat input. At this amount of reburning fuel, the overall mixture composition remains fuel-lean. Thus, after complete oxidation of the reburning fuel, some amount of O2 is still present in flue gas. Injection of OFA at such small amount of the reburning fuel is optional since complete oxidation of the reburning fuel can be achieved by oxygen already present in flue gas. Additional control of CO and hydrocarbon emissions, if required, can be provided by installing an afterburner or an oxidation catalytic unit in the post-combustion zone downstream of reburning fuel injection. As an option, the gaseous and solid gasification products can be separated before injection into the combustion system. Some solid fuels (for example, coal and some types of waste fuels) consist of approximately equal fractions of volatile matter and fixed carbon. Complete gasification of such fuels requires high temperatures, long residence times and is difficult to achieve. Splitting the fuel stream exiting the gasifier allows the volatile matter to be used for reburning and the fixed carbon to be injected into the high-temperature main combustion zone. Thus, fuels with low volatile content can also be used in the present invention. FIG. 3 illustrates how the present invention can be applied to a coal-fired power plant. The integrated system 300 is an example of integrating a coal-fired boiler 302 with a waste gasifier 304 for achieving reduction of NOx emissions. Although a wall-fired boiler 302 is illustrated, the technology is equally applicable to all firing configurations. Waste fuel 306 is gasified in gasifier 304 . Gasification products 308 are conveyed to the furnace 310 and injected into a post combustion zone 312 . The amount of the syngas injected into the boiler is controlled to maintain an overall fuel-lean stoichiometry in the upper furnace. Therefore, no additional OFA is required in this configuration. However, OFA could optionally be injected. The following experimental and modeling examples are given to illustrate the methods and systems of the present invention, and are not intended to limit the scope of the invention. A Fluidized Bed Gasifier (HFBG) for use in the integrated system of the present invention may be comprised of several sections. For instance, the gasifier 400 as shown in FIG. 4 includes a natural gas burner 402 that supplies auxiliary heat to the fluidized bed 404 during gasification. The firing rate is, for example, about 97,000 Btu/hr. The combustor section 406 may have, for example, an internal diameter of 10″ and may be 24″ tall. The lower part may be refractory lined, while the upper part may be water-cooled. A stainless steel distributor plate 408 separates the combustor section 406 from the fluidized bed 404 . Waste fuel 410 is injected into the fluidized bed 404 , such as previously described and shown in FIG. 3 . The gasification products leaving the bed pass through a freeboard section 412 . The gasification products are conveyed via a stainless steel duct 414 to be used as a reburning fuel in the SFTF (see FIG. 5 ). Liquid Petroleum Gas (LPG) 416 , consisting mostly of propane, can be used as an auxiliary fuel and may be injected into the bed to increase the temperature prior to injecting waste fuel 410 . The LPG increased bed temperatures from about 1100° F. to 1550° F. As shown in FIG. 5, an exemplary Solid Fuels Test Facility (SFTF) 500 is comprised of a horizontal barrel section 502 , a vertical controlled temperature tower 504 , and an exhaust stack 510 . The conditions in the SFTF may be, in one instance, set to simulate a biomass-fires stoker boiler. In one particular arrangement, for example, the horizontal barrel section may have an 18″ inner diameter and be about 9 ft long. The main gas burner 512 for the furnace is located in this section. The control temperature tower also has an 18″ ID and is about 15 ft tall. During testing of the arrangement of FIG. 5, the main burner 512 was at 375,000 Btu/hr and the afterburner 514 was at 125,000 Btu/hr. The natural gas and combustion air flow rates for both the main burner and the afterburner as well as the grate air 516 were controlled by flow meters, such as those manufactured by Waukee. Dwyer rotameters, for example, were used to monitor the flow of the OFA, the syngas combustion air, and the waste fuel transport air. The SFTF exit Continuous Emissions Monitoring system (CEM) consists of a water-cooled sample probe 518 , a chiller for removing moisture, a particulate filter, a sample pump, and the following exemplary analyzers: a Servomex Paramagnetic O2 Analyzer (0-100% O2); a Thermo Environmental gas filter correlation IR CO Analyzer (0-2,500 ppm); and a Thermo Environmental Chemiluminescent NO/NOx Analyzer (0-10,000 ppm). The following description discusses test fuels and composition of gasification products. Five waste fuels were selected for testing: 1) almond shells; 2) walnut tree prunings (Wood “P”); 3) whole tree wood chips (Wood “W”); 4) non-recyclable waste paper; and 5) rice straw (fresh). These fuels generally have characteristics that make direct combustion in biomass boilers not feasible. Some of these properties are characterized by, (a) low heating value, (b) high ash content, (c) high chlorine and/or metal content, and (d) inhomogeneous composition. Tables 1 and 2 show ultimate and ash analysis of waste fuels. TABLE 1 Ultimate analysis of waste fuels. Walnut Tree Whole Tree Non Rice Almond Prunings Wood Chips Recyclable Straw Shells (Wood “P”) (Wood “W”) Waste Paper Carbon 38.50 36.27 48.20 51.15 49.11 Hydrogen 3.56 3.94 4.41 3.40 5.08 Nitrogen 0.55 0.79 0.59 0.35 0.14 Sulfur 0.06 0.05 0.03 0.05 0.06 Ash 21.03 26.57 2.43 2.68 1.05 Oxygen 36.30 32.38 44.34 42.37 44.56 Chlorine 0.58 0.03 <0.01 <0.01 0.03 During the testing, waste fuels were gasified in the fluidized bed. During a given test the feed rate of the waste fuel was varied to provide syngas of different heating values and compositions. The primary constituents of the syngas were inert species such as CO2 and N2, which together made up 75-90% of the exit gas. FIG. 6 shows the composition of combustible gases as a function of waste fuel feed rate for almond shells. Note that smaller amounts of heavier hydrocarbons that may be present in gas are not shown here. TABLE 2 Ash analysis of waste fuels. Non- Rice Almond Wood Wood Recyclable Straw Shell “P” “W” Paper SiO 2 76.36 64.32 5.80 33.77 25.30 Al 2 O 3 0.99 12.70 2.25 7.69 23.11 TiO 2 0.05 0.45 0.09 0.34 2.07 Fe 2 O 3 0.31 4.32 1.23 1.25 1.37 CaO 2.17 4.20 43.90 29.00 19.50 MgO 1.71 2.10 8.08 3.54 4.56 Na 2 O 0.30 1.87 0.31 1.21 6.31 K 2 O 11.90 8.54 10.60 9.01 4.44 P 2 O 5 1.55 0.72 2.32 1.83 5.75 SO 3 0.67 0.22 0.56 0.43 2.73 Cl 2.39 0.08 0.15 0.19 0.25 CO 2 0.22 0.48 23.68 3.36 1.52 Undetermined 1.38 0.00 1.03 8.38 3.09 Total: 100.00 100.00 100.00 100.00 100.00 The stoichiometric ratio (SR) in the bed, as shown on the secondary y-axis, varied from 0.96 to 0.29 and decreased as the almond shell feed rate increased. As more waste fuel was added to the fluidized bed, the levels of CO, H2 and hydrocarbons increased. At the highest feed rate, the syngas consisted of over 11% carbon monoxide, 5% hydrogen, 3% methane, and about 1% ethylene. The gas composition shown corresponded to a dry, particulate free, sample that is collected at the exit of the gasifier. FIG. 7 compares compositions of main combustible components of gasification gas products from different waste fuels at SR of 0.3, which corresponds to about 20% reburning heat input to the SFTF. The fluidized bed temperature for these tests varied between 1330° F. and 1430° F. The relative levels of CO, H2 and hydrocarbons were a function of stoichiometric ratio, bed temperature and fuel composition. Fuels with higher carbon content gave higher CO emissions. Waste paper had the highest concentration of CO and rice straw had the highest concentration of hydrocarbons. A process model was developed to describe NOx reduction in the integrated gasification-reburning process. Process modeling helps to understand and predict the effect of system components and conditions on NOx control. In modeling, a set of homogeneous reactions representing the interaction of reactive species was assembled. Each reaction was assigned an appropriate rate constant and heat release or heat loss parameters. Numerical solution of differential equations for time-dependent concentrations of the reagents made it possible to predict the concentration-time curves for all reacting species under selected process conditions. Using the modeling revealed the process conditions required for significant improvements in NOx removal. Natural gas reburning chemistry-mixing model (RCMM) was used to describe reburning by waste fuel gasification products. The following describes the modeling approach and presents modeling results. The RCMM includes a combination of a detailed kinetic mechanism with a simplified representation of mixing and utilizes well-stirred and plug-flow reactors to describe processes that occur in the boiler. This approach was successfully used to describe natural gas basic and Advanced Reburning. The characteristic feature of RCMM is utilization of the integrated approach to describe the reburning process. This approach includes: 1) evaluation of mixing characteristics of the combustion facility under investigation using model of single jet in crossflow; 2) utilization of plug flow reactors to describe processes that occur in the boiler; 3) the distributed addition of reagents; and 4) the inverse mixing approach. The mixing can be described as a secondary stream distributed along the primary stream in a continuous fashion over a certain period of time. It is assumed that composition of products, except for NOx, exiting the primary combustion zone corresponds to equilibrium conditions at the experimental values of temperature. The kinetic mechanism used in RCMM to describe natural gas reburning included 447 reactions of 65 C—H—O—N gas phase species. Since main combustion components of waste fuel gasification products (CH4, H2 and CO) were included in the RCMM mechanism, it gave confidence that RCMM could be applied to describe reburning by fuel gasification products. Reactions of C3 species from GRI-Mech 3.0 kinetic mechanism were added to the natural gas reburning mechanism to enable modeling of LPG reburning. The chemical kinetic code ODF, for “One Dimensional Flame” was employed to model experimental data. ODF treats a system as a series of one-dimensional reactors. Each reactor may be perfectly mixed (well-stirred) or unmixed (plug-flow). Each ODF reactor may be assigned a variety of thermodynamic characteristics, including adiabatic, isothermal, or specified profiles of temperature or heat flux, and/or pressure. Process streams may be added over any interval of the plug flow reactor, with arbitrary mixing profiles along the reactor length. The flexibility in model setup allows for many different chemical processes to be simulated under a wide variety of mixing conditions. The adopted approach was similar to that used to describe natural gas reburning. The reburning process was treated as a series of four plug-flow reactors. Each reactor described one of the physical and chemical processes occurring in a boiler, for example: addition of the reburning fuel; NOx reduction as a result of reaction with the reburning fuel; addition of overfire air; and oxidation of partially oxidized products. The mixing was described by adding flue gas to the injecting stream (inverse mixing) over mixing time. For example, mixing in the reburning zone was described by adding flue gas to the flow of gasification products; mixing of OFA was described by adding flue gas to the OFA. The mixing time in the reburning zone was an adjustable parameter. For the reburning fuel and OFA jets, the mixing time was adopted to be 120 ms, the same as was estimated for experimental conditions. This is also the same value that was estimated for similar conditions using a model of a single jet in cross flow for natural gas reburning. Modeling showed that the value of the mixing time had a relatively small effect on the efficiency of NOx reduction. For example, a 100% decrease in mixing time resulted in about 30% improvement in the reburning efficiency. As in experiments, flue gas compositions in the main and OFA zones corresponded to SR1=1.1 and SR3=1.25, respectively. Initial NOx (NOi) was 300 ppm. Next we consider the composition of gasification products in modeling. The presence of fuel-N and sodium in gasification gas has to be taken into account to explain experimental observations. The concentration of N in waste fuels (Table 1) is less than 1% and is less than is usually found in coals (1%-2%). However, this amount of fuel-N can contribute to NOx production and reduction. Because of the large volatile content of waste fuels, it can be expected that most fuel-N is released into the gas phase. When injected in the reburning zone, and depending on conditions in this zone, N-containing species can be partially reduced to molecular nitrogen N2, partially oxidized by excess air coming from the main combustion zone to form NOx, or can react with NO from flue gas and reduced to N2. Ash analysis (Table 2) showed that sodium content in some waste fuels was significant. Adding sodium compounds to the reburning and overfire (in presence of N-agent) zones can increase NOx reduction. Reactions of Na with components of flue gas have been studied in connection with reduction of NO and N2O emissions in SNCR and reburning processes. The chemistry of NaOH decomposition and reactions with C—H—O—N species at high temperatures were incorporated into the kinetic model by adding reactions of Na species to the reaction mechanism used to describe waste fuel reburning. Concentrations of N- and Na-containing species in gasification products were estimated. It was assumed that as waste fuel was gasified, 80% of the fuel-N was released, comprising approximately 50% as NH3 and 50% as N2. The remaining 20% was assumed to be bound in the char residue. It was also assumed that NH3 concentration in gasification products increased with the increase in the reburning fuel heat input. This assumption was based on the following consideration. In tests, an increase in the reburning fuel heat input was achieved by increasing the amount of waste fuel in the gasifier while supply of air was constant. This produced gasification products with larger concentrations of hydrocarbons, H2 and CO. It is reasonable to assume that concentrations of N-containing species in gasification products also increased with an increase in waste load in the gasifier. Estimations of NH3 concentration in gasification products made using this approach agreed reasonably well with experimental measurements. For example, concentration of NH3 in gasification products of almond shells at 7.3% reburning heat input was estimated using this approach to be 1,100 ppm. This estimate qualitatively agrees with value 750 ppm measured using the Drager tube. It should be noted that the Drager tube measurements have low accuracy and should be used only for the order of magnitude estimate of NH3 concentration. The concentration of sodium containing species (represented in modeling as NaOH) in reburning fuel was estimated using the following approach. First, equilibrium concentrations of Na-containing species in the gas phase in the gasifier were calculated using NASA equilibrium code/standard CET93. These calculations were done for the temperature in the gasifier at 1500° F. for each waste fuel using data on Na content from Table 2. Equilibrium calculations predicted that most stable Na-containing species in the gas phase were atomic Na and NaOH(g). Second, concentrations of Na-containing species in the reburning fuel were determined using calculated equilibrium Na and NaOH concentrations in gasification products and volumes of streams of gasification products and dilution streams of N2 (carrier for the reburning fuel) and CO2 (fluidizing media in the gasifier). The following are examples of determining the efficacy of NOx reduction in the integrated direct combustion and gasification system of the present invention. In a first example, tests were conducted to evaluate efficiency of gasification products as a reburning fuel. The SFTF was fired on natural gas at a baseline firing-rate of 500,000 Btu/hr. The gasification products were injected as reburning fuel. Temperature of flue gas at the location of reburning fuel injection was 2150° F. The OFA was injected at flue gas temperature of 1850° F. FIG. 8 shows NO reduction as a function of reburning heat input for various waste fuels. For comparison the reburn performance of LPG is also shown. Presented data correspond to initial NO levels of 300 ppm (at 0% O2). Initial NO level was controlled by ammonia injection in the main burner. FIG. 8 shows that the reburning performance of gasified waste fuel increased with an increase in reburning fuel heat input. However, with the exception of waste paper, the performance dipped at 20% reburning. The waste fuels contain varying amounts of nitrogen (see Table 1) and sodium (see Table 2). The fuel nitrogen can form nitrogenous species such as ammonia and hydrogen cyanide in the gasification products. Measurements of NH3 concentration in gasification products confirmed that a significant fraction of fuel-N in waste fuel was converted to NH3 in the gasifier. Measurements using Drager tube revealed that at 7.3% of the reburning fuel heat input, NH3 concentrations in almond shells and sewage sludge gasification products were 750 ppm and 850 ppm, respectively. NH3 can form NO in the presence of excess oxygen supplied by the OFA. Because a higher amount of reburning fuel corresponded to a higher biomass feed rate, the impact of fuel nitrogen on reburning performance was enhanced at higher reburning rates. The greatest dip in performance was observed for the almond shells and rice straw that had 0.79% and 0.55% fuel nitrogen, respectively. No performance dip was observed for the waste paper, which has only 0.14% fuel nitrogen. This example demonstrates that for fuels with relatively high fuel-N content, there is a maximum in reburning NOx control efficiency corresponding to approximately 7-15% of reburning fuel heat input. In a second example, tests were conducted under the same conditions as those in the first example. FIG. 9 shows reburning performance at 20% reburning fuel heat input for waste fuels as a function of fuel nitrogen content. FIG. 9 demonstrates linear correlation between fuel-N waste fuel content and NO reduction at large heat input of the reburning fuel and confirms that fuel-N plays an important role in NOx reduction/formation at large levels of heat input of the reburning fuel. This example demonstrates that the presence of NH3 in gasification products results in a decrease in efficiency of NOx reduction at large heat input of the reburning fuel because NH3 was oxidized to form NOx. In a third example, tests were conducted under the same conditions as those in the first example. FIG. 8 shows that NOx reduction at small heat input of the reburning fuel (approximately 6%-15%) is different for different waste fuels. These differences are due to differences in compositions of gasification products of waste fuels. FIG. 10 shows correlation between NOx reduction and concentrations of fuel-N and sodium in waste fuel at 8% reburning fuel heat input. This example demonstrates that both fuel-N and sodium content of waste fuel determine the efficiency of NOx reduction by gasification products at relatively small heat input of the reburning fuel. The larger fuel-N and sodium content of waste fuel results in a deeper NOx reduction. In a fourth example, tests using the pilot scale facilities of FIG. 2 were conducted to determine the effect of flue gas temperature at the location of the reburning fuel injection on NOx reduction. The efficiency of NO reduction in reburning increases with an increase in flue gas temperature at which reburning fuel is injected. This is because at higher temperatures reburning fuel is oxidized faster, resulting in faster generation of active species involved in NO reduction. Tests conducted with gasification products of waste paper confirmed this expectation. FIG. 11 shows that the efficiency of NO reduction increased by about 5 percent at 20% reburning fuel heat input as temperature increased from 2150° F. to 2350° F. This example demonstrates that for fuels with relatively low fuel-N content, the efficiency of NO reduction in reburning increases with an increase in flue gas temperature at which reburning fuel is injected. In a fifth example, tests in the pilot scale facilities of FIG. 2 were conducted to determine the effect of flue gas temperature at the location of the reburning fuel injection and reburning fuel heat input on NOx reduction. One unexpected finding of the invention was that performance of gasification products as a reburning fuel of some waste fuels improved with a decrease in temperature. FIG. 12 compares reburning performance of almond shells gasification products at 1830° F. and 2150° F. FIG. 12 shows that maximum NO reduction increased from 40% to 65% as reburning fuel injection temperature decreased from 2150° F. to 1830° F. Optimum NO reduction at 1830° F. was achieved at 7-10% reburning fuel heat input while at 2150° F. optimum was achieved at 10-15% reburning fuel heat input. This example demonstrates that NOx control achieved with gasification products as reburning fuel can be significantly higher at lower reburning fuel injection temperatures. A high level of NOx control can be achieved at a low reburning fuel heat input of 7-10%. In a sixth example, fuel nitrogen and sodium impacts on reburning performance were evaluated through the above-described modeling study. FIGS. 13-16 present comparison of modeling predictions (curves) and experimental data (points). As in experiments, reburning fuel and OFA were injected in the model at flue gas temperatures of 2150° F. and 1850° F., respectively. Modeling predicted that performance of LPG improved as the amount of reburning fuel increased. The same behavior was predicted for waste paper for which fuel-N content (Table 1) was very low. The model predicts that the efficiency of NOx reduction for almond shells and Wood P, on the other hand, decreases when the amount of the reburning fuel is over 15% by heat input. The model explains this effect as oxidation of the NH3 present in the reburning fuel to NO at 2150° F. Predicted effects of Na and NH3 on NOx reduction in almond shells reburning are demonstrated in FIG. 17 . The efficiency of NOx reduction without Na and NH3 was relatively lesser at 15% reburning heat input and greater at 20% reburning heat input. At 20% reburning heat input, the amount of NH3 in reburning fuel was too large, which led to the undesired result of some NH3 being oxidized to NOx. This example demonstrates that the model correctly predicts NOx reduction for reburning with gasification products with different gas composition, including the concentration of NH3 and sodium compounds in gasification products. The model also correctly predicts NOx reduction at reburning heat inputs in the range of 0-20%. In a seventh example, close agreement of modeling predictions and experimental data for different gasified fuels, as demonstrated in the sixth example, provides confidence that the model correctly predicts key benefits of the inventive process. In this example, the model is used to determine the effect of temperature on reburning with syngas containing a high amount of fuel-N and Na. FIG. 18 shows predicted efficiency of NOx reduction (curve) in reburning with almond shells gasification products as a function of flue gas temperature at which reburning fuel was injected at 10% reburning fuel heat input. Experimental data are also shown (points). Modeling predicted that efficiency of NOx reduction could be increased up to 70% by lowering flue gas temperature at which reburning fuel is injected. The efficiency of NOx reduction increased with a decrease in temperature because optimum temperatures for NOx reduction by NH3 are in the range of 1800° F.-2000° F. The model predicts that an optimum in NOx reduction occurs even at lower temperatures in the presence of CO and H2 syngas components. Since concentrations of CO and H2 in gasification products of all tested waste fuels are high (see FIG. 7 ), the efficiency of NOx reduction in almond shells reburning reaches maximum at about 1750° F.-1800° F. This example demonstrates that the efficiency of NOx control with gasification products increases at lower temperatures and can be as high as approximately 70% at only 10% of reburning fuel by heat input. The optimum temperature of NOx control is largely defined by the composition of gasification products (CO, H2, hydrocarbons, N- and alkali-containing compounds), composition of the flue gas at the point of reburning fuel injection, and the temperature of flue gas at the point of reburning fuel injection. As observed in examining the results of the various examples and tests, the present invention provides a method of decreasing the concentration of nitrogen oxides in combustion systems and utilization of low grade solid fuels. One example of a process for achieving the benefits of the present invention includes the following described steps. A first step of causing combustion of the main fuel in a combustion system resulting in generating a combustion flue gas in a post combustion zone. The combustion flue gas includes nitrogen oxides. The next step involves the gasification of solid fuels in a gasifier so as to generate gaseous product containing solid particles. The gaseous product includes at least one or more of the group consisting of carbon monoxide, hydrogen, hydrocarbons, steam, carbon dioxide, ammonia and other reduced N-containing species, and small amounts of alkali-containing compounds. Next, the gaseous products are injected into the post combustion zone of the combustion system to create a reaction zone in which nitrogen oxides are reduced to molecular nitrogen. In addition, this exemplary embodiment of the present invention may involve one or more of the following aspects. The main fuel may be selected from coal, biomass, waste products, or combinations of thereof. The gasified solid fuel may be selected from biomass, waste products, coal or combination of thereof. The concentrations of carbon monoxide, hydrogen, and hydrocarbons in gasification products may be in the range of 0.1%-30% each. In one preferred embodiment, the concentrations of hydrocarbons in gasification products are in the range of 0.5%-10%. The concentrations of ammonia and other reduced N-containing species in gasification products may be in the range of 50-10,000 ppm. The molar ratio of ammonia and other reduced N-containing species in gasification products injected in the combustor to the NO in the post combustion zone may be in the range of 0.2-2.0. In one preferred embodiment, the molar ratio of ammonia and other reduced N-containing species in gasification products injected in the combustor to the NO in the post combustion zone may be in the range of 0.8-1.5. The concentrations of alkali-containing species in the gaseous product may be in the range of 1-300 ppm. In one embodiment, the preferred concentrations of alkali-containing species in the gaseous product may be in the range of 20-100 ppm. The temperatures of flue gas at the location of the gaseous product injection may be in the range of 1600° F.-2300° F. The amount of the gaseous products injected in the post combustion zone may be in the range of 5-25% of the total fuel by heat input. In one embodiment, the preferred amount of the gaseous products injected in the post combustion zone may be in the range of 7-12% of the total fuel by heat input. The overfire air may be injected downstream of the gaseous products injection point to oxidize remaining combustible products. Further, overfire air can be injected or an afterburner may be installed downstream of the gaseous products injection point to oxidize remaining combustible products. A catalytic unit may be installed downstream of the gaseous products injection point to oxidize remaining combustible products. Solid particles, such as char, soot, and fly ash, may be separated from the gaseous product before injection in the post combustion zone. In addition, such solid particles may be separated from the gaseous product before injection in the post combustion zone and directed to the main combustion zone. While the invention has been described with reference to particular embodiments and examples, those skilled in the art will appreciate that various modifications may be made thereto without significantly departing from the spirit and scope of the invention.
The methods and systems of the present invention reduce NOx emissions in combustion systems, e.g., power plants, boilers, furnaces, incinerators, engines, and any combinations thereof. The inventive process decreases NOx emissions from stationary combustion sources and provides improved utilization of low-grade biomass and other waste fuels without slagging and fouling problems. The invention reduces NOx emissions while utilizing gasified fuels, including biomass and low-grade waste fuels, by gasifying solid fuels and injecting produced gas into a reburning zone of, for example, a boiler at relatively low temperatures and in relatively small amounts. By feeding the gas directly into a reburning zone, the need for gas cleaning is eliminated or substantially reduced as tars are burned in the flame and alkali species may be present at much lower levels than is the case with direct combustion applications.
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CROSS-REFERENCE TO RELATED APPLICATION(S) [0001] This application claims the benefit of U.S. Provisional Patent Application No. 60/426,834, filed Nov. 15, 2003, the entire disclosure of which is incorporated herein by reference. BACKGROUND [0002] Electrophysiology catheters are commonly used for mapping electrical activity in a heart. By mapping the electrical activity in the heart, one can detect ectopic sites of electrical activation or other electrical activation pathways that contribute to heart malfunctions. This type of information may then allow a cardiologist to intervene and destroy the malfunctioning heart tissues. Such destruction of heart tissue is referred to as ablation, which is a rapidly growing field within electrophysiology and obviates the need for maximally invasive open heart surgery. [0003] Such electrophysiology mapping catheters typically have an elongated flexible body with a distal end that carries one or more electrodes that are used to map or collect electrical information about the electrical activity in the heart. The distal end can be deflectable to assist the user in properly positioning the catheter for mapping in a desired location. Typically, such catheters can be deflected to form a single curve. It is desirable to have a catheter that can be deflective to form a variety of curves to thereby map an entire region where a single curve may not be sufficient. SUMMARY OF THE INVENTION [0004] The present invention is directed to an improved catheter that is particularly useful for mapping electrical activity in a heart of a patient and that allows the user to vary curve preferences as well as the number of electrodes to be used to map a particular area of tissue. [0005] In one embodiment, the invention is directed to a catheter comprising an elongated catheter body having a proximal end, a distal end and a lumen extending longitudinally therethrough. A control handle is attached to the proximal end of the catheter body. The control handle includes a first member, such as housing, that is moveable relative to a second member, such as a piston slidably mounted in the housing. The catheter body is attached to the second member. [0006] An inner member is slidably mounted in the lumen of the catheter body. The inner member comprises an elongated stiffening member, having proximal and distal ends, that is surrounded by and connected to a non-conductive covering. The non-conductive covering has a free distal end on which is mounted one or more electrodes. The proximal end of the inner member is attached to the first member of the control handle. Longitudinal movement of the first member relative to the second member results in longitudinal movement of the inner member relative to the catheter body to cause the inner member to extend out of and retract into the catheter body. DESCRIPTION OF THE DRAWINGS [0007] These and other features and advantages of the present invention will be better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings wherein: [0008] [0008]FIG. 1 is a perspective view of a catheter according to the invention. [0009] [0009]FIG. 2 is an end cross-sectional view of the catheter body of the catheter of FIG. 1 taken along line 2 - 2 . [0010] [0010]FIG. 3 is an end cross-sectional view of the inner member of the catheter of FIG. 1 taken along line 3 - 3 . [0011] [0011]FIG. 4 is a side cross-sectional view of the control handle of the catheter of FIG. 1. DETAILED DESCRIPTION OF THE INVENTION [0012] The invention is directed to a telescoping catheter having an extendable and retractable mapping assembly at the distal end of the catheter that is deflectable. As shown in FIG. 1, the catheter comprises an elongated catheter body 12 having proximal and distal ends, an elongated telescoping inner member 14 extending through the catheter body, and a control handle 16 at the proximal end of the catheter body. The catheter body 12 comprises an elongated tubular construction having a single, axial or central lumen 15 , as shown in FIG. 2, but can optionally have multiple lumens along all or part of its length if desired. The catheter body 12 is flexible, i.e., bendable, but substantially non-compressible along its length. The catheter body 12 can be of any suitable construction and made of any suitable material. A presently preferred construction of the catheter body 12 comprises an outer wall 18 made of polyurethane or PEBAX® (polyether block amide). The outer wall 18 preferably comprises an imbedded braided mesh of stainless steel or the like, as is generally known in the art, to increase torsional stiffness of the catheter body 12 so that, when the control handle 16 is rotated, the distal end of the catheter body 12 will rotate in a corresponding manner. [0013] The length of the catheter body 12 is not critical, but preferably ranges from about 90 cm to about 120 cm, and more preferably is about 110 cm. The outer diameter of the catheter body 12 is also not critical, but is preferably no more than about 8 french, more preferably about 7 french. Likewise, the thickness of the outer wall 18 is not critical, but is preferably thin enough so that the central lumen 15 can accommodate all necessary wires and other components extending through the catheter body 12 . [0014] In the depicted embodiment, two ring electrodes 17 are mounted, preferably evenly-spaced, along the distal end of the catheter body 12 . As would be recognized by one skilled in the art, the number and arrangement of the electrodes on the catheter body can vary as desired, or the electrodes can be eliminated altogether. Each ring electrode 17 is electrically connected to an electrode lead wire 19 , which in turn is electrically connected to a connector 34 at the proximal end of the catheter, which is connected to an appropriate mapping or monitoring system (not shown). Each electrode lead wire 19 extends from the connector 34 , through the control handle 16 , and into the central lumen 15 of the catheter body 12 where it is attached to its corresponding ring electrode 17 . Each lead wire 19 , which includes a non-conductive coating over almost all of its length, is attached to its corresponding ring electrode 17 by any suitable method. [0015] The inner member 14 is slidably mounted within the central lumen 15 of the catheter body 12 . As best shown in FIG. 3, the inner member 14 comprises an elongated stiffening member 20 surrounded by a flexible non-conductive cover 22 . The stiffening member 20 preferably comprises a superelastic material, for example a nickel-titanium alloy such as nitinol, but can comprise any other suitable material, such as stainless steel or plastic. The non-conductive cover 22 preferably comprises a biocompatible plastic tubing, such as a polyurethane or polyimide tubing. In the depicted embodiment, the non-conductive cover 22 has an outer wall 24 with a single lumen 26 extending therethrough, but could alternatively include multiple lumens. The non-conductive cover 22 , and thus the inner member 14 , has a free distal end, i.e., a distal end that is not connected or attached to any other part of the inner member, to the catheter body, or to any other external structure that confines movement of the distal end. [0016] In the depicted embodiment, the distal end of the inner member 14 has an atraumatic tip comprising a plastic cap 28 , preferably made of polyurethane. The plastic cap 28 is glued or otherwise fixedly attached to the distal end of the inner member 14 . Other atraumatic tip designs could be used in connection with the invention, or the use of an atraumatic tip can be eliminated. [0017] The inner member 14 carries one or more electrodes along its distal end. In the depicted embodiment, twelve ring electrodes 30 are mounted, preferably evenly-spaced, along the distal end of the non-conductive cover 22 . As would be recognized by one skilled in the art, the number and arrangement of the electrodes on the inner member can vary as desired. For example, the inner member 14 could carry a tip electrode (not shown) on the distal end of the spine in place of the plastic cap 28 . Each ring electrode 30 has a length preferably up to about 2 mm, more preferably from about 0.5 mm to about 1 mm. The distance between the ring electrodes 28 preferably ranges from about 1 mm to about 10 mm, more preferably from about 2 mm to about 5 mm. Preferably the inner member 14 carries from 2 to about 20 electrodes, more preferably from 3 to about 15 electrodes. [0018] Each ring electrode 30 is electrically connected to an electrode lead wire 32 , which in turn is electrically connected to the connector 34 , which is connected to an appropriate mapping or monitoring system (not shown). In the depicted embodiment, the inner member electrode lead wires 32 are connected to the same connector as the catheter body electrode lead wires 19 , but could also be connected to a different connector depending on the desired application. Each electrode lead wire 32 extends from the connector 34 , through the control handle 16 , and into the non-conductive cover 22 of the inner member 14 where it is attached to its corresponding ring electrode 30 . Each lead wire 32 , which includes a non-conductive coating over almost all of its length, is attached to its corresponding ring electrode 30 by any suitable method. [0019] A preferred method for attaching a lead wire 19 or 32 to a ring electrode 17 or 30 involves first making a small hole through the outer wall of the catheter body 12 or non-conductive cover 22 . Such a hole can be created, for example, by inserting a needle through the outer wall and heating the needle sufficiently to form a permanent hole. The lead wire 19 or 32 is then drawn through the hole by using a microhook or the like. The end of the lead wire 19 or 32 is then stripped of any coating and welded to the underside of the corresponding ring electrode 17 or 30 , which is then slid into position over the hole and fixed in place with polyurethane glue or the like. Alternatively, each ring electrode 19 or 30 may be formed by wrapping the lead wire 17 or 32 around the catheter body 12 or non-conductive cover 22 a number of times and stripping the lead wire of its own non-conductive coating on its outwardly facing surfaces. In such an instance, the lead wire functions as a ring electrode. [0020] The inner member 14 is moveable between a retracted position, where the entire inner member is contained within the central lumen 15 of the catheter body 12 , and a fully extended position, where all of the electrodes 30 mounted on the inner member extend beyond the distal end of the catheter body. The length of the exposed portion of the inner member 14 when in the fully extended position preferably ranges from about 10 mm to about 200 mm. The inner member 14 can also be moved to one or more intermediate extended positions where the distal end of the inner member 14 extends beyond the distal end of the catheter body 12 , but one or more of the electrodes 30 are still contained within the central lumen 15 of the catheter body. To affect such movement, the proximal end of the stiffening member 20 is attached to the control handle 16 , as discussed in more detail below. [0021] In the depicted embodiment, the distal end of the stiffening member 20 is attached to the distal end of the inner member 14 , and indirectly to the distal end of the non-conductive cover 22 , by being glued or otherwise attached to the plastic cap 22 . The stiffening member 20 can be attached, directly or indirectly, to the non-conductive cover 22 in any other manner and at any other position along the length of the inner member 14 . However, it is currently preferred that the stiffening member 20 be attached to the non-conductive cover 22 closer to the distal end of the inner member 14 to permit the user to have better control when extending and retracting the inner member. [0022] In the depicted embodiment, the non-conductive cover 22 extends the full length of the catheter body 12 with its proximal end in the control handle 16 . However, if desired, the non-conductive cover 22 can terminate at its proximal end at any position within the catheter body 12 . The non-conductive cover 22 should be sufficiently long so that, when the inner member 14 is in its fully extended position, at least a portion of the non-conductive cover is maintained within the catheter body 12 . [0023] Within the catheter body 12 , the inner member 14 extends through a sleeve 38 , preferably made of plastic, such as nylon. The sleeve 38 serves as a lumen for the inner member 14 within the catheter body 12 . In particular, the sleeve 38 protects the inner member 14 from interfering or getting tangled with the lead wires 19 that extend through the catheter body 12 when the inner member 14 is being extended or retracted. [0024] Additionally, a mechanism is provided for deflecting the distal end of the inner member 14 . Specifically, a puller wire 36 extends through the non-conductive cover 22 with a distal end anchored at or near the distal end of the inner member 14 and a proximal end anchored to the control handle 16 , as described further below. The puller wire 36 is made of any suitable metal, such as stainless steel or Nitinol, and is preferably coated with Teflon® or the like to impart lubricity to the puller wire. The puller wire 36 preferably has a diameter ranging from about 0.006 to about 0.010 inches. [0025] A preferred mechanism for anchoring the puller wire 36 to the inner member 14 comprises a T-bar anchor 39 anchored within the plastic cap 28 by glue or the like. If the inner member 14 includes multiple lumens, the T-bar anchor 39 can be anchored to the plastic cap 28 as generally described in U.S. Pat. Nos. 5,893,885 and 6,066,125, the entire disclosures of which are incorporated herein by reference. If the inner member 14 carries a tip electrode, the puller wire 36 can be anchored in the tip electrode, as also described in U.S. Pat. No. 6,066,125. Alternatively, the puller wire 36 can be anchored to the side of the inner member 14 , as generally described in U.S. Pat. No. 6,123,699, the entire disclosure of which is incorporated herein by reference. Other arrangements for anchoring a puller wire 36 to the distal end of the inner member 14 are included within the scope of the invention. If desired, a compression coil (not shown) may be provided in surrounding relation to the puller wire 36 within the catheter body 12 , as described in U.S. Pat. No. 6,066,125. [0026] Longitudinal movement of the stiffening member 20 to affect extension and retraction of the inner member 14 is accomplished by suitable manipulation of the control handle 16 . Similarly, longitudinal movement of the puller wire 36 relative to the catheter body 12 , which results in deflection of the inner member 14 , is accomplished by suitable manipulation of the control handle 16 . [0027] As shown in FIGS. 1 and 4, a preferred control handle comprises a generally cylindrical housing 40 having a piston chamber 42 at its distal end. A generally cylindrical piston 44 is disposed within and generally coaxial with the piston chamber 42 . The piston 44 includes a circumferential O-ring notch 46 that carries an O-ring 48 to provide a snug, watertight fit between the piston and the wall of the piston chamber 42 . The piston 44 has an axial bore 50 along its length. The diameter of the axial bore 50 is approximately the same as the outer diameter of the catheter body 12 . The proximal end of the catheter body 12 extends into the axial bore 50 and is fixedly attached, for example, by glue, to the piston 44 . The stiffening member 20 , puller wire 36 , and electrode lead wires 19 and 32 extend from the inner member 14 or catheter body 12 , through the axial bore 50 of the piston 44 and into the control handle 16 . [0028] The distal end of the piston 44 extends beyond the distal end of the housing 40 so that it can be manually controlled by the user. An annular thumb control 52 is attached at or near the distal end of the piston 44 to facilitate lengthwise movement of the piston relative to the housing 40 . [0029] For longitudinal movement of the stiffening member 20 , the housing includes a longitudinal slot 56 extending therethrough. A slider 58 is slidably mounted in the longitudinal slot 56 , as best shown in FIG. 1. The proximal end of the stiffening member 20 is anchored to the portion of the slider 58 that is contained within the handle housing 40 by any suitable method. A suitable method for anchoring the stiffening member 20 to the slider 58 involves use of a short stainless steel tubing 60 or the like mounted on the proximal end of the stiffening member. The slider 58 includes an opening 62 for receiving the stainless steel tubing 60 and a channel 64 distal to the opening having a size that permits the stiffening member 20 to pass therethrough but that prevents the stainless steel tubing from passing therethrough. Other mechanisms for anchoring the stiffening member 20 to the slider 58 are within the scope of the invention. [0030] For longitudinal movement of the puller wire 36 , the puller wire is anchored to the housing 40 by any suitable method. In the depicted embodiment, the puller wire 36 is anchored to the housing by means of an anchor 54 that extends into a transverse hole in the housing proximal to the piston chamber 42 . Such a design is described in more detail in U.S. Pat. No. 5,383,923, the entire disclosure of which is incorporated herein by reference. In use, the distal end of the inner member 14 , once moved to an extended position, can be curved or bent by moving the piston 44 distally out of the piston chamber 42 by pushing outwardly on the thumb control 52 . [0031] The precise control handle mechanisms used for deflection of the puller wire 36 and for extension of the inner member 14 can be modified as desired. For example, the slider 58 could instead be used for manipulation of the puller wire 36 , and the piston 42 can be used for manipulation of the stiffening member 20 . Other control handles capable of manipulating a plurality of wires can also be used in connection with the invention. Examples of such handles are disclosed in U.S. Pat. No. 6,066,125 and U.S. patent application Ser. No. 09/710,210, entitled “Deflectable Catheter with Modifiable Handle,” the disclosures of which are incorporated herein by reference. [0032] If desired, a catheter body puller wire (not shown) can also be provided for deflection of the distal end of the catheter body 12 . With such a design, the catheter puller wire is anchored at its distal end to the distal end of the catheter body, as generally described in U.S. Pat. No. 6,123,699, and is anchored at its proximal end to the control handle 16 . To manipulate the catheter body puller wire, the control handle would contain an additional deflection mechanism, such as an additional slider (not shown) in a separate slot. If desired, the distal end of the catheter body 12 can comprise a piece of tubing (not shown) that is more flexible than the rest of the catheter body and that contains an off-axis lumen (not shown) into which the distal end of the catheter puller wire extends, as generally described in U.S. Pat. No. 6,123,699. [0033] If desired, the inner member 14 and/or the distal end of the catheter body 12 can also include one or more location sensors (not shown), such as an electromagnetic location sensor, for conveying locational information about the electrodes on the inner member and/or catheter body. Use and design of such location sensors are described in more detail in U.S. application Ser. No. 10/040,932, entitled “Catheter Having Multiple Spines Each Having Electrical Mapping and Location Sensing Capabilities,” the disclosure of which is incorporated herein by reference. [0034] The preceding description has been presented with references to presently preferred embodiments of the invention. Persons skilled in the art and technology to which this invention pertains will appreciate that alterations and changes in the described structures can be practiced without meaningfully departing from the principle, spirit and scope of this invention. Accordingly, the foregoing description should not be read as pertaining only to the precise structures described and shown in the accompanying drawings, but rather should be read as consistent with and as support for the following claims, which are to have their fullest and fairest scope.
A catheter that is particularly useful for mapping electrical activity in the heart of a patient is provided. The catheter comprises an elongated catheter body having a lumen extending longitudinally therethrough. A control handle is attached to the proximal end of the catheter body and includes first and second members that are moveable relative to each other. The second member is attached to the catheter body. An inner member is slidably mounted in the lumen of the catheter body. The inner member comprises an elongated stiffening member that is surrounded by and connected to a non-conductive covering having a free distal end on which is mounted one or more electrodes. The proximal end of the inner member is attached to the first member of the control handle. Longitudinal movement of the first member relative to the second member results in longitudinal movement of the inner member relative to the catheter body to cause the inner member to extend out of and retract into the catheter body.
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BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to the large-scale manufacture of pharmaceutical compounds, in particular the large-scale manufacture of 2,4-pyrimidinediamines and intermediates used therein. Background of the Invention International patent application WO 2005/016893 discloses 2,4-pyrimidinediamine compounds, and pharmaceutically acceptable salts thereof and processes thereto, which are useful in the treatment and prevention of various diseases. International patent application WO 2006/078846 discloses prodrugs of 2,4-pyrimidinediamine compounds and processes thereto. International patent application WO 2011/002999 discloses a process for preparing a 2,4-pyrimidinediamine compound of formula (I): The compound of formula (I) is being developed as an active pharmaceutical compound. SUMMARY OF THE INVENTION Appropriate methods for the cost-effective, efficient and environmentally sensitive manufacture of the compound of formula (I) are desirable. It is also desirable to utilize manufacturing conditions that reduce product degradation and improve reaction selectivity. The present invention provides processes for the large-scale manufacture of a compound of formula (I) as well as hydrates (such as hexahydrates) thereof In a first aspect of the invention, there is provided a process for preparing a compound of formula (I) or hydrate thereof which comprises: (a) contacting an amide solvate of the compound of formula (II) with an amine under conditions suitable for forming an amine salt of the compound of formula (II); and (b) contacting the amine salt with a reagent comprising sodium ions under conditions suitable for forming the compound of formula (I) or hydrate thereof. In an embodiment of the invention, the compound of formula (I) produced by this method is a hydrate. In a particular embodiment the compound of formula (I) produced by this method is a hexahydrate. In some embodiments, the amide component of the amide solvate of the compound of formula (II) is R 30 CON(R 2 ) 2 where each R 2 is independently —H or C 1-4 alkyl, or both R 2 groups together with the nitrogen to which they are attached form a 4 to 6-membered heterocyclic ring, and R 30 is —H or C 1-4 alkyl; or R 30 and one of the R 2 groups together with the nitrogen to which they are attached, respectively, combine to form a 4 to 6-membered heterocyclic ring, and the other R 2 group is independently —H or C 1-4 alkyl. In some embodiments, the amide component is selected from N,N-di-(C 1-4 alkyl)-formamide, N,N-di-(C 1-4 alkyl)-acetamide, N—C 1-6 alkyl-pyrrolidinone or N—C 1-6 alkyl-piperidinone. In a yet further embodiments, the amide component is N,N-dimethylformamide (DMF). In a particular embodiment, the amide solvate is of formula (III): In a still further embodiment, the amine component of the amine salt of the compound of formula (II) is N(R 40 ) 3 where each R 40 is independently —H or C 1-12 alkyl, or two R 40 groups together with the nitrogen to which they are attached form a 4 to 6-membered heterocyclic ring and the remaining R 40 group is —H or C 1-12 alkyl. In a yet further embodiment, the amine component of the amine salt of the compound of formula (II) is N(R 40 ) 3 where each R 40 is independently C 1-12 alkyl, or two R 40 groups together with the nitrogen to which they are attached form a 4 to 6-membered heterocyclic ring and the remaining R 40 group is C 1-12 alkyl. In a further embodiment the amine component is selected from N(C 1-6 alkyl) 3 , N-methyl morpholine or N-methyl piperidine. In a still further embodiment, the amine component is N(C 1-6 alkyl) 3 such as trimethylamine, dimethylethylamine, triethylamine, tripropylamine, tributylamine or di-isopropylethylamine. In a further embodiment, the amine component is triethylamine. In a further embodiment, the amine salt of the compound of formula (II) is the triethylammonium salt. In a still further embodiment, the stoichiometric ratio of triethylamine to the compound of formula (II) is between 0.5:1 and 2.5:1, for example between 1.5:1 and 2.5:1, such as about 2:1. In a yet further embodiment, the amine salt is the bis(triethylammonium) salt of the compound of formula (II) (the compound of formula (IV)): In a further embodiment, the conditions suitable for forming an amine salt of the compound of formula (II) comprises combining a solution of the amine in a polar solvent and water with the amide solvate of the compound of formula (II). In a further embodiment, the conditions suitable for forming an amine salt of the compound of formula (II) comprise: (i) combining a solution of the amine in a polar solvent and water with the amide solvate of the compound of formula (II); and (ii) filtering the reaction mixture. In a still further embodiment, the polar solvent is selected from an alcohol, acetone, acetonitrile and dimethylsulfoxide. In a yet further embodiment the polar solvent is an alcohol, such as isopropanol. In a further embodiment, the formation of the amine salt is carried out at a temperature not exceeding 70° C., for example from about 0° C. and not exceeding 60° C., 50° C., 40° C., 30° C., 20° C. or 10° C., such as from about 10° C. to about 30° C. In a still further embodiment, the formation of the amine salt is carried out at ambient temperature. In a yet further embodiment, the solution of the amine in a polar solvent and water is added to the amide solvate. In a further embodiment, the conditions suitable for forming the compound of formula (I) or hydrate thereof comprises combining a solution of the reagent comprising sodium ions in a polar solvent and water with the solution of the amine salt of the compound of formula (II) as obtained from the preceding step. In a still further embodiment, the polar solvent is selected from an alcohol, acetone, acetonitrile and dimethylsulfoxide. In a yet further embodiment the polar solvent is an alcohol, such as isopropanol. In a still further embodiment, the polar solvent is the same as the polar solvent used in the preceding step. In a further embodiment, the reagent comprising sodium ions is selected from sodium chloride, sodium acetate, sodium carbonate, sodium sulphate or sodium 2-ethylhexanoate, for example sodium chloride or sodium ethylhexanoate, such as sodium 2-ethylhexanoate. In a further embodiment, the reagent comprising sodium ions is added to the solution of the amine salt. In a further embodiment, the formation of the compound of formula (I) or hydrate thereof is carried out at a temperature not exceeding 70° C., for example not exceeding 60° C., 50° C., 40° C., 30° C., 20° C. or 10° C. In a still further embodiment, the formation is carried out at a temperature not exceeding 40° C. In a yet further embodiment, the solution of the amine salt is warmed to the required reaction temperature prior to the addition of the reagent comprising sodium ions. In a still further embodiment, the combined solution of the reagent comprising sodium ions with the solution of the amine salt of the compound of formula (II) further comprises a seed of the compound of formula (I) or hydrate thereof. In a further embodiment, a proportion of the reagent comprising sodium ions (for example less than 50%, such as less than 40%, 30%, 20%, 10% or 5%, for example less than 5%) and a seed of the compound of formula (I) or hydrate thereof is added to the solution of the amine salt of the compound of formula (II). The reaction mixture is then held for a period of time (for example at least 2 hours, such as at least 3 hours, 4 hours, 5 hours, 12 hours or 24 hours) before the remaining reagent comprising sodium ions is added. In a further embodiment, the reagent comprising sodium ions is added over an extended period of time (for example at least 2 hours, such as at least 3 hours, 4 hours, 5 hours, 12 hours or 24 hours). In a further embodiment, the reaction mixture is cooled to a temperature not exceeding 30° C., for example not exceeding 20° C. or 10° C., prior to filtration. In a still further embodiment, the reaction mixture is cooled to ambient temperature prior to filtration. In a further embodiment, the conditions suitable for forming the compound of formula (I) or hydrate thereof further comprise washing the reaction mixture with a polar solvent and water after filtration. This process of converting an amide solvate of a compound of formula (II) into a compound of formula (I) or hydrate thereof provides a number of advantages over previously described processes and is more suited to large-scale manufacture. This process improves the product yield compared to previous disclosures from a product yield of 77% for this conversion as described in WO 2011/002999, to a product yield of greater than 90%. This process reduces the overall process volume as described previously, such as, for example, enabling use of 8 relative volumes compared to 15 relative volumes. This is a factor in the improved product yield. A reduction in overall volume also provides economic and environmental advantages. The skilled person will be aware that in the manufacture of active pharmaceutical compounds, the incorporation of a filtration step for solutions of all materials used in the final process step is a requirement to eliminate particulate matter from the isolation process and from the final product. The amine salt (a triethylammonium salt, such as the bis(triethylammonium) salt) generated in this process can be prepared and the resulting solution filtered at ambient temperature without significant undesired product degradation. The amine salt can also be prepared and the resulting solution filtered at ambient temperature without significant undesired premature precipitation of solids. Previously described processes required a filtration step at elevated temperatures (e.g., in excess of 80° C.) in order to ensure complete solution. Significant product degradation may occur under such conditions, thereby requiring that such procedures are carried out rapidly. This may lead to premature product precipitation and/or poor control of product crystallization and may lead to difficulties in adapting the processes to a very large scale. Furthermore, the additional step of forming an amine salt allows for the formation of a stable solution. The formation of a stable solution enables the use of a seed of the compound of formula (I) or hydrate thereof. This allows for improved control of product crystallization and improved control of the hydration of the final product solid form. Previously described processes did not readily allow the use of a controlled seeded crystallization. This process further utilizes sodium 2-ethylhexanoate as the reagent comprising sodium ions. This reagent is highly soluble in organic solvents and can be added in relatively high concentration whilst minimizing the risk of precipitation of unwanted impurities. This is a factor in the improved product yield. Further, the weakly basic nature of this reagent allows high concentrations to be added without significantly affecting the overall pH of the process system. This allows improved control of product formation without degradation. Previously described processes required the use of sodium hydroxide which did not readily provide the desired control of pH when added in large quantities, the resulting increase in pH leading to increased product degradation and reduced product yield. The conditions selected to carry out the formation of the compound of formula (I) or hydrate thereof as described in this process allows for the reaction to be carried out at a temperature less than or equal to 40° C. Previously described processes carried out this step at temperatures in excess of 60° C. The present process significantly reduces product degradation and hence improve product yield (from a degradation rate of over 10% after 3 hours for previously described processes, to a degradation rate of about 1% after 24 hours). Furthermore, the introduction of an amine salt and the use of sodium 2-ethylhexanoate in this process instead of sodium hydroxide reduces the risk of precipitation of an undesired salt, for example the monosodium salt. The solubility of the amine salt is such that any potential intermediate salts thereof is significantly more soluble than the desired disodium salt of formula (I) or hydrate thereof. Previously described processes would have passed through an intermediate monosodium salt species which led to an increased risk of unwanted precipitation of the monosodium salt. The present process maintains a consistent pH level at which the monosodium salt species is unlikely to form. In a second aspect of the invention, there is provided a compound which is a triethylammonium salt of the compound of formula (II). In an embodiment, there is provided a triethylammonium salt of the compound of formula (II) wherein the stoichiometric ratio of triethylamine to the compound of formula (II) is between 0.5:1 and 2.5:1, for example between 1.5:1 and 2.5:1, such as about 2:1. In a still further embodiment, there is provided the bis(triethylammonium) salt of the compound of formula (II) (a compound of formula (IV)): In a further embodiment, there is provided a compound of formula (IV) for use as an intermediate in the manufacture of a compound of formula (I) or hydrate thereof. A process for preparing an amide solvate of a compound of formula (II) is described in WO 2011/002999. Specifically, the amide solvate is prepared from the acetic acid solvate of formula (V): In a further aspect of the invention, there is provided a process for preparing an amide solvate of a compound of formula (II) comprising contacting a compound of formula (V) with an amide at a temperature exceeding 60° C., such as 65° C., for example from about 65° C. to about 100° C., such as to about 85° C. or from about 60° C. to about 75° C. In an embodiment, the amide is R 30 CON(R 2 ) 2 where each R 2 is independently —H or C 1-4 alkyl, or both R 2 groups together with the nitrogen to which they are attached form a 4 to 6-membered heterocyclic ring, and R 30 is —H or C 1-4 alkyl; or R 30 and one of the R 2 groups together with the nitrogen to which they are attached, respectively, combine to form a 4 to 6-membered heterocyclic ring, and the other R 2 group is independently —H or C 1-4 alkyl. In a further embodiment, the amide is selected from the group consisting of a N,N-di-(C 1-4 alkyl)-formamide, N,N-di-(C 1-4 alkyl)-acetamide, N—C 1-6 alkyl-pyrrolidinone and N—C 1-6 alkyl-piperidinone. In a yet further embodiment, the amide is N,N-dimethylformamide (DMF). In a further embodiment, the amide solvate is of formula (III): In a still further embodiment, the reaction mixture is heated to a temperature exceeding 60° C., such as 65° C., maintained at that temperature for at least 10 minutes (for example at least 30 minutes, such as at least 1 hour) and thereafter cooled to a temperature not exceeding 50° C. (for example not exceeding 40° C., such as not exceeding 30° C.). In a further embodiment the reaction mixture is cooled over a period of at least 1 hour (for example at least 2 hours, such as at least 4 hours) and thereafter heated again to a temperature not exceeding 60° C. In a still further embodiment the reaction mixture is heated to that temperature over a period of at least 1 hour, such as 2 hours. In a still further embodiment, the reaction mixture is cooled to ambient temperature over a period of at least 1 hour (for example at least 4 hours, such as at least 8 hours). In a further embodiment, the reaction mixture further comprises a seed of the amide solvate of a compound of formula (II), for example a seed of the amide solvate of formula (III). This process of preparing an amide solvate of a compound of formula (II) provides a number of advantages over previously described processes and is more suited to large-scale manufacture. The process is carried out at a higher temperature than previously disclosed (exceeding 60° C. Compared to about 50° C.). The process further utilizes a temperature cycling and controlled cooling profile. These, together or independently, provide both improved product physical form and improved filterability, hence improving the process from a large-scale manufacturing perspective. In a further aspect of the invention, there is provided a process for preparing a compound of formula (V) comprising contacting a compound of formula (VI) with acetic acid and water under conditions suitable for forming the compound of formula (V): wherein R 3 and R 4 are each independently C 1-6 alkyl. In an embodiment, R 3 and R 4 are both tert-butyl. In a still further embodiment, the conditions suitable for forming the compound of formula (V) comprises combining a solution of a compound of formula (VI) in a polar solvent with a solution of acetic acid and water. In a further embodiment, the polar solvent is selected from methyl tert-butyl ether (MATE) or isopropyl acetate, such as isopropyl acetate. In a further embodiment, the solution of a compound of formula (VI) in a polar solvent is added to the solution of acetic acid and water. In a yet further embodiment, the addition of the solution of a compound of formula (VI) is carried out over a period of several hours, for example up to 6 hours, such as up to about 5 hours. In a further embodiment, the combined solution is heated to 50-90° C. In a yet further embodiment, the solution is heated to 70° C. In a further embodiment, the filtering is carried out at an elevated temperature, for example about 50° C. In a still further embodiment, the solution of acetic acid and water further comprises a seed of the compound of formula (V). In a further embodiment, the conditions suitable for forming the compound of formula (V) further comprise washing the reaction mixture with a polar solvent. In another embodiment, the compound of formula (VI) may be added directly in solid form to the solution of acetic acid and water. This process of converting a compound of formula (VI) into an acetic acid solvate of formula (V) provides a number of advantages over previously described processes and is more suited to large-scale manufacture. This process involves the addition of a seed of the compound of formula (V). It further involves the controlled addition of the solution of a compound of formula (VI) over a period of several hours. This significantly improves the product filtration rate. This allows for a significantly easier filtering process (for example, a filtration rate of 0.46 h/kg for previously described processes, compared to a filtration rate of 0.21 h/kg for the present process). Furthermore, this process discloses filtering of the reaction mixture at an elevated temperature. This also improves the ease of filtering. An inefficient filtering step can be a significant problem in the large-scale manufacture of pharmaceutical products. The present disclosure therefore provides significant economic and environmental advantages over processes previously described. In a further aspect of the present invention there is provided a process for preparing a compound of formula (VI) comprising contacting a compound of formula (VIA): with a compound of formula (III): in the presence of a tetra-alkylammonium salt (such as tetra-n-butylammonium chloride (TBAC)) under conditions suitable for forming a compound of formula (VI), and wherein R 3 and R 4 are each independently C 1-6 alkyl, and X is halogen. In an embodiment, the compound of formula (VIII) 15 di-tert-butyl chloromethyl phosphate (IX): In a still further embodiment, the conditions sufficient to produce the compound of formula (VI) comprise: (i) combining the compound of formula (VII) with the compound of formula (VIII) with tetra-n-butylammonium chloride and a base in a polar solvent; and (ii) washing the product obtained from (i) with water. In a further embodiment, the base is an inorganic base, for example caesium carbonate, potassium carbonate or potassium tert-butoxide, such as potassium carbonate. In a yet further embodiment, the polar solvent comprises N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylformamide, sulfolane, methyl tert-butyl ether, 2-methyltetrahydrofuran, or isopropyl acetate (IPAC), or a mixture thereof. In a further embodiment, the polar solvent comprises a mixture of N,N-dimethylacetamide (DMAC) and isopropyl acetate (IPAC). In a further embodiment, the reaction in step (i) is carried out at a temperature of between 20-50° C., such as about 40° C. In a further embodiment, a solution of the compound of formula (VIII) in a polar solvent (such as isopropyl acetate) is added to a solution of the compound of formula (VII), a tetra-alkylammonium salt (such as tetra-n-butylammonium chloride) and a base (such as potassium carbonate) in a polar solvent (such as N,N-dimethylacetamide). In a further embodiment, after completion of the reaction in step (i), the reaction mixture is cooled (such as to about 5° C.), further polar solvent (such as isopropyl acetate) added and the reaction mixture washed with water. In a still further embodiment, the temperature of the solution during work-up is maintained at less than 25° C. This process of converting a compound of formula (VIII) into a compound of formula (VI) provides a number of advantages over previously described processes and is more suited to large-scale manufacture. In particular, the alkylation reaction may be difficult to control, in particular the selectivity between the desired amide N-alkylation and the undesired amide O-alkylation. This process improves reaction selectivity (for example by improving the N:O selectivity from about 6:1 to about 14:1 compared to previously disclosed processes). This process further improves overall product yield on a manufacturing scale (for example by about 5-10% over previously disclosed processes). This process discloses the use of tetra-n-butylammonium chloride. Without wishing to be bound by theory, it is believed that the introduction of this reagent has a subtle effect on the solubility of the base used and on the subsequent solubility and reactivity of the anion of the compound of formula (VII), which leads to an improvement in both the rate and the selectivity of the reaction. Previously disclosed processes do not utilize tetra-n-butylammonium chloride and therefore do not have the desired rate or selectivity profile. Furthermore, this process introduces isopropyl acetate as additional solvent, which was not disclosed as solvent in previous processes. The introduction of a mixed N,N-dimethylacetamide/isopropyl acetate solvent allows for a reduced total process volume, as a lower N,N-dimethylacetamide burden reduces the volume of water required during reaction work-up. In addition, isopropyl acetate can be used as both a reaction solvent and an extraction solvent, again reducing the overall process volume (for example from 23 relative volumes of solvent for previously described processes, to 18 relative volumes of solvent for the present process). Further, the introduction of isopropyl acetate leads to a simplified work-up procedure, consisting of a single wash, rather than the multiple washes previously described. In a further aspect of the present invention there is provided a process for preparing di-tert-butyl chloromethyl phosphate (IX) comprising contacting a mixture of potassium di-tert-butylphosphate, tetra-n-butylammonium hydrogen sulphate (TBAHS) and sodium hydrogen carbonate in a polar solvent and water with chloromethylchlorosulphate. In an embodiment, the polar solvent is selected from 2-methyltetrahydrofuran, methyl tert-butyl ether and isopropyl acetate, such as isopropyl acetate. In a further embodiment, the solution comprises a mixture of water and isopropyl acetate. In a further embodiment, the solution is heated to a temperature exceeding ambient temperature (such as exceeding 30° C., for example exceeding 35° C.). This process of preparing di-tert-butyl chloromethyl phosphate (IX) provides a number of advantages over previously described processes. In particular, the previous process required the addition of DMAC to control the decomposition of di-tert-butyl chloromethyl phosphate (IX). This process resulted in a difficult distillation to remove residual solvents from the DMAC solution prior to use in the subsequent process. The use of isopropyl acetate as solvent removes the need to use DMAC and allows for a much more straightforward distillation process, more suited to large-scale manufacture. In a further aspect of the present invention, there is provided a process for preparing a compound of formula (I) or hydrate thereof: comprising: (a) contacting a compound of formula (VI): wherein R 3 and R 4 are as previously described; with acetic acid and water under conditions suitable for forming the compound of formula (V): contacting the compound of formula (V) with an amide under conditions suitable for forming an amide solvate of the compound of formula (II): (b) contacting the amide solvate of the compound of formula (II) with an amine under conditions suitable for forming an amine salt of the compound of formula (II); and (c) contacting the amine salt of the compound of formula (II) with a reagent comprising sodium ions under conditions suitable for forming the compound of formula (I) or hydrate thereof. In an embodiment, the compound of formula (I) produced by this method is a hydrate, such as a hexahydrate. Each of the embodiments described with respect to a particular process step above can be performed independently or combined with one or more embodiments for other process steps. For example, in the process above, or independently, the amide in (b) can be R 30 CON(R 2 ) 2 , such as N,N-di-(C 1-4 alkyl)-formamide, alkyl)-acetamide, N—C 1-6 alkyl-pyrrolidinone, N—C 1-6 alkyl-piperidinone or a combination thereof. Independently, the amine recited in (c) above can be N(R 40 ) 3 , such as N(C 1-6 alkyl) 3 , N-methyl morpholine or N-methyl piperidine, or more particularly, selected from trimethylamine, dimethylethylamine, triethylamine, tripropylamine, tributylamine, di-isopropylethylamine and combinations thereof. Similarly and independently the reagent comprising sodium ions in (d) is selected from sodium chloride, sodium acetate, sodium carbonate, sodium sulphate, sodium 2-ethylhexanoate and combinations thereof. DETAILED DESCRIPTION OF THE INVENTION “Alkyl” refers to monovalent saturated aliphatic hydrocarbyl groups having, unless expressly stated otherwise, from 1 to 8 carbon atoms, such as, 1 to 6 carbon atoms or 1 to 4 carbon atoms. This term includes, by way of example, linear and branched hydrocarbyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and neopentyl. Also by way of example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group and a tert-butyl group are all represented by the term C 1-4 alkyl. Likewise terms indicating larger numerical ranges of carbon atoms (for example C 1-6 alkyl) are representative of any linear or branched hydrocarbyl falling within the numerical range. “Ambient temperature” refers to a temperature of between 15° C. to about 25° C., for example between 18° C. to 22° C., such as about 20° C. “Base” refers to a substance that can accept protons. Examples of bases include, but are not limited to, inorganic bases, for example carbonates (such as cesium carbonate, sodium carbonate, sodium bicarbonate, potassium carbonate) and hydroxides (such as sodium hydroxide, potassium hydroxide or lithium hydroxide), and organic bases, for example nitrogen-containing organic bases (such as ammonia, methylamine, dimethylamine, ethylamine, diethylamine, dimethylethylamine, triethylamine or di-isopropylethylamine). “Halogen” refers to fluoro, chloro, bromo or iodo. “Heterocyclic” means a C-linked or N-linked, 4 to 6-membered, monocyclic saturated ring system containing 1-3 heteroatoms independently selected from N, S and O. By way of example, such heterocyclic rings include morpholinyl, piperidinyl, piperazinyl, and pyrrolidinyl rings, including N-alkylated version of such rings, such as N-methyl morpholinyl and N-methyl piperidinyl. “Solvate” refers to a complex formed by combination of at least one solvent molecule with at least one molecule or ion of the solute. One of ordinary skill in the art will appreciate that the stoichiometry of the solvent to the solute in a solvate may be greater than one, equal to one, or less than one. The solvent can be an organic compound, an inorganic compound, or a mixture of both. Some examples of solvents include, but are not limited to, acetic acid, N,N-di-(C 1-4 alkyl)-formamide, N,N-di-(C 1-4 alkyl)-acetamide, N—C 1-6 alkyl-pyrrolidinone, N—C 1-6 alkyl-piperidinone, N,N-dimethylformamide and water. When used herein, the term “solvate” is not intended to restrict the solvate compounds described herein to any particular sort of bonding (such as ionic or covalent bonds). In a salt, proton transfer occurs between the compound of formula (II) and the counter ion of the salt (such as triethylamine). The skilled person will be aware that in some cases proton transfer may not be complete and the solid is not therefore a true salt. In such cases the compound of formula (II) and the “co-former” molecules in the solid primarily interact through non-ionic forces such as hydrogen bonding. It is accepted that proton transfer is a continuum, and can change with temperature, and therefore the point at which a salt is better described as a co-crystal can be somewhat subjective. The compound of formula (II) may therefore form a mixture of salt and co-crystal forms and it is to be understood that the present invention encompasses the salt forms, co-crystal forms and salt/co-crystal mixtures, as well as any solvates (including hydrates) thereof. The synthesis of di-tert-butyl chloromethyl phosphate (IX) is illustrated in Scheme I below. The synthesis of the compound of formula (VI) wherein R 3 and R 4 are both tert-butyl (formula (X)) from the compound of formula (VII) is illustrated in Scheme II below. The synthesis of the compound of formula (V) from the compound of formula (X) is illustrated in Scheme III below. The synthesis of the compound of formula (III) from the compound of formula (V) is illustrated in Scheme IV below. The synthesis of the bis(triethylammonium) salt of the compound of formula (II) (the compound of formula (IV)) is illustrated in Scheme V below. The synthesis of the compound of formula (I) or hydrate thereof from the compound of formula (IV) is illustrated in Scheme VI below. EXAMPLES The invention is further understood by reference to the following examples, which are intended to be purely exemplary of certain aspects of the invention and are not intended to limit the scope. In the examples below as well as throughout the specification, the following abbreviations have the following meanings. If not defined, the terms have their generally accepted meanings. AcOH=acetic acid DMAC=N,N-dimethylacetamide DMF=N,N-dimethylformamide DMI=1,3-dimethyl-2-imidazolidinone DMSO=dimethylsulfoxide g=gram IPA=isopropanol IPAC=isopropyl acetate kg=kilogram L=liter mbar=millibar ml=milliliter mol eq=molar equivalent MTBE=methyl tert-butyl ether TBAC=tetra-n-butylammonium chloride TBAHS=tetra-n-butylammonium hydrogen sulphate w/v=weight/volume w/w=weight/weight General Procedures Proton ( 1 H) and carbon ( 13 C) nuclear magnetic resonance (NMR) spectra were acquired using Bruker Avance 400 spectrometer at 300 K. Samples were prepared as solutions in d 6 -DMSO (d 6 -dimethyl sulfoxide) containing trimethylsilane (TMS), or d 4 -MeOD (d 4 -methanol). NMR data is reported as a list of chemical shifts (δ, in ppm) with a description of each signal, using standard abbreviations (s=singlet, d=doublet, m=multiplet, t=triplet, q=quartet, br=broad, etc.). Spectra were referenced d 6 -DMSO (δ=2.50 ppm) or d 4 -MeOD (δ=3.30 ppm). J-Coupling constants are listed, where measured, in the descriptions of the resonances. Slight variation of chemical shifts and J-coupling constants may occur, as is well known in the art, as a result of variations in sample preparation, such as analyte concentration variations. Mass spectrometry data was obtained using a Bruker micrOTOF-Q quadrupole time-of-flight mass spectrometer. Samples were analyzed using positive ion electrospray ionization. Accurate mass measurement was used to determine the elemental formula of the resulting ions. Large scale reactions were carried out in glass-lined steel reactors fitted with heat transfer jackets and serviced with appropriate ancillary equipment. Standard laboratory glassware and equipment was used for smaller scale processes. Starting materials, solvents and reagents were purchased commercially and used as supplied. Example 1 Preparation of disodium [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl phosphate hexahydrate Step A: Preparation of 6-[(2-chloro-5-fluoro-pyrimidin-4-yl)amino]-2,2-dimethyl-4H-pyrido[3,2-b][1,4]oxazin-3-one 5-fluoropyrimidine-2,4-diol (525 kg, 1.00 mol eq) is mixed with phosphorous oxychloride (1545 kg, 2.50 mol eq) and heated to about 100° C. with stirring under a nitrogen atmosphere. N,N-dimethylaniline (980 kg, 2.00 mol eq) is then added over a period of about 9 hours and the resulting mixture stirred at about 100° C. for up to 4 hours. This is then cooled to about 20° C. over about 2 hours and then quenched into a mixture of water (3150 kg) and dichloromethane (1915 kg), maintaining the temperature below 40° C. The contents are then stirred at about 20° C. for at least 3 hours and then the layers separated. The aqueous phase is washed with dichloromethane (1915 kg) and the layers again separated. The combined organics are then washed with concentrated aqueous hydrochloric acid (525 kg) at least once, sometimes more than once, then with 5% w/w aqueous sodium hydrogen carbonate solution (2625 kg). The resulting organic solution is then distilled at atmospheric pressure down to about 1310 kg to give a solution of 2,4-dichloro-5-fluoro-pyrimidine in dichloromethane, with typical solution strength of about 50% w/w and yield of about 95%. This solution is then used directly in the next process. 6-amino-2,2-dimethyl-4H-pyrido[3,2-b][1,4]oxazin-3-one (450 kg, 1.00 mol eq) is stirred in a mixture of methanol (1971 kg) and water (1610 kg) under a nitrogen atmosphere with heating to about 65° C. To this is added a solution of 2,4-dichloro-5-fluoro-pyrimidine in dichloromethane (545 kg 2,4-dichloro-5-fluoro-pyrimidine, 1.40 mol eq, about 50% w/w solution) over a period of about 4 hours, during which dichloromethane is distilled off. The mixture is then stirred at about 70° C. until distillation is complete and then at reflux for about 15 hours. This is then cooled to about 45° C. and filtered. The filtered solid is washed twice with methanol (2×675 kg) and then dried under vacuum at about 55° C. Once dry, the solid is slurried in 85% w/w aqueous formic acid (3150 kg) at about 50° C. for about 6 hours and then filtered. This slurry may be repeated. The resulting damp solid is cooled to about 20° C., washed twice with methanol (2×1800 kg) and dried under vacuum at about 80° C. to give the title compound (577 kg, 77%) as a colored solid. 1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 1.42 (s, 6H) 7.41 (d, J=8.5 Hz, 1H) 7.46 (dd, 0.5 Hz, 1H) 8.34 (d, J=3.3 Hz, 1H) 10.10 (br. s, 1H) 11.12 (br. s, 1H). m/z 324 [MH] + . Step B: Preparation of 6-[[5-Fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-4H-pyrido[3,2-b][1,4]oxazin-3-one 6-[(2-chloro-5-fluoro-pyrimidin-4-yl)amino]-2,2-dimethyl-4H-pyrido[3,2-b][1,4]oxazin-3-one (Step A) (568 kg, 1.00 mol eq) is mixed with 3,4,5-trimethoxyaniline (402 kg, 1.25 mol eq) in N-methylpyrrolidin-2-one (2835 kg) with stirring under a nitrogen atmosphere. To this is added water (11 kg) and the mixture heated to about 120° C. and stirred for about 10 hours. This is then cooled to about 65° C. and the pH adjusted to pH 8.5 with 4% w/w aqueous sodium hydroxide solution. The resulting slurry is further cooled to about 20° C., stirred for at least 6 hours and then filtered. The filtered solid is washed twice with water (2×1440 kg) then twice with acetone (2×1140 kg) and finally dried under vacuum at about 40° C. to give the title compound (754 kg, 91%) as a colored solid. 1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 1.42 (s, 6H) 3.59 (s, 3H) 3.66 (s, 6H) 7.04 (s, 2H) 7.32 (d, J=8.5 Hz, 1H) 7.68 (d, J=8.5 Hz, 1H) 8.13 (d, J=3.4 Hz, 1H) 9.10 (br. s, 1H) 9.14 (br. s, 1H) 11.06 (br. s, 1H). m/z 471 [MH] + . Step C: Preparation of ditert-butyl [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl phosphate A mixture of 6-[[5-Fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-4H-pyrido[3,2-b][1,4]oxazin-3-one (Step B) (382 kg, 1.00 mol eq), tetra-n-butylammonium chloride (57.5 kg, 0.25 mol eq) and potassium carbonate (252 kg, 2.25 mol eq) in N,N-dimethylacetamide (1792 kg) is warmed to about 40° C. with stirring. To this is added a solution of ditert-butyl chloromethyl phosphate (Example 2) in isopropyl acetate (229 kg ditert-butyl chloromethyl phosphate, 1.10 mol eq, about 25% w/v solution). The resulting mixture is stirred for about 8 hours and then cooled to about 5° C. Isopropyl acetate (1329 kg) is added and then water (2292 kg) slowly, maintaining the temperature at <25° C. The layers are then separated, retaining the upper layer of the three observed. To this is added acetic acid (99 kg) and the resulting solution of the sub-title compound is used directly in the next step. Step D: Preparation of [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl dihydrogen phosphate; acetic acid solvate A mixture of acetic acid (2605 kg) and water (860 kg) along with [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl dihydrogen phosphate; acetic acid solvate seed (synthesised according to the method described in WO 2011/002999) (15 kg, 0.03 mol eq) are heated to about 70° C. To this is then added the solution of ditert-butyl [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl phosphate (Step C) over about 5 hours. The resulting mixture is further stirred for about 1 hour, cooled to about 50° C. and then filtered, washing twice with acetone (2×605 kg). The damp solid is finally dried under vacuum at about 40° C. to give the sub-title compound (317 kg, 61%) as an off white solid. 1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 1.45 (s, 6H) 1.90 (s, 3H) 3.61 (s, 3H) 3.68 (s, 6H) 5.81 (d, J=6.9 Hz, 2H) 7.06 (s, 2H) 7.40 (d, J=8.5 Hz, 1H) 7.95 (d, J=8.5 Hz, 1H) 8.18 (d, J=3.4 Hz, 1H) 9.20 (br. s, 2H). m/z 581 [MH] + . Step E: Preparation of [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl dihydrogen phosphate; N,N-dimethylformamide solvate To [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl dihydrogen phosphate; acetic acid solvate (Step D) (3.50 kg) in a heated vessel at about 65° C. is added hot N,N-dimethylformamide (17.5 kg, preheated to about 70° C.). The mixture is stirred at about 65° C. for about 30 minutes, [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl dihydrogen phosphate; N,N-dimethylformamide solvate seed (synthesised according to the method described in WO 2011/002999) (0.04 kg) is added, and then the mixture is cooled to about 40° C. over about 4 hours. This is then warmed again to about 60° C. over about 1 hour, held for about 30 minutes and then cooled to about 20° C. over about 8 hours. The resulting slurry is stirred for at least 10 hours, filtered and then washed twice with methyl-t-butyl ether (2×7.88 kg). The damp solid is finally dried under vacuum at about 40° C. to give the sub-title compound (2.82 kg, 88%) as a white to off white solid. 1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 1.45 (s, 6H) 2.72 (d, J=0.6 Hz, 3H) 2.88 (d, J=0.6 Hz, 3H) 3.61 (s, 3H) 3.68 (s, 6H) 5.81 (d, J=6.9 Hz, 2H) 7.06 (s, 2H) 7.40 (d, J=8.6 Hz, 1H) 7.94-7.96 (m, 2H) 8.18 (d, J=3.4 Hz, 1H) 9.21 (br. s, 2H); m/z 581 [MH] + . Step F: Preparation of bis(triethylammonium) [6-[[5-fluoro-2-[(3,4,5-trimethoxyphenyl)amino]pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl phosphate To [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl dihydrogen phosphate; N,N-dimethylformamide solvate (Step E) (1.00 kg, 1.00 mol eq) is added a solution of triethylamine (0.34 kg, 2.20 mol eq) in isopropanol (1.32 kg) and water (3.33 kg). This is stirred at about 20° C. to give a solution which is then filtered. The resulting solution of the sub-title compound is used directly in the next step. Step G: Preparation of disodium [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl phosphate hexahydrate The solution of bis(triethylammonium) [6-[[5-fluoro-2-[(3,4,5-trimethoxyphenyl)amino]pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl phosphate (Step F) is warmed to about 40° C. and then a solution of sodium 2-ethylhexanoate (0.05 kg, 0.20 mol eq) in isopropanol (0.04 kg) and water (0.10 kg) is added over about 20 minutes. To the resulting solution is then added disodium [6-[[5-fluoro-2-(3,4,5-trimethoxyanilino)pyrimidin-4-yl]amino]-2,2-dimethyl-3-oxo-pyrido[3,2-b][1,4]oxazin-4-yl]methyl phosphate hexahydrateseed (synthesised according to the method described in WO 2011/002999)(0.01 kg, 0.01 mol eq) and the mixture is held for about 3.5 hours. A solution of sodium 2-ethylhexanoate (0.97 kg, 3.80 mol eq) in isopropanol (0.75 kg) and water (1.90 kg) is next added over about 6 hours. The resulting slurry is cooled to about 20° C. over at least 1 hour, stirred for about 1 hour and then filtered, washing with a mixture of isopropanol (0.53 kg) and water (1.33 kg) and then with acetone (1.58 kg). The damp solid is finally dried under vacuum (about 400 mbar) at about 40° C. to give the title compound (1.03 kg, 92%) as a white to off white solid. 1 H NMR (500 MHz, Methanol-d 4 ) δ ppm 1.52 (s, 6H) 3.78 (s, 3H) 3.80 (s, 6H) 5.86 (d, J=4.9 Hz, 2H) 6.97 (s, 2H) 7.24 (d, J=8.6 Hz, 1H) 8.00 (d, J=3.6 Hz, 1H) 8.10 (d, J=8.6 Hz, 1H); m/z 581 [MH] + . Example 2 Preparation of Ditert-Butyl Chloromethyl Phosphate To a mixture of potassium ditert-butyl phosphate (261 kg, 1.00 mol eq), tetra-n-butylammonium hydrogensulphate (18.5 kg, 0.05 mol eq) and sodium hydrogencarbonate (400 kg, 4.50 mol eq) in water (1150 kg) is added isopropyl acetate (1275 kg). The mixture is warmed to about 35° C. and then to this is added chloromethylchlorosulphate (313 kg, 1.80 mol eq) over about 4 hours. The mixture is further stirred for about 45 minutes, cooled to about 25° C. and then the layers separated. The organic phase is cooled to about 10° C. and washed twice with 2% w/v aqueous potassium hydrogencarbonate solution (2×800 kg) and then with a mixed 2% w/v potassium hydrogencarbonate and 20% w/v potassium hydrogencarbonate aqueous solution (640 kg). The resulting organic solution is then distilled at <100 mbar to half volume, maintaining the temperature below 45° C. The resulting mixture is filtered, washing the filter with isopropyl acetate (115 kg), to give the title compound as a solution, with typical solution strength of about 25% w/v and yield of about 90%. This solution is then used directly in Example 1, Step C.
The present disclosure provides for processes and intermediates in the large-scale manufacture of the compound of formula (I) or hydrates thereof.
2
BACKGROUND OF THE INVENTION This application is a continuation of U.S. patent application, Ser. No. 126,978, filed Mar. 3, 1980, now abandoned, and entitled FOUR CYCLE ROTARY ENGINE EMPLOYING ECCENTRICAL MOUNTED ROTOR. This invention relates to an internal combustion engine employing an eccentrically mounted rotor with radial unbiased blades slidable therein so as to form with the external wall of the rotor and the internal wall of the casing surrounding it, a plurality of chambers the volumes of which vary constantly during rotation of the rotor. More particularly, a very simple four cycle rotary engine is disclosed employing a novel power shaft on which are pressed by hand, if so desired, all of the parts to form a lightweight super charged rotary engine. DESCRIPTION OF THE PRIOR ART U.S. Pat. No. 3,103,920 discloses an internal combustion engine having an eccentrically mounted rotor with radial blades slidable therein which employs circular links on the inside ends of the vanes in order to keep these vanes in line with the outer circular combustion chamber. U.S. Pat. No. 3,213,838 discloses an internal combustion rotary motor of the four cycle type having a power stroke for each half revolution of the rotor. Only two vanes are used 180 degrees apart and are coil spring biased. U.S. Pat. No. 3,215,129 discloses a rotary internal combustion motor in which a single rotor confined within a housing is divided to provide a combustion unit on one side thereof and a compression unit on the other side thereof and a transfer valve for intermittently admitting fuel air mixture from the compression unit into the combustion unit in timed relation with the operation of the rotor. Rocking guides are used to enclose the vanes in order to keep them in line with the offset circular combustion chamber. A separate gear driven timing mechanism is arranged between the two rotors. U.S. Pat. No. 3,324,840 discloses an engine and compressor arrangement of the rotary vane type wherein a compressor apparatus is adapted to supply a compressed charge of air-fuel mixture to the engine. Extra connecting links are used on the inside ends of the vanes to keep them in line with the outer circular combustion chamber. U.S. Pat. No. 3,537,432 discloses a rotary engine having an eccentrically mounted rotor with radial blades slidable therein employing extra connecting links to hold and operate the blades. Each blade or vane is made in two parts and held apart by a coil spring. U.S. Pat. No. 3,568,645 discloses a rotary combustion engine employing radial positioning of the vanes during the rotation of the engine rotor shaft for positive positioning relative to the outer shell of the engine independent of the contact of the outer end of the vane and the inner surface of the outer shell. U.S. Pat. No. 3,713,426 discloses a vaned rotor engine and compressor having vanes projecting through slots in a cylindrical rotor mounted off-center on bearings in a casing. The rotor drives through gear means an accessory shaft. The vanes revolve around a shaft that is in the center of the outer circular combustion chamber but they operate through an off-center cylindrical rotor. U.S. Pat. No. 4,024,840 discloses an engine and compressor arrangement wherein a conduit connects the compression charge outlet of the compressor to the intake part of the engine so that a compressed charge may be fed into the engine. The vanes are controlled by links on the ends of the vanes. U.S. Pat. No. 4,154,208 discloses a rotary engine having an annular space formed between the housing and the rotor, the annular space being divided into an intake compression chamber and air expansion exhaust chamber. None of these patents disclose the particular hardware configuration claimed which is believed to be economical to manufacture and more efficient to operate than prior art structures. SUMMARY OF THE INVENTION In accordance with the invention claimed, an improved very simple four cycle rotary internal combustion engine employing a novel power shaft is provided which has only two cycles of operation per rotation of the rotor. Accordingly, it is one object of this invention to provide an improved rotary internal combustion engine employing a novel power shaft on which is mounted two rotors confined within a housing with the rotor being divided to provide an intake and compression compartment and an expansion and exhaust compartment with the fuel injection nozzle, glow plug and firing chamber therebetween, as shown in FIG. 7. Another object of this invention is to provide an improved rotary internal combustion engine employing a novel power shaft on which are mounted two rotors employing movable vanes which are radially operable in an elliptical working chamber without the use of links and springs. A further object of this invention is to provide an improved rotary internal combustion engine employing a novel power shaft on which are press fit mounted all of its component parts which may be quickly assembled and disassembled for service or repair purposes. A still further object of this invention is to provide an improved rotary internal combustion engine employing two rotor portions operating in tandem in two elliptical working chambers or compartments to form two engine sections. A still further object of this invention is to provide a simple, efficient and practical rotary internal combustion engine. Further objects and advantages of the invention will become apparent as the following description proceeds and the features of novelty which characterize the invention will be pointed out with particularity in the claims annexed to and forming a part of this specification. BRIEF DESCRIPTION OF THE DRAWINGS The present invention may be more readily described by reference to the accompanying drawings in which: FIG. 1 is a perspective view of the disclosed rotary internal combustion engine embodying the invention; FIG. 2 is an exploded perspective view of the rotary internal combustion engine shown in FIG. 1; FIG. 3 is a perspective view of the power shaft of the rotary internal combustion engine shown in FIGS. 1 and 2; FIG. 4 is a cross-sectional end view of the rotary internal combustion engine shown in FIGS. 1 and 2; FIG. 5 is an exploded perspective view of one end of the rotor showing a vane and a plurality of vane slots; FIG. 6 is a perspective view similar to FIG. 5 of the other end of the rotor and showing the vanes in position in the vane slots; FIG. 7 is a cross-sectional view partly in elevation of the rotary internal combustion engine shown in FIG. 1 taken along the line 7--7 of FIG. 4; and FIG. 7A is a cross-sectional view of FIG. 1 taken along the line 7A--7A. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring more particularly to the drawings by characters of reference, FIGS. 1-7A disclose a rotary internal combustion apparatus or engine 10 comprising a cylindrical housing 11 having end plates 12 and 13 which hold and rotatably support a shaft 14 therein. The ends of the shaft penetrate each end plate to transmit the rotation of the shaft out of the housing. Between the housing 11 and shaft 14 are provided at least two annular spaces 15 and 16 which are mutually separated by dividing wall or center plate 17. One of the annular spaces, such as space 15, constitutes the intake compression engine chamber for intake and compression and the other space 16 comprises the expansion and exhaust chamber with the center plate 17 separating the two chambers. Between the two engine spaces or chambers 15 and 16 is a passage 18 extending over center plate 17 which is open and closed by the vanes upon rotation of a rotor mounted on shaft 14 as hereinafter explained. The intake compression engine chamber 15 is equipped with an intake air port 19 and the expansion exhaust chamber 16 is equipped with an exhaust port 20. Center plate 17 is provided with a glow plug 21 the tip of which extends into passage 18 and a fuel intake port 22 communicating with passage 18 for the injection of a suitable combustion fuel 23. As noted from the drawings, shaft 14 is mounted within thrust bearings 24 and 25 formed in end plates 12 and 13, respectively, such that it is eccentrically positioned relative to chambers 15 and 16. A rotor structure 26 comprising two rotors 26A and 26B is mounted on shaft 14 such that one rotor lies within each of these chambers as shown. A plurality of radially disposed slots 27 are spacedly arranged around the outer periphery of each of the rotors 26A and 26B of rotor structure 26 and extend therethrough to their hollow interiors for slidingly receiving therein a plurality of vanes 28. A pair of cylindrical members 29 forming guiding surfaces 30 around their outer peripheries are mounted on center plate 17 eccentrically to shaft 14. The cylindrical members are arranged one in each of chambers 15 and 16 to function as a cam member for moving vanes 28 in and out of their respective slots 27 in rotor structure 26 as shaft 14 rotates. The length of the vanes 28 in a radial direction of shaft 14 is such that their ends 28A and 28B are always in contact with the inside periphery of housing 11 and the outside periphery of cylindrical member 30. This feature occurs because the longitudinal axis of guiding member 30 is eccentrically arranged with the longitudinal axis of shaft 14. For this reason, no springs or linkage arrangements are necessary to positively control the movement of vanes 28. They are constantly moved upon rotation of shaft 14 in their respective slots 27 in rotors 26A and 26B about the outer periphery of member 30 and the inside periphery of housing 11. The guiding members 30 act as guides or cams for keeping the tips 28A of vanes 28 against the inside periphery of the outside circular combustion chamber walls of housing 11 at all times while working or being controlled by guiding member 30. Power shaft 14 is offset to its housing 11 and the vanes 28 are arranged in perfect alignment with the center of the combustion chamber formed in housing 11 in only two places which are 180 degrees apart. At all other times, the inside ends 28B of vanes 28 are slightly out of line with the center of the combustion chamber and if the guiding member 30 was perfectly round, vanes 28 would be too short to form a tight seal with the inside surface of housing 11 around the combustion chamber. Vanes 28 move radially outwardly of shaft 14 at substantially a 90 degree angle to the power shaft 14 as they rotate in rotor structure 26. These vanes, although loosely arranged in slots 27, do not shuttle back and forth in relation to the combustion chamber. They rotate in perfect balance and when the motor is running, centrifugal force holds them against the inner walls of housing 11 thus forming a good seal with the walls of the combustion chamber. Actually, the rotor moves radially of the vanes. As noted from FIG. 7 of the drawing, the arcuate pear shaped guiding members 30 comprising its two parts are fixedly attached one to each of the side surfaces of center plate 17. Each part of member 30 is substantially identical. However, it should be recognized that for timing purposes, one part may be angularly positioned relative to the other so that it may cause its cycle of operation of the associated vanes 28 to function a few degrees ahead of the vanes operating on the other part of the guiding member 30. Since the working pressure of this apparatus is within the outer periphery of housing 11, the only pressure seals required on the power shaft 14 or elsewhere are those seals 31 mounted adjacent the outer periphery of the rotors 26A and 26B in the end and center plates 12, 13 and 17, respectively. These seals may be metal rings which make contact with the rotors all around the outer periphery and on both sides of the rotor portions 26A and 26B. These rings have installed behind them light, flexible metal expanders (not shown and well known in the art) which will be secured so that the rings or seals will not turn with the associated rotors. As noted from FIGS. 3 and 7, the power shaft 14 is provided with a unique shape for purposes of simplicity. It is machined down to several different sizes on each end after being measured and cut to the proper length. The center section 32 is the largest portion of the shaft and it is provided for rotating within the center plate 17 and guiding member 30. The power end 33 of the shaft is machined down to form a shoulder 34 and a short splined section 35 for engaging matching teeth 36 (shown in FIG. 6) on the inside periphery of the rotor portion 26B. The next portion on the power end 33 of the shaft is machined down to provide a smooth bearing surface 37 for bearing 25. The remaining power input portion 37A of the power end of shaft 14 is machined down further for ease in replacing the bearing and may be provided with splines for a gear for both the starter and accessory drive gear and must be on the outside of engine housing. It should be recognized that any number of shapes may be formed on this power end of the shaft depending on the work function used with it. The other end 38 of the power shaft 14 is also machined down leaving a shoulder 39 to provide a splined section 40 for engaging teeth 36 of the intake compression rotor portion 26A. A smooth bearing engaging portion 41 is provided next to splined section 40 in the same manner as portion 37 at the power end 33 of shaft 14. A further splined section 42 is provided next to the bearing engaging portion 41 for engaging with the cooperating teeth of an associated blower or fan 43 mounted therearound. The end of this portion of the power shaft is further machined down below the level of the splines in portion 42 to provide a threaded portion 44 for a streamlined lock nut 45 shown in FIGS. 1 and 7. This power shaft is the support on which the rotary engine is assembled. It is designed and milled down so that all major parts can be easily assembled and removed therefrom for repair. As noted from FIG. 3, the center section is the largest part of the shaft and comprises a given diameter with each end being measured off and milled down four times and splined two times for the correct and easy reception of their respective parts. All parts assembled on the power shaft may be pressed on by hand including the rotor and thrust bearings. When the parts are assembled, the long bolts shown in FIG. 7 hold all of the parts together forming a simple, lightweight engine that may be easily disassembled for repair and servicing functions. It should be noted that the two rotors 26A and 26B provide a complete four cycle rotary engine. However, if a centrifugal blower or fan 43 is added to the power shaft 14 in the position shown and blowing into the intake compression portion of the apparatus, this fan acts as a simple but very effective super charger that would give a substantial boost in power with a small increase in weight of the apparatus. This super charger feature and increased manifold pressure can more easily be applied to a rotary engine than to a piston type engine without harmful effects. As noted from the drawing, the engine or apparatus disclosed has no mechanical valves and needs none. It is provided with intake and exhaust ports 19 and 20 which may be placed in any chosen position for maximum power and economy purposes. The oiling or lubricating system for engine 10 is simple since only the two main bearings 24 and 25 need attention with further lubrication being applied to the ends 28A and 28B of the vanes 28 where they scrape or rub on the inside periphery of housing 11 and on the outside periphery of their guiding means 30. None of these oiling requirements need oil under high pressure and consequently can be fed into the combustion chamber formed in housing 11 with a variable displacement pump at a rate depending on engine speed, load, etc. in the same manner as the late model two cycle gas engines. The cooling system for the disclosed engine may comprise either an air cooled or water cooled arrangement. Housing 11 comprises a double wall structure having an outer cylindrical wall 46 and an inner cylindrical wall 47 enclosing a hollow space 48 extending longitudinally of and through the rotors 26A and 26B and center plate 17. A plurality of guiding tubes 49 are spacedly arranged around the periphery of the rotors 26A and 26B and center plate 17 within the hollow space 48 and longitudinally thereof for receiving elongated bolts 50. These bolts extend between the end plates 12 and 13 to hold the parts of the engine together as shown. Water or air is circulated through this cooling chamber formed by the hollow space 48 in the usual known manner and exits from the housing through ports 48A in end plate 13. The enclosure around blower or fan 43 need not be cooled because it handles only cool fresh air and is merely bolted onto the rotary housing 11 which is water or air cooled. Suitable hose connections (not shown) may be secured one to each end plate of the engine with water flowing only one way or each connection may be mounted on the same end of the engine with the cooling fluid making a complete round trip through both the combustion chambers 15 and 16 first up one side of the engine and back the other side. If the engine is air cooled, it could employ only the outer wall 46 with a plurality of cooling fins (not shown) running along the outer periphery of wall 46 lengthwise of the power shaft 14. It should be noted that fan 43 may be enlarged so that it can act as the air cooling means for the engine in addition to the super charger feature heretofore explained. If used for the dual purpose disclosed, the center section of the fan blades can be made of one type of fan blade surrounded by a metal band for its super charger function and the outer section can have a different type of blade configuration for functioning as an engine cooling means with both fan blade portions interconnected for long and trouble free life. As in the usual rotary internal combustion engine, the initial movement of the drive shaft 14 is imparted thereto by any suitable means such as an electric starting motor of the type commonly utilized with internal combustion engines. The initial rotational displacement of the rotor means 26 will cause vanes 28 operatively associated therewith to induce a uni-directional flow of the fuel and air mixture components introduced into passage 18 from fuel intake port 22 and air intake port 19 through the annular spaces 15 and 16 of the engine. It is seen that this fuel and air mixture will be substantially continuous as long as the engine is operating. As the air enters the compression section 15 of the working portion of the engine, it will be compressed due to the tapering nature of the space, chamber or area 51 located between the rotor 26A (shown in FIG. 4) and the inner wall 48 of housing 11. The air is compressed between rotor 26A, inner wall 48 of housing 11 and the operatively associated vanes 28. The compression may reach a suitable compression at approximately 150 degrees of rotation from slot 52 introducing the air into the engine from the air input port 19. In operation, this blower fan blade in front forces all the air under a positive pressure to the intake compression rotor chamber 15 giving it a super charged effect and giving more power to the engine. The air is further compressed here as it makes another partial revolution and as it enters into the expansion and exhaust chamber 16, a fuel is continuously injected into this air stream by an injection nozzle 22 to form the proper fuel mixture. The vanes 28 carry this mixture past the glow plug where it is ignited and it starts to expand, but immediately it is passed into the expansion exhaust chamber 16 where it does the work. The combustion of the fuel air mixture causes a rapid increase in pressure contained within this portion of space 16 as well as an increase in temperature of housing 11. The gases expand into the increasing tapering space 53 of engine 10. As a result of this increase in pressure and temperature, all in accordance with well known scientific principles, vanes 28 will be displaced in the direction of the arrow in FIG. 4. The pressure of the combused fuel and air mixture causes vanes 28 and the associated rotors 26A and 26B to move in a clockwise or counterclockwise direction depending on the engine design configuration until the combusted fuel air mixture reaches the spacedly arranged discharged slots or ports 54 formed to extend through the walls 46 and 47 of housing 11 as shown in FIG. 4 where the residue of the combusted fuel and air mixture is scavenged from the tapering space or channel 53. In summation, the present invention comprises a rotary engine built upon a novel power shaft for any air or land vehicle use wherein a means for the continuous igniting of an air fuel mixture is employed. A dual compression section and combustion section is employed with one power shaft using two separate rotors or rotor portions. Thus, an efficient, simple engine mounted upon a novel power shaft is provided with ample cooling and super charger features employed which may be easily assembled and disassembled for repair services. The engine described incorporates only a few moving assemblies comprising the rotors 26A and 26B so that wear and mechanical energy losses are held to a minimum. The relatively simple mechanical construction also lends itself to the realization of a low manufacturing cost. The rotor in the expansion exhaust zone which is exposed to high temperature can be made out of any suitable material that has been developed for internal combustion engines which will give it a greater heat range and more power. Although but a single embodiment of the invention has been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit of the invention or from the scope of the appended claims.
A four cycle rotary internal combustion engine employing two cycles of operation per rotation of the rotor and wherein an eccentrically mounted rotor with radial unbiased blades slidable therein form with the external wall of the rotor and the internal wall of the casing surrounding it, a plurality of chambers, the volumes of which vary constantly during rotation of the rotor.
5
FIELD OF THE INVENTION [0001] The present invention relates to fabrics made for apparel, tents, sleeping bags and the like, in various composites, constructed such that a combination of substrate layers and insulation layers is configured to provide improved thermal insulation. BACKGROUND OF THE INVENTION [0002] In the present invention the use of metallization to create infrared reflecting barriers is adopted for clothing or outdoor equipment such as sleeping bags or tents. These radiant barriers, require careful insulation from heat loss via conduction. [0003] Corrosion, particularly in salty environments, of these metal layers through oxidisation can be considerable and methods known in the art are adopted to help prevent oxidisation. [0004] When a moisture vapor permeable substrate is coated over substantially an entire surface using conventional methods such as air knife coating, flexographic printing, gravure coating, etc., the coating reduces the moisture vapor permeability of the substrate. If the starting substrate has an open structure and is highly air permeable, the substrate can retain sufficient moisture vapor permeability after coating to be useful in certain end uses, such as apparel. For example, fabrics described in U.S. Pat. No. 5,955,175 to Culler are both air permeable and moisture vapor permeable after being metalized and coated with an oleophobic coating. [0005] When the starting moisture vapor permeable substrate is a non-porous monolithic membrane, conventional coatings result in significant covering of the surface of the substrate. This results in a coated substrate having significantly lower moisture vapor permeability than the starting substrate. This is undesirable in apparel or outdoor equipment products, which are desirably permeable to moisture vapor while at the same time forming a barrier to infiltration by air and water. As described by Sympatex in U.S. Pat. No. 6,800,573 it is possible to coat these non-porous vapour permeable substrates using a plasma treated vapour deposition metalization process and maintain good vapour permeability. [0006] US Patent Application Publication US 2004/0213918 A1 (Mikhael et al.) discloses a process for functionalizing a porous substrate, such as a nonwoven fabric or paper, with a layer of polymer, and optionally a layer of metal or ceramic. According to one embodiment, the process includes the steps of flash evaporating a monomer having a desired functionality in a vacuum chamber to produce a vapor, condensing the vapor on the porous substrate to produce a film of the monomer on the porous substrate, curing the film to produce a functionalized polymeric layer on the porous substrate, vacuum depositing an inorganic layer over the polymer layer, and flash evaporating and condensing a second film of monomer on the inorganic layer and curing the second film to produce a second polymeric layer on the inorganic layer. Mikhael et al. also discloses another embodiment including the steps of flash evaporating and condensing a first film of monomer on the porous substrate to produce a first film of the monomer on the porous substrate, curing the film to produce a functionalized polymeric layer on the porous substrate, vacuum depositing a metal layer over the polymer layer, and flash evaporating and condensing a second film of monomer on the metal layer and curing the second film to produce a second polymeric layer on the metal layer. [0007] US Patent Applications US 2007/0166528 A1 (Barnes et al.) discloses a process for oxidising the surface of a metal coating with an oxygen-containing plasma to form a synthetic metal oxide coating, making a superior resistance to corrosion of the metallized porous sheet. [0008] Methods for both improving the moisture vapour permeability of the composite and insulating the metal layer from conduction are disclosed in the present invention. SUMMARY OF THE INVENTION [0009] A first embodiment of the present invention relates to fabrics made for apparel, in various composites, and are constructed such that there is at least one metal layer, forming a radiant barrier for heat loss via radiation from the human body and at least one insulating layer protecting the said metal layer from heat loss via conduction. [0010] In a preferred embodiment of the present invention the said metal layer is adjacent to at least one insulation layer designed to help insulate the metal layer from heat loss via conduction, while maintaining low emissivity and optimising the infrared reflectance. The said insulating layer can be optimised to maintaining good infrared reflectance of said metal layer, preferably within the range primarily radiated by the human body, which is dominant in the 12 micrometer wavelength and typically in the infrared spectrum between 7 micrometer and 14 micrometers. Said insulating material could be a natural or synthetic feather, down, or fibre insulation. [0011] In a preferred embodiment of the present invention, the said metal layer is applied to a woven, knitted or non woven substrate that has been produced via the process of vapour deposition in a vacuum. In another preferred embodiment of the present invention, said metal layer is applied to a moisture vapour permeable substrate formed of a film, textile, or textile and film composite. In other embodiments, the metal layer is applied to a moisture vapour permeable and substantially liquid impermeable substrate formed of a film, textile, or textile and film composite. [0012] In a further aspect of the present invention, additional organic and inorganic coating layers may be deposited before or after said metal layer in order to improve adhesion to said substrate and/or prevent corrosion and/or achieve a lower emissivity by creating a smoother reflective surface. In addition the metal layer can have increased corrosion resistance by oxidising the surface of a metal coating with an oxygen-containing plasma to form a self protective metal oxide coating. [0013] Functionalization of the various coatings can also be optionally included, and alternative embodiments of the present invention may also have extra material layers in the composite. Any layer may be coated for functionalization, preferably during the same plasma treated vacuum vapour deposition process, and preferably via vapour deposition utilising flash evaporation, to be flame retardant, UV absorbing, self cleaning, hydrophobic, hydrophilic, or antibacterial. [0014] In another preferred embodiment of the present invention, said metal layer may be produced by means of coating the substrate with a thin metallic film by means of sputtering, rotary screen printing, block screen printing, transfer printing, jet printing, spraying, sculptured roller or other methods. In an alternative embodiment, said metal layer is applied to said substrate by means of transfer metallization whereby a thin metal film or foil is coated onto a release substrate via vacuum vapour deposition or other method and then adhered onto said substrate. [0015] An alternative embodiment of the present invention relates to fabrics made for apparel, in various composites, and are constructed such that there is a first substrate and first insulation layer adjacent to the first surface of said substrate and a second insulation layer adjacent to the second layer of said substrate. Whereby the said substrate layer positioned between the two insulation layers provides improved thermal resistance of the total composite. BRIEF DESCRIPTION OF THE DRAWINGS [0016] FIGS. 1A , 1 B, 2 A, 2 B, 2 C, 2 D, 2 E, and 2 F are schematic diagrams showing various embodiments of the present invention, including layering combinations of substrates, metal layers and insulating layers. [0017] FIGS. 3A and 3B are graphs showing testing data of composites comprising insulation layers and/or substrates and/or radiant barrier layers. [0018] FIG. 4A shows an embodiment of the invention that includes a fiber based insulation layer. [0019] FIG. 4B shows an embodiment of the invention that includes a perforated insulation layer. [0020] FIG. 4C shows an embodiment of the invention that includes an insulation layer with cavities. DETAILED DESCRIPTION OF THE INVENTION [0021] As used herein, the term “metal” includes metal alloys as well as metals. [0022] The inclusion of a metallized radiant barrier into a garment requires insulation of the radiant barrier to conduction in order for the radiant barrier to provide improved thermal resistance. Said insulation layer is preferably provided by use of an insulated gap adjacent to the radiant barrier, thereby providing good thermal insulation whilst also maintaining good exposure of the radiant barrier to reflect infra-red radiation. [0023] One aspect of the present invention relates to an infra-red reflective, moisture vapour permeable composite formed by coating at least one side of a moisture vapour permeable substrate with at least one metal layer and combining this said metal layer with at least one insulating layer. [0024] A preferred embodiment of the present invention shown in FIG. 1A features substrate 110 coated with metal layer 120 , insulation layer 130 adjacent to said metal layer and additional substrate 140 adjacent to opposing surface of insulating layer to said metal layer. In an alternative embodiment shown in FIG. 1B , a second metal layer 150 is coated on substrate 140 on the surface adjacent to said insulating layer. [0025] According to a particular embodiment of the invention as shown in FIG. 1A , the substrate 110 is a woven textile, stretch woven textile, and/or composite with moisture vapour permeable and substantially liquid impermeable film or coating. The metal layer 120 is applied to the substrate. The insulation 130 is about 5 mm thick with an emissivity between about 0.3 and about 1. The insulation layer 130 has other thicknesses and emissivities in other embodiments, such as an emissivity between about 0.3 and about 0.4. The substrate 140 is a woven textile, stretch woven textile or knitted textile. [0026] FIG. 2A shows a particularly advantageous embodiment of the present invention. Substrate 110 is disposed between first insulation layer 130 and second insulation layer 230 . In this embodiment, each of the substrate 110 , first insulation layer 130 and second insulation layer 230 are moisture vapour permeable so that the entire composite is moisture vapour permeable. Substrate 110 is a film, textile, or film composite and the insulation layers 130 and 230 are formed of natural or synthetic feather or fibre insulation. In this embodiment, layers 140 and 240 shown in the figure are not used. [0027] Another preferred embodiment of the present invention is shown in FIG. 2A and features substrate 110 coated with metal layer 120 , insulation layer 130 adjacent to said metal layer and additional substrate 140 adjacent to the opposing surface of insulating layer 130 to said metal layer. An additional insulating layer 230 is adjacent to the opposite surface of substrate 110 to the said metal layer and additional substrate layer 240 is adjacent to the opposing surface of insulating layer 230 to substrate 110 . Said insulation layer 230 provides additional insulation to conduction of said metal layer 120 . In other embodiments, additional metal layers are added to the substrate layers to further increase the thermal resistance of said composite. [0028] At least one of the first insulation layer 130 and the second insulation layer 230 is selected to have a thermal resistance between about 0.05 and about 0.5 m 2 K/W. In some embodiments, both insulation layers have a thermal resistance in this range. The type, density, and thickness of insulation material used for these layers is controlled to arrive at the desired thermal resistance. The composition and design of the metal layer 120 is varied to obtain a thermal resistance between 0.0 and about 0.03 m 2 K/W. [0029] According to a particular embodiment of the invention as shown in FIG. 2A , the substrate 110 is a woven textile, stretch woven textile, and/or composite with moisture vapour permeable and substantially liquid impermeable film or coating. The metal layer 120 is applied to the substrate. The insulation 130 is about 5 mm thick with an emissivity between about 0.3 and about 1. The insulation layer 230 is about 5 mm thick with an emissivity between about 0.05 and about 0.5. The insulation layers 130 and 230 have other thicknesses and emissivities in other embodiments, such as an emissivity between about 0.3 and about 0.4. The substrate 140 is a woven textile, stretch woven textile or knitted textile. The substrate 240 is a woven textile, stretch woven textile, and/or composite with moisture vapour permeable and substantially liquid impermeable film or coating. [0030] In another embodiment shown in FIG. 2B , a second metal layer 220 is coated on substrate 110 on the surface opposite to metal layer 120 . In yet another embodiment shown in FIG. 2C , a second metal layer 250 is coated on substrate 240 on the surface adjacent to insulating layer 230 . In another embodiment shown in FIG. 2D , a second metal layer 220 is coated on substrate 110 on the surface opposite to metal layer 120 , a third metal layer 250 is coated on substrate 240 on the surface adjacent to insulating layer 230 and a fourth metal layer 150 is coated on substrate 140 of the surface adjacent to insulating layer 130 . [0031] According to a particular embodiment of the invention as shown in FIG. 2C , the substrate 110 is a woven textile, stretch woven textile, and/or composite with moisture vapour permeable and substantially liquid impermeable film or coating. The metal layer 120 is applied to the substrate 110 . The insulation 130 is about 5 mm thick with an emissivity between about 0.3 and about 1. The insulation layer 230 is about 5 mm thick with an emissivity between about 0.3 and about 1. The insulation layers 130 and 230 have other thicknesses and emissivities in other embodiments, such as an emissivity between about 0.3 and about 0.4. The substrate 140 is a woven textile, stretch woven textile or knitted textile. The substrate 240 is a woven textile, stretch woven textile, and/or composite with moisture vapour permeable and substantially liquid impermeable film or coating. Metal layer 250 is applied to the substrate 240 . [0032] In a further aspect of the present invention shown in FIG. 2E , said composite is provided with 2 insulation layers 130 and 230 with inner substrate 110 and outer substrates 140 and 240 . Said composite has been shown to provide improved thermal resistance compared to the same composite without inner substrate layer 110 by reducing heat loss due to convection. [0033] In another aspect of the present invention, embodiments shown in FIG. 1A , 1 B, 2 A, 2 B, 2 C, 2 D, 2 E, or 2 F could be inversed as to produce layers in the opposite configuration of those described. [0034] FIG. 2F shows an embodiment of the present invention that utilizes a third insulation layer 260 . This embodiment includes a first substrate 110 with a metal layer 120 disposed thereon. A first insulation layer 130 is disposed on the metal layer 120 , and a second substrate—intended to face the heat source, such as the body of the wearer—is disposed on the surface of the first insulation layer 130 opposite to the metal layer. A second insulation layer 230 is disposed on the side of the first substrate 110 opposite of the metal layer 120 . The second insulation layer 230 is disposed on second metal layer 250 which is itself disposed on the third substrate 240 . The third insulation layer 260 is disposed on the third substrate 240 opposite second metal layer 250 . Finally, fourth substrate 270 , which has third metal layer 280 disposed thereon, is disposed on the surface of third insulation layer 260 opposite third substrate 240 . [0035] According to a particular embodiment of the invention as shown in FIG. 2F , the substrate 110 is a woven textile, stretch woven textile, and/or composite with moisture vapour permeable and substantially liquid impermeable film or coating. The metal layer 120 is applied to the substrate 110 . The insulation 130 is about 5 mm thick with an emissivity between about 0.3 and about 1. The insulation layer 230 is about 5 mm thick with an emissivity between about 0.3 and about 1. The substrate 140 is a woven textile, stretch woven textile or knitted textile. The substrate 240 is a woven textile, stretch woven textile, and/or composite with moisture vapour permeable and substantially liquid impermeable film or coating. Metal layer 250 is applied to the substrate 240 . The insulation layer 260 is about 5 mm thick with an emissivity between about 0.3 and about 1. The insulation layers 130 , 230 , and 260 have other thicknesses and emissivities in other embodiments, such as an emissivity between about 0.3 and about 0.4. The substrate 270 is a woven textile, stretch woven textile, and/or composite with moisture vapour permeable and substantially liquid impermeable film or coating. Metal layer 280 is applied to the substrate 270 . [0036] The present invention provides an insulation layer adjacent to said metal layer in order to provide a substantially open area adjacent to the radiant barrier that provides structural support to maintain a consistent air gap between the heat source and radiant barrier. Said insulation layer is preferably a natural or synthetic fiber based insulation with good resistance to compression. The thickness and density of said insulation layer should be optimized to provide insulation to conduction to the radiant barrier whilst allowing reflection of infra-red radiation by the radiant barrier. [0037] FIG. 3A shows the thermal resistance (Rct) of a metalized substrate with an emissivity of 0.236 compared with a substrate without metallization with emissivity 0.797 at air gap spacings of 0 mm, 5 mm, 10 mm, 15 mm, 20 mm and 25 mm. With an air gap of 0 mm no benefit is provided through the addition of the metallized layer as no insulation to conduction is provided. The optimal air gap size to enhance thermal resistance was shown to be 10 mm with an Rct of 0.240 m 2 K/W, which is 36% higher than the substrate with no metallization. When a substrate with a metallized coating of lower emissivity 0.033 was tested at 10 mm air gap, an improvement in Rct of 90% was observed compared to the substrate with no metallization. [0038] FIG. 3B shows the thermal resistance (Rct) of a composite comprising 1 or more polyester fiber insulation layers combined with 2 or more moisture vapor permeable substrates with optional metallization in various configurations. [0039] A composite comprising said polyester fiber insulation layer with thickness of approximately 5 mm and emissivity of around 0.35 and a moisture vapor permeable substrate adjacent to each outside surface of said insulation layer, an Rct measurement of 0.1281 m 2 K/W was measured. When the substrate on the surface of the insulation layer opposite to the heat source was replaced with a metallized substrate with emissivity 0.236 with metal layer facing the insulation an Rct of 0.1926 m 2 K/W was measured thereby giving an improvement of around 50%. When the insulation thickness was increased to around 10 mm an Rct of 0.2603 was measured for the composite without any metal layer and an Rct of 0.3074 m 2 K/W was measured for the composite with the metal layer thereby giving an increase in thermal resistance of 18%. [0040] When additional insulation layers and/or substrate layers and/or metal layers are added, further increases in thermal resistance were observed. When an additional moisture permeable substrate layer was positioned between two 5 mm insulation layers, an Rct of 0.3130 m 2 K/W was measured giving an increase in thermal resistance of 20% compared to the composite without the middle substrate layer. When the middle substrate was metalized with metal layer facing the heat source an Rct of 0.336 m 2 K/W was measured. When both middle and outer substrate layers has metalized layers facing the heat source an Rct of 0.3715 m 2 K/W is measured thereby showing an improvement of thermal resistance of 42% compared to composite of same insulation thickness without any radiant barriers and 190% compared to the composite with 5 mm insulation without any radiant barrier. [0041] In one aspect of the present invention said insulating layer consists of a material that has relatively low thermal conductivity as compared to said metal layer. Thermal conductivity is the reciprocal of thermal resistance. Said insulation layer preferably consists of natural or synthetic feathers or fibres whereby the size and density of said feathers or fibres are selected as to provide high thermal insulation to conduction. Said insulation layer(s) can be combined with said substrate(s) by the process of lamination using an adhesive, high frequency weld, or a melt film, or a melt fibre between surfaces or a stitching/needling process. [0042] In one aspect of the present invention, said insulation consists of synthetic fibres of between about 5 to about 20 micron in diameter and can consist of fibres that are all the same diameter or varying diameters. In another aspect of the present invention, said insulation may consist of a natural feather or down contained between two substrates whereby said substrates are of a knitted woven, non-woven or film that is able to resist the migration of said feathers through the said substrates. In one embodiment of the present invention, thickness and density of the fibres of at least one insulation layer is configured as to provide good infra red transparency, thus maintaining good infrared reflectance of the metal layer(s). FIG. 4A shows the use of a fibre insulation 130 adjacent to metal layer 120 whereby the spacing between the fibres of said insulation layer provide exposure of the metal layer through the insulation. In one embodiment, the density of fibres in insulation layer adjacent to the metal layer is selected such that the ratio of the volume of fibre in the insulation to the volume of air in the insulation is between 1:30 and 1:100. In other embodiments this ratio is within the range of 1:1-1:200. This provides exposure of the metal layer, or air gaps, that improve the infrared reflectance of the metal layer by improving the infrared transparency of the adjacent insulation. [0043] In another embodiment of the present invention, at least one insulation layer is disposed in a pattern, density or texture such that a high percentage of the metal layer is still exposed through the air gaps of the said insulation layer, thus maintaining good infrared reflectance of the metal layer(s). FIG. 4B shows one preferred embodiment whereby said insulation layer is perforated to provide increased exposure of the said metal layer. Perforations may be provided in a regular or irregular pattern or produced by gaps between multiple sheets or segments of insulation. FIG. 4C show another preferred embodiment whereby said insulation layer is embossed or moulded to produce cavities adjacent to the metal layer thereby increasing exposure of said metal layer. The perforations and cavities are designed and/or selected such that at least 50% of the area of the surface of the metal layer on which the first insulation layer is disposed is not in direct contact with the insulation layer. [0044] In another embodiment of the present invention, the thickness and density of the fibres of at least one insulation layer is configured so as to absorb infra red radiation. [0045] In a preferred embodiment of the present invention the insulation layer adjacent to the metal layer(s) has an emissivity of between about 0.1 to about 1 and preferably, about 0.3 to about 1 to allow infrared radiation to pass through said insulation layer and be reflected back by the said metal layer. In embodiments that include two layers of insulation, it is advantageous for one or both layers to have an emissivity in the range of about 0.3 to about 1. More particularly, the emissivity of one or both layers is between about 0.3 and about 0.4. In one embodiment, the insulation layer adjacent to the metal layer is positioned closest to a heat source, such as a person's body, and the second insulation layer on the opposite side of the substrate bearing the metal layer. In this embodiment, the emissivity of the substrate is selected to be substantially higher than the emissivity of the second insulation layer. For example, the emissivity of the substrate is about 0.5 to about 1 while the emissivity of the second insulation layer is about 0.05 to about 0.5. Further, the insulation layer adjacent to the metal layer in such an embodiment would preferably have an emissivity of between about 0.3 and about 1, while the second insulation layer would have an emissivity of between about 0.05 and about 0.5. [0046] In a preferred embodiment, said insulation layer 130 adjacent metal layer is between about 2 mm and about 10 mm thick to allow increased benefit of the addition of said metal layer with reduced overall composite thickness. A second insulation layer 230 adjacent to said substrate on the opposite side of said metal layer may be configured to have a very low emissivity to provide improved insulation to metal and substrate layers. In a preferred embodiment of the present invention, said insulation layer 130 is configured to provide very high resistance to compression to maintain the optimum thickness for high thermal insulation of the composite. The second insulation layer 230 can also have a thickness of between about 2 mm and about 10 mm. [0047] In one aspect of the present invention, said substrate consists of a moisture vapour permeable non woven fabric, woven fabric, knitted fabric, moisture vapour permeable film or composites thereof, including Nylon, polyester, spandex, polypropylene, cotton, wool, or a mix of these materials. In another embodiment of the present invention, at least one textile fabric such as a woven, stretch woven, non-woven, or knitted fabric is applied to the substrate after coating with said organic and metal layers, where the said textile is combined with the substrate by process of lamination. Lamination can occur by using an adhesive, or a melt film, or a melt fibre between surfaces or a stitching/needling process. [0048] In a further aspect of the present invention said substrate is comprised of a textile fabric such as a woven, stretch woven, non-woven, or knitted fabric that is combined with at least one moisture vapour permeable and substantially liquid impermeable coating and/or film lamination. [0049] In a further aspect of the present invention, said substrate consists of a tightly woven textile consisting of fibres of between 5-80 denier as to allow a smooth surface to apply said metal layer and produce a low emissivity. Said textile could be produced from natural or synthetic fibres or blend thereof. In a preferred embodiment said textile is compressed through a series of hot rollers in a cire process before or after metalisation to produce a more smooth surface to produce a lower emissivity of said metal layer. [0050] In a further aspect of the present invention, said substrate consists of a stretchable tightly woven textile consisting of fibres of between 5-80 denier as to allow a smooth surface to apply said metal layer and produce a low emissivity. Said textile could be produced from natural or synthetic fibres or blend thereof. In a preferred embodiment said textile is compressed through a series of hot rollers in a cire process before or after metalisation to produce a more smooth surface to produce a lower emissivity of said metal layer. [0051] In a preferred embodiment of the present invention, the said metal layer(s) can feature an organic or inorganic coating to protect it from moisture and oxidisation. Preferably, a thin organic or inorganic coating layer is also deposited on the surface of the substrate between the substrate layer and the metal coating layer to effectively encapsulate the metal layer and further protect it from moisture and oxidisation. Said organic or inorganic layers can have functionalization useful in the application, such as oliophobic, hydrophobic, UV absorbing, antibacterial polymerisation and the like. The coatings are preferably formed under vacuum using vapor deposition techniques under conditions that substantially coat the substrate without significantly reducing its moisture vapor permeability. [0052] In a further embodiment of the present invention, the said organic or in-organic coatings comprise one or more functional components. Functionalities include hydrophilic coatings from monomers functonalised with groups including hydroxyl, carboxyl, sulphonic, amino, amido and ether. Hydrophobic coatings from monomers with hydrofluoric functional groups and/or monomers that create nanostructure on the textile surface. Antimicrobial coatings from a monomer with antimicrobial functional groups and/or encapsulated antimicrobial agents (including chlorinated aromatic compounds and naturally occurring antimicrobials). Fire retardant coatings from monomers with a brominated functional group. Self cleaning coatings from monomers and/or sol gels that have photo-catalytically active chemicals present (including zinc oxide, titanium dioxide, tungsten dioxide and other metal oxides). Ultraviolet protective coating from monomers and/or sol-gels that contain UV absorbing agents (including highly conjugated organic compounds and metal oxide compounds). [0053] According to one aspect the present invention, the metal and organic or in-organic coating layers are deposited on said substrate using methods that do not substantially reduce the moisture vapor permeability of the substrate. The metal and organic or in-organic coating layers are deposited via a vacuum vapour deposition method, this provides a coated composite substrate that has a moisture vapor permeability that is at least about 80%, even at least about 85%, and even at least about 90% of the moisture vapor permeability of the starting substrate material. Vacuum vapor deposition methods known in the art are preferred for depositing the metal and organic or in-organic coatings. The thickness of the metal and organic or in-organic coatings are preferably controlled within ranges that provide a composite substrate having an emissivity no greater about 0.35. In a preferred embodiment the said substrate is pre-treated by plasma in a vacuum or at atmospheric pressure to improve adhesion of said metal and/or organic and/or inorganic layers. [0054] In embodiment of the present invention the said metal layer(s) are deposited on said substrate by means of vacuum vapour deposition in one or multiple coating layers to achieve the desired thickness of said metal layer to provide optimal reflection of infra-red radiation. Said multiple coating layers may be deposited in the same process in a single vacuum chamber or in multiple processes in the same or different vacuum chambers. This method of vacuum deposition includes a step of flash evaporation in some embodiments. In some embodiments, the surface of the substrate is treated with plasma prior to the step of vacuum depositing of the metal layer. The vacuum depositing step is performed two or more times in some embodiments to make two or more coatings of metal to achieve a thickness of the metal layer of between about 10 nm and about 200 nm. [0055] In another embodiment of the present invention, said substrate is degassed to reduce the water and/or solvent content before coating via vacuum vapour deposition by a process including winding said substrate on a heated drum. Said degassing process is preferably undertaken within a vacuum to allow sufficient degassing at a temperature of between 40-80° C. whereby the lower degassing temperature prevents thermal damage to said substrate. Additional degassing and drying processes maybe also be required at higher temperature to remove other solvents present in said substrate from the manufacturing process. In one preferred embodiment where said substrate is a Polyurethane film, said substrate is pre-dried at a temperature above 120° C. to remove Dimethylformamide and/or other solvents. [0056] In another embodiment of the present invention, said substrate is coated via vacuum vapour deposition using an additional support substrate to provide stability and ease of handling during said coating process. [0057] According to another aspect of the present invention, said metal layer may be produced by means of coating the substrate with a thin metallic film by means of sputtering, rotary screen printing, block screen printing, transfer printing, jet printing, spraying, sculptured roller or other methods. [0058] In another aspect of the present invention, said metal layer is applied to said substrate by means of a transfer metallization process whereby a thin metal film or foil is coated onto a release substrate such as paper sheet, polypropylene sheet, polyester sheet or other material via vacuum vapour deposition or other method and then adhered onto said substrate. [0059] In a further aspect to the present invention, said metal layer may be applied to said substrate in a continuous or discontinuous pattern whereby said metal layer covers the entire surface of the said substrate or part of the surface of said substrate. Such a continuous or non-continuous metal layer is typically in the form of a film that is adhered to the surface of the substrate. [0060] Moisture vapor permeable monolithic (non-porous) films are formed from a polymeric material that can be extruded as a thin, continuous, moisture vapor permeable, and substantially liquid impermeable film. The film layer can be extruded directly onto a first nonwoven, woven or knitted layer using conventional extrusion coating methods. Preferably, the monolithic film is no greater than about 3 mil (76 micrometers) thick, even no greater than about 1 mil (25 micrometers) thick, even no greater than about 0.75 mil (19 micrometers) thick, and even no greater than about 0.60 mil (15.2 micrometers) thick. In an extrusion coating process, the extruded layer and substrate layer are generally passed through a nip formed between two rolls (heated or unheated), generally before complete solidification of the film layer, in order to improve the bonding between the layers. A second nonwoven, woven or knitted layer can be introduced into the nip on the side of the film opposite the first substrate to form a moisture vapor permeable, substantially air impermeable laminate wherein the monolithic film is sandwiched between the two textile layers. [0061] Polymeric materials suitable for forming moisture vapor permeable monolithic films include block polyether copolymers such as a block polyether ester copolymers, polyetheramide copolymers, polyurethane copolymers, poly(etherimide) ester copolymers, polyvinyl alcohols, or a combination thereof. Preferred copolyether ester block copolymers are segmented elastomers having soft polyether segments and hard polyester segments, as disclosed in Hagman, U.S. Pat. No. 4,739,012 that is hereby incorporated by reference. Suitable copolyether ester block copolymers include Hytrel® copolyether ester block copolymers sold by E. I. du Pont de Nemours and Company (Wilmington, Del.), and Arnitel® polyether-ester copolymers manufactured by DSM Engineering Plastics, (Heerlen, Netherlands). Suitable copolyether amide polymers are copolyamides available under the name Pebax® from Atochem Inc. of Glen Rock, N.J., USA. Pebax® is a registered trademark of Elf Atochem, S.A. of Paris, France. Suitable polyurethanes are thermoplastic urethanes available under the name Estane® from The B. F. Goodrich Company of Cleveland, Ohio, USA. Suitable copoly(etherimide) esters are described in Hoeschele et al., U.S. Pat. No. 4,868,062. The monolithic film layer can be comprised of multiple layers moisture vapor permeable film layers. Such a film may be co-extruded with layers comprised of one or more of the above-described breathable thermoplastic film materials. [0062] A moisture vapour permeable and substantially liquid impermeable substrate is also achieved using a microporous film or coating, in some embodiments. [0063] The thickness and the composition of the outer organic or in-organic coating layer is selected such that, in addition to not substantially changing the moisture vapor permeability of the substrate layer, it does not significantly increase the emissivity of the metalized substrate. The outer organic or in-organic coating layer preferably has a thickness between about 0.2 μm and 2.5 μm, which corresponds to between about 0.15 g/m 2 to 1.9 g/m 2 of the coating material. In one embodiment, the outer coating layer has a thickness between about 0.2 μm and 1.0 μm (about 0.15 g/m 2 to 0.76 g/m 2 ), or between about 0.2 μm and 0.6 μm (about 0.15 g/m 2 to 0.46 g/m 2 ). The combined thickness of the intermediate and outer organic or in-organic layers is preferably no greater than about 2.5 μm, even no greater than about 2.0 μm, even no greater than about 1.5 μm. In one embodiment, the combined thickness of the intermediate and outer organic or in-organic coating layers is no greater than about 1.0 μm. In one embodiment, the intermediate coating layer has a thickness between about 0.02 μm and 1 μm (0.015 g/m 2 and 0.76 g/m 2 ), or between about 0.02 μm and 0.6 μm (0.015 g/m 2 and 0.46 g/m 2 ). When additional metal and organic or in-organic layers are deposited, the thickness of each organic or in-organic coating layer is adjusted such that the total combined thickness of all the organic or in-organic coating layers is no greater than about 2.5 μm, or no greater than about 1.0 μm. If the outer organic or in-organic coating layer is too thin, it may not protect the metal layer from oxidation, resulting in an increase in emissivity of the composite substrate. If the outer organic or in-organic coating layer is too thick, the emissivity of the composite substrate can increase, resulting in lower thermal barrier properties. [0064] Suitable compositions for the organic coating layer(s) include polyacrylate polymers and oligomers. The coating material can be a cross-linked compound or composition. Precursor compounds suitable for preparing the organic coating layers include vacuum compatible monomers, oligomers or low MW polymers and combinations thereof. Vacuum compatible monomers, oligomers or low MW polymers should have high enough vapor pressure to evaporate rapidly in the evaporator without undergoing thermal degradation or polymerization, and at the same time should not have a vapor pressure so high as to overwhelm the vacuum system. The ease of evaporation depends on the molecular weight and the intermolecular forces between the monomers, oligomers or polymers. Typically, vacuum compatible monomers, oligomers and low MW polymers useful in this invention can have weight average molecular weights up to approximately 1200. Vacuum compatible monomers used in this invention are preferably radiation polymerizable, either alone or with the aid of a photoinitiator, and include acrylate monomers functionalized with hydroxyl, ether, carboxylic acid, sulfonic acid, ester, amine and other functionalities. The coating material may be a hydrophobic compound or composition. The coating material may be a crosslinkable, hydrophobic and oleophobic fluorinated acrylate polymer or oligomer, according to one preferred embodiment of the invention. Vacuum compatible oligomers or low molecular weight polymers include diacrylates, triacrylates and higher molecular weight acrylates functionalized as described above, aliphatic, alicyclic or aromatic oligomers or polymers and fluorinated acrylate oligomers or polymers. Fluorinated acrylates, which exhibit very low intermolecular interactions, useful in this invention can have weight average molecular weights up to approximately 6000. Preferred acrylates have at least one double bond, and preferably at least two double bonds within the molecule, to provide high-speed polymerization. Examples of acrylates that are useful in the coating of the present invention and average molecular weights of the acrylates are described in U.S. Pat. No. 6,083,628 and WO 98/18852. [0065] Suitable compositions for the in-organic coating layers include metal oxide components including but not limited to Silicone dioxide, titanium dioxide, tungsten dioxide, zinc oxide. Inorganic coating layer(s) can be made by the sol-gel process of depositing a partially reacted metal alkoxide onto the substrate in the presence of water and an alcohol. The layer can also be produced from the deposition of a metal chloride solution. After application layers may be reduced in thickness by dry or moist heat treatment. The most effective method for deposition of metal alkoxide or metal chloride solutions onto the substrate is by flash evaporation and deposition in a vacuum environment. [0066] Metals suitable for forming the metal layer(s) of the composites of the present invention include aluminum, gold, silver, zinc, tin, lead, copper, titanium and their alloys. The metal alloys can include other metals, so long as the alloy composition provides a low emissivity composite substrate. Each metal layer has a thickness between about 15 nm and 200 nm, or between about 30 nm and 60 nm. In one embodiment, the metal layer comprises aluminum having a thickness between about 15 and 150 nm, or between about 30 and 60 nm. In other embodiments, the metal layer comprises a silver precipitate with antibacterial properties. Methods for forming the metal layer are known in the art and include resistive evaporation, electron beam metal vapor deposition, or sputtering. If the metal layer is too thin, the desired thermal barrier properties will not be achieved. If the metal layer is too thick, it can crack and flake off and also reduce the moisture vapour permeability of the composite. Generally it is preferred to use the lowest metal thickness that will provide the desired thermal barrier properties. When the composite of the present invention is used in a garment the metal layer reflects infrared radiation providing a radiant thermal barrier that reduces energy loss and keeps the person wearing the garment warmer. [0067] The thermal barrier properties of a material can be characterized by its emissivity. Emissivity is the ratio of the power per unit area radiated by a surface to that radiated by a black body at the same temperature. A black body therefore has an emissivity of one and a perfect reflector has an emissivity of zero. The lower the emissivity, the higher the thermal barrier properties. Each metal layer, intermediate organic coating and adjacent outer organic coating layer is preferably deposited sequentially under vacuum without exposure to air or oxygen so that there is no substantial oxidation of the metal layer. Polished aluminum has an emissivity between 0.039-0.057, silver between 0.020 and 0.032, and gold between 0.018 and 0.035. A layer of uncoated aluminum generally forms a thin aluminum oxide layer on its surface upon exposure to air and moisture. The thickness of the oxide film increases for a period of several hours with continued exposure to air, after which the oxide layer reaches a thickness that prevents or significantly hinders contact of oxygen with the metal layer, reducing further oxidation. Oxidized aluminum has an emissivity between about 0.20-0.31. By minimizing the degree of oxidation of the aluminum by depositing the outer organic coating layer prior to exposing the aluminum layer to the atmosphere, the emissivity of the composite substrate is significantly improved compared to an unprotected layer of aluminum. The outer organic coating layer also protects the metal from mechanical abrasion during roll handling, garment production and end-use. [0068] Reference throughout this 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 present invention. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments. [0069] Similarly it should be appreciated that in the above description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the Detailed Description are hereby expressly incorporated into this Detailed Description, with each claim standing on its own as a separate embodiment of this invention. [0070] Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination. [0071] In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In other instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description. [0072] Although the present invention has been described with particular reference to certain preferred embodiments thereof, variations and modifications of the present invention can be effected within the spirit and scope of the following claims.
Fabrics made for apparel, tents, sleeping bags and the like, in various composites, constructed such that a combination of substrate layers and insulation layers is configured to provide improved thermal insulation. The fabric composites are constructed to form a radiant barrier against heat loss via radiation and via conduction from a body.
1
BACKGROUND OF THE INVENTION 1. Technical Field This invention relates in general to an improved disk drive and in particular to detecting displacement of the actuator in a disk drive. Still more particularly, the invention relates to using the micro actuator transducer in a disk drive as a sensor for sensing head displacement due to contact with a rotating disk. 2. Description of the Prior Art A disk drive utilizes actuators for reading and writing data to its rotating disks. The radial positions of the actuators, relative to tracks on the disks, are typically controlled by a transducer in a closed-loop servo system. Some disk drives utilize two-stage actuators for reading and writing to the disks. A two-stage actuator comprises a primary actuator arm and a micro actuator arm that is pivotally mounted to and extends from a distal end of the primary actuator arm. The micro actuator arm has one or more heads on its distal end for interacting with a respective disk. The micro actuator arm also has a smaller mass and therefore significantly higher mechanical bandwidth than the primary actuator arm. During operation of the disk drive, the heads on the micro actuator arms occasionally will contact the spinning disks, thereby subjecting the micro actuator arms to radial displacement relative to the disks. In the prior art, in-situ schemes such as magnetic envelope or thermal MR sensing are used to detect this displacement. Magnetic sensing is difficult in that one must distinguish between track misregistrations from head-disk contact events. Moreover, thermal MR measurements require additional drive circuitry which adds significant cost to the device. However, the relative displacement of the distal and proximal ends of the micro actuator arms are indicative of the sliding forces generated during head-disk contacts. Since these contact-generated displacements did not originate from the controlling servo system, they appear as intermittent signals that are unlikely to occur during position error signal measurements. Thus, it would be desirable to control the micro actuator arm while distinguishing disk contact with the micro actuator arm without adding additional circuitry. Such a system for controlling and monitoring the actuator would be both simpler and more robust than prior art methods. SUMMARY OF THE INVENTION The present invention utilizes a disk drive with a simple detector circuit that is connected to the distal end of a two-stage actuator. The actuator has a micro actuator that is used for fine track positioning of a read/write head relative to a disk. Intermittent contact between the head on the micro actuator and the disk produces forces that are detected and measured by the micro actuator drive circuitry. These measurements are used to determine if excessive contact is occurring between the head and its respective disk, and for predictive failure analysis or recovery operations. Alternatively, the present invention also comprises a differential method where the output signals from multiple micro actuators are compared in order to improve noise immunity. In addition, comparisons between the forces at the proximal and distal ends of any of the micro actuators are used to better identify the source of such forces. For example, this allows the system to distinguish between common mode forces such as those generated by windage and flex cable bias, from forces generated by intermittent head-disk contacts. Another embodiment of the invention is to use the micro actuator as a detector for slider-disk contact that does not utilize a position error signal. In this mode, the track position is maintained by using the arm actuator. A signal from the micro actuator is used to electronically detect the slider-disk contact. The signal is available since the motor also functions as a generator, e.g., piezoelectric or voice coil-based micro actuators, or any micro actuator that is capable of generating a signal in response to an applied force or displacement. Accordingly, it is an object of the present invention to provide an improved disk drive. It is an additional object of the present invention to provide a system and method for detecting displacement of the actuator in a disk drive. Still another object of the present invention is to use the micro actuator transducer in a disk drive as a sensor for sensing head displacement due to contact with a rotating disk. The foregoing and other objects and advantages of the present invention will be apparent to those skilled in the art, in view of the following detailed description of the preferred embodiment of the present invention, taken in conjunction with the appended claims and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS So that the manner in which the features, advantages and objects of the invention, as well as others which will become apparent, are attained and can be understood in more detail, more particular description of the invention briefly summarized above may be had by reference to the embodiment thereof which is illustrated in the appended drawings, which drawings form a part of this specification. It is to be noted, however, that the drawings illustrate only a preferred embodiment of the invention and is therefore not to be considered limiting of its scope as the invention may admit to other equally effective embodiments. FIG. 1 is a schematic drawing of a disk drive. FIG. 2 is an enlarged schematic isometric view of a first embodiment of a disk drive constructed in accordance with the invention. FIG. 3 is an enlarged schematic isometric view of a second embodiment of the disk drive of FIG. 2 . FIG. 4 is a block diagram of a signal detection and classification system for the disk drives of FIGS. 2 and 3. FIG. 5 is a schematic diagram of a third embodiment of the disk drive of FIG. 2 . FIGS. 6A and 6B are plots of micro actuator output signals over time indicating sliding and intermittent contact, respectively. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. 1, a schematic drawing of an information storage system comprising a magnetic hard disk file or drive 11 for a computer system is shown. Drive 11 has an outer housing or base 13 containing a plurality of stacked, parallel magnetic disks 15 (one shown) which are closely spaced apart. Disks 15 are rotated by a spindle motor located therebelow about a central drive hub 17 . A plurality of stacked, parallel actuator arms 21 (one shown) are pivotally mounted to base 13 about a pivot assembly 23 . A controller 19 is mounted to the base for selectively moving arms 21 relative to disks 15 . In the embodiment shown, each arm 21 comprises a mounting support 25 , a pair of parallel, cantilevered load beams or suspensions 27 extending from each mounting support 25 , and a head gimbal assembly 29 having at least one magnetic read/write head secured to each suspension 27 for magnetically reading data from or magnetically writing data to disks 15 . Suspensions 27 have a spring-like quality which biases or maintains them in parallel relationship relative to one another. A motor assembly 31 having a conventional voice coil motor is also mounted to pivot assembly 23 opposite head gimbal assemblies 29 . Movement of an actuator driver 33 (indicated by arrow 35 ) moves head gimbal assemblies 29 radially across tracks on the disks 15 until the heads on assemblies 29 settle on the target tracks. The head gimbal assemblies 29 operate in a conventional manner and always move in unison with one another, unless drive 11 uses a split actuator (not shown) wherein the arms move independently of one another. Referring now to FIG. 2, a first embodiment of a disk drive 101 constructed in accordance with the invention is shown, along with a Cartesian coordinate system 103 for reference purposes. Drive 101 has a magnetic disk 105 that rotates at an angular velocity 106 about an axis that is parallel to the z-axis of coordinate system 103 . Drive 101 also has an actuator assembly 113 for reading data from and writing data to disk 105 . Although only one disk 105 and actuator assembly 113 are shown, it should be apparent that a plurality of components may be employed simultaneously in drive 101 . A head or slider 121 is suspended above the surface of the spinning disk 105 by a head/gimbal assembly (HGA) 118 . The HGA 118 is mounted to the distal end of a micro actuator arm 109 . The proximal end of micro actuator arm 109 is pivotally mounted near the distal end of a primary actuator arm 107 at pivot point 111 . The surface velocity of disk 105 , represented by vector 123 , is at an angle 124 relative to a longitudinal axis 125 of actuator assembly 113 . Axis 125 is parallel to the x-axis of coordinate system 103 . Occasionally, slider 121 will physically contact the spinning disk 105 and a contact force develops in the same direction as the disk velocity vector 123 . The contact force has a y-axis component 129 that is perpendicular to longitudinal axis 125 . Force component 129 of the contact force acts at a distance 119 from the micro actuator pivot point 111 to the location 117 of the slider/disk contact. When force component 129 acts at distance 119 , a moment 127 is produced about micro actuator pivot point 111 . Moment 127 causes undesirable rotation of micro actuator arm 109 , relative to primary actuator arm 107 . The rotation of micro actuator arm 109 must be counteracted by the drive's servo track positioning system or transducer, indicated schematically at block 128 . Displacements due to head-disk contact are detectable as back-EMF if the micro actuator is a voice coil, or voltage spikes at the input driver if the micro actuator is piezoelectric, for example. The resulting error signal produced by transducer 128 as a result of the rotation of micro actuator arm 109 therefore detects and gives an indication of the slider/disk contact. For example, if slider 121 is in near-constant or constant sliding contact with disk 105 , the error signal will have primarily lower frequency signals as shown by plot 601 in FIG. 6 A. However, if the contact between slider 121 and disk 105 is intermittent in nature, the error signal will have higher frequencies as shown by plot 603 in FIG. 6 B. In this sense, the existing transducer 128 in disk drive 101 is adapted to perform two functions: it controls the radial position of the actuator assembly 113 relative to disk 105 , and it senses displacement of slider 121 due to contact with disk 105 . Referring now to FIG. 3, a second embodiment of the invention is illustrated as disk drive 201 . Like drive 101 , drive 201 has an actuator assembly 202 that pivots relative to a rotating disk 203 . A slider 221 is suspended above disk 203 on actuator assembly 202 . Slider 221 has magnetic elements 229 for reading data from and writing data to filamentary recording tracks 231 (one shown). The magnetic elements 229 are mounted to a movable portion 225 on slider 221 . Portion 225 can be moved laterally (left or right in FIG. 3) relative to slider 221 via a drive element 207 . In the embodiment shown, portion 225 is elastically attached to slider 221 and drive element 207 is a rotary gear with a longitudinal axis 208 and teeth 209 that interface with a gear 211 on portion 225 . Gear 207 rotates as shown at arrows 205 . Other interfacing means between portion 225 and slider 221 also may be employed. In normal operation, movable portion 225 is driven by gear 207 so that reading and writing elements 229 remain over the desired track 231 for interaction therewith. However, occasionally contact will occur between portion 225 and disk 203 , e.g., a mechanical protrusion 232 on disk 203 will physically contact the movable portion 225 . Such contact produces a lateral force (represented by vector 233 ), which produces a slight rotation of gear 207 . This rotation is counteracted by the driver's servo track positioning system or transducer 228 . The resulting error signal produced as a result of the rotation of portion 225 therefore detects and gives an indication of the slider/disk contact, as described above for the previous embodiment. Thus, transducer 228 in disk drive 201 controls the radial position of the actuator assembly 202 relative to disk 203 , and it senses displacement of slider 221 due to contact with disk 203 . Referring now to FIG. 4, a block diagram of a signal detection and classification system 301 for the disk drives 101 , 201 is shown. As illustrated at block 303 , a read signal is obtained from a magnetic reproducing head, which comprises both recorded data and servo information read from the disk. Read signal 303 is processed by a servo demodulator, as depicted at block 305 . Servo demodulator 305 generates a resulting or position error signal (PES) 307 . The PES 307 is distributed to a plurality of elements for classification of the displacement. For example, the PES 307 is processed by a high frequency, electronic bandpass filter, illustrated at block 309 , which is tuned to detect PES frequencies that correspond to intermittent contact (depicted at block 315 ). The PES 307 is also delivered to an electronic bandpass filter 311 which is tuned to detect lower PES frequencies that correspond to continuous or near-continuous slider/disk contact, as illustrated at block 317 . In addition, the PES 307 is sent to the servo micro actuator control loop 319 for correcting any track misregistration. Although only two PES detection filters are shown and described, additional filters may be added to detect PES frequencies that correspond to other mechanical phenomenon. In one version of the invention, the outputs at blocks 315 and 317 are compared against thresholds 321 , 323 to determine if the energy of PES 307 is excessive in regard to the intermittent or continuous contact, respectively. Thresholds 321 , 323 may be determined and set in a variety of ways. For example, if the drive is operating in an environment with excessive noise or vibration, the thresholds may be set accordingly to reduce false alarms. Alternatively, the thresholds can be triggered based on statistical analysis to determine, for example, if any of the individual heads or micro actuators have deviated as statistical outliers. In the preferred embodiment, thresholds 321 , 323 are determined during the manufacturing of the disk drive by analyzing the PES signals from each head to determine the normal operational range of outputs 315 , 317 (e.g., without intermittent or sliding contact). Thus, system 301 has a look-up table for these threshold values for each head. Moreover, the inner, middle, and outer disk tracks for each head may be provided with different thresholds to account for conditions such as air turbulence and disk flutter at the outer disk diameter, for example. When a particular head is selected, the appropriate look-up threshold is compared with the values of outputs 315 , 317 . A third embodiment of the invention is illustrated as disk drive 400 in FIG. 5 . Disk drive 400 uses a micro actuator 407 as a transducer or detector for detecting contact between its slider 405 and disk 403 without the use of a position error signal. Slider 405 has a read element 408 and flies above disk 403 as disk 403 rotates about an axis 401 . Slider 405 is maintained over a desired track on disk 403 by amplifying the readback signal 421 from read element 408 and using an arm electronics module 417 which amplifies and filters readback signal 421 . The amplified signal 416 from the arm electronics module 417 is passed to a servo control 415 which provides a control signal 413 to a voice coil motor (VCM) 411 . The VCM 411 controls the radial position of slider 405 via a suspension 409 . The servo control 415 also may control the position of the read element 408 through the micro actuator 407 via a control signal 418 . In addition, an output signal 423 from micro actuator 407 is delivered to an amplifier 425 . The output signal 423 comprises back EMF, piezoelectric signals, or other signals obtained from micro actuator 407 . In the embodiment shown, the amplified signal 427 is passed through one or more filters 429 , 433 to isolate signal frequencies which indicate the type of slider-disk contact that is occurring, as described for the previous embodiment. The filters 429 , 433 may be bandpass filters or other suitable filters and produce filtered output signals 431 , 435 that type the slider-disk contact as intermittent or continuous. The outputs 431 , 435 are compared against thresholds 437 , 439 , respectively, to determine if they are excessive. Thus, drive 400 also has a look-up table for the threshold values for each head. Note that the invention could use a filter bank of any size in order to discriminate between sliding contact, intermittent contact, or other sources. Alternatively, a frequency analysis of the PES 307 (FIG. 3) or output signal 423 (FIG. 4) may be performed. If these signals are in digital form, for example, a Fast Fourier Transform (FFT) could be used to analyze the frequency content of the signals. From the spectrum, one could determine if sliding or intermittent contact is present by comparing the magnitude of the frequencies in an appropriate frequency band to a threshold. The invention has several advantages including the ability to allow the system to distinguish between track misregistrations and head-disk contact events with a simpler and more robust design as compared to other in-situ techniques. When a micro actuator is used, displacements due to head-disk contact are detectable as back-EMF if the micro actuator is a voice coil, or voltage spikes at the input driver if the micro actuator is piezoelectric. The system also distinguishes between track misregistrations and head-disk contact events. Furthermore, the system requires no additional drive circuitry thereby minimizing the cost of the feature. The invention also may be used for predictive failure analysis or recovery operations. While the invention has been shown or described in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the scope of the invention.
A disk drive with a detector circuit is connected to the distal end of a two-stage actuator. The actuator has a micro actuator for fine track positioning of a read/write head relative to a disk. Intermittent contact between the head and the disk produces forces that are detected and measured by the micro actuator drive circuitry. These measurements are used to determine if excessive contact is occurring between the head and the disk. Alternatively, the present invention also uses a differential method where the output signals from multiple micro actuators are compared to improve noise immunity. In addition, comparisons between the forces at the proximal and distal ends of the micro actuators are used to better identify the source of such forces. For example, this allows the system to distinguish between common mode forces such as those generated by windage and flex cable bias, from forces generated by intermittent head-disk contacts.
6
This application is the national phase entry under 35 U.S.C. §371 of International Application No. PCT/EP2008/059388, filed Jul. 17, 2008, which claims priority to German Patent Application No. 102007033861.0, filed Jul. 20, 2007 and German Patent Application No. 102007036411.5, filed Aug. 2, 2007, each of which is hereby incorporated by reference in its entirety. BACKGROUND The invention relates to an inhaler with improved operability for inhaling powdered medicaments from capsules that are inserted in a capsule holder arranged in the inhaler prior to use. After the capsules have been placed in the capsule holder, the patient can press an actuating member, which can be set in motion from a resting position and thereby interacts with at least one pin adapted to be pushed into the capsule holder. Using the minimum of one pin the capsule is pierced and the medicament is released. An inhaler of this kind is described for example in EP 0 703 800 B1 or EP 0 911 047 A1. The inhaler known from the above mentioned specifications has a dish-shaped lower part and an equally dish-shaped cover which fits it, these two parts being capable of being flipped apart for use, about a joint provided in the edge portion. Between the lower part and the cover, a mouthpiece which can also be flipped open and a plate below it with a capsule holder provided underneath also act on the joint. After the individual assemblies have been flipped open the patient can insert a drug-filled capsule in the capsule holder, pivot the plate and capsule holder and the mouthpiece into the lower part and pierce the capsule by means of a spring loaded actuating member projecting laterally from the lower part. The patient being treated then draws the pharmaceutical composition into his airway by sucking on the mouthpiece. SUMMARY OF THE INVENTION The intention is to improve the known inhalers still further in terms of their handling. This aim is achieved according to the invention with an inhaler in which the actuating member is enlarged and is constructed such that the pin holder is situated above the point of application of the force and below the suspension of the push-button. This results in a genuine reduction in the force required by the user to press the pin or pins through the capsule wall In addition there is a subjective reduction in force for the user on account of the enlarged surface of the push-button compared with the devices known from the prior art. For an inhaler known from the prior art the user has to apply about 35 Newtons in order to pierce the capsule with the pin or pins using the actuating member. In the inhaler according to the invention, 10-25 Newtons, preferably 15-20 Newtons are required. The cover has an inwardly or outwardly extending bead, which is not externally visible. This bead serves to close the cover at the button, which is located on the lower part of the inhaler. To enable the cover to be removed from the lower part the actuating member comprises on its upper side a recess which is inclined so as to form a sliding surface for the closure element in the form of a sloping plane and to release the cover from the lower part on actuation and hence when the actuating member is advanced. The recess in the actuating member may vary in size. The minimum size must be sufficient to enable the cover to be released from the lower part in the manner of a pocket watch. The maximum size depends on the top of the actuating member. The actual opening movement of the cover can then be carried out as before, by the patient grasping the cover and flipping it fully open. The mouthpiece that can be flipped away may be provided with one or two gripping aids that ensure quick and reliable opening of the mouthpiece. Each gripping aid may be arranged so that the contact with the mouthpiece is outside the area that the patient requiring treatment has to place in his mouth for suction. The contact surface for opening and the contact surface for suction are clearly separated from one another by the shape and design of the mouthpiece. Preferably, the gripping aids are located to the left and right of the button and the two gripping aids do not converge in the region of the button. This gives the mouthpiece an optically and practically improved appearance that allows intuitive handling for the user and at the same time provided optimum hygiene conditions. This is particularly important in the area around the mouthpiece, as this component is placed in the oral cavity when the inhaler is used. In one embodiment, to assist the opening movement, at least one other spring element may be disposed between the plate and lower part, which are of suitable dimensions to allow the cover and/or mouthpiece to snap open. Alternatively, an embodiment without a spring element is also possible. The actuating member is of particular importance at the start of an asthma attack. Thanks to the effective arrangement of the actuating member combined with the reduced force required from the patient the inhaler is significantly easier to operate. This is particularly valuable when patients are suffering from arthritis or similar diseases or have restricted movement in their fingers for other reasons. The actuating member consists of a two-part construction, having an inner part and an outer part that are snap-fitted to one another. The inner part has two parallel guide arms (see below). When the actuating member is actuated, the outer part presses with a part of a circle on the inner part, which then moves in a linear manner to push the pins into the capsule. The actuating member is attached to the plate that can be latched to the lower part. This can be done, for example, by means of snap-fit hooks, latching hooks or similar technical means. Preferably the actuating member is displaceably mounted on the plate or capsule holder. The plate and/or the capsule holder thus form(s) an abutment for the multi-functional actuating member, which slides along the plate as it moves from the resting position into the desired functional position and is thereby guided by means of a guide rail, for example. In a favourable embodiment the actuating member is spring-loaded. The restoring force which is already present in the resting position ensures that after the inhaler has been used the actuating member is returned to the resting position and thus the inhalation process can be started or continued. Advantageously the actuating member comprises a main body and two parallel guide arms engaging thereon. The guide arms project into the lower part and by means of corresponding built-in parts, for example with guide sleeves arranged on the outside of the capsule holder, serve to guide the actuating member during the movement from the resting position into the respective functional positions and back into the resting position. The guide arms may comprise end stops at their end remote from the main body, which abut on the guide sleeves in the resting position. In this way the actuating member is put under tension. The guide arms may be of any desired shape and arrangement (e.g. convergent or divergent). In addition, more than two guide arms may be provided. In all, the actuating member has two abutment regions; one is for the inside of the button and the other is for the outside of the button. In a preferred embodiment the main body of the actuating member may have a grooved surface. This grooved surface may be on the top or at the side. Preferably, the grooved surface will be in a gripping depression provided in the actuating member. The gripping surface acts both as a design element and as a means to provide optimum grip during actuation. It is located on the main body of the actuating member outside the inhaler region and therefore does not come into contact with the patient's mouth. In addition, the grooved surfaces may be smaller in area than the overall surface of the actuating member while still guaranteeing safe and rapid use of the inhaler. Advantageously the upper grooved surface in the resting position has a recess in its region close to the cover for accommodating the closure element of the cover. Within the recess the side wall directed towards the lateral grooved surface is inclined so that as the main body is pushed in, this side wall forms a sliding surface for the closure element and in this way the closure element together with the cover is lifted out of the latched position. Advantageously the plate latched to the lower part can be detached from the lower part so that the plate can be pivoted away from the lower part. This pivot function makes cleaning of the inhaler easier. The engagement between plate and lower part can be achieved using the retaining flaps mentioned earlier. It is also possible to construct the inhaler according to all the embodiments so that the actuating member having the minimum of one pin which can penetrate into the capsule holder is attached to the plate such that it can be released from the lower part and swivelled away together with the plate latched to the lower part. Preferably, the actuating member is attached to the plate so that the two parts together form a pivotable unit. BRIEF DESCRIPTION OF THE DRAWING To assist in the understanding of the invention it will now be described more fully by reference to the FIGURE ( FIG. 1 ) that follows, wherein: FIG. 1 : is an exploded view with actuating member and mouthpiece with gripping aid DETAILED DESCRIPTION OF THE INVENTION FIG. 1 shows the inhaler in an exploded view. The essential assemblies are the lower part 6 which accommodates the plate 3 and is covered by the latter, the mouthpiece 2 which can be latched to the lower part 6 via the retaining lugs of the screen housing 12 and the cover 1 which is formed to complement the lower part 6 . In the closed position of the inhaler the closure element 14 on the cover 1 engages on the plate 3 and is held there by frictional engagement. It is also possible to obtain interlocking engagement by the provision of bead-like structures on the closure element 14 . For the closure element 14 on the cover 1 to engage on the plate 3 , the outer actuating member 7 comprises a recess 26 into which the closure element 14 is lowered during the closing operation. The recess 26 is provided with an inclined side wall and is located in the area nearest the cover. The actuating member consists of an outer actuating member 7 , suspended from plate 3 by suspension means 20 and 22 together, and an inner actuating member 10 . The outer actuating member 7 has a lateral grooved surface 28 on its outer surface which remains outside the inhaler. In order to open the cover 1 first of all the outer actuating member 7 is moved or pressed in the direction of the inhaler. The closure element 14 on the cover 1 impacts the inclined side wall of the recess, which, as the closure element 14 continues to advance, acts as a sliding surface and ensures release of the cover 1 . The recess 16 connects the outer and inner actuating members 7 and 10 by means of a suspension in the form of a snap-fit hook, pin or other suspension means, for example. The recess 16 may be round or oval in shape. The oval may be arranged in a horizontal or vertical position or in any position. Preferably, the recess 16 is a so-called oblong hole, i.e. an elongate hole or oval which allows optimum guidance of the pins 8 and 11 in the axial direction, so as to ensure precise piercing of the capsule. The lower part 6 is cup-shaped and accommodates the whole of the capsule holder 5 arranged on the underside of the plate 3 . However, in order to insert a capsule filled with medicament (not shown) in the capsule holder 5 , the mouthpiece 2 must also be flipped out of the way. In the embodiment according to FIG. 1 this is done by acting on the outer actuating member 7 . In this opened position of the cover 1 and mouthpiece 2 the capsule can be placed in the capsule holder 5 through an opening in the plate 3 . Then the mouthpiece 2 is swivelled back again and closed again by latching the retaining lugs of the screen housing 12 in the plate 3 . The screen housing 12 contains the screening mesh 13 in its centre. The screening mesh 13 is made of standard commercial materials such as metal or plastics, for example. In the latter case, the screen may be made by injection moulding. For releasing the active substance the outer actuating member 7 is actuated. Its construction is such that the inner actuating member 10 contacts the pin or pins and is located above the point of application of the force and below the point of suspension of the push-button. On the inner actuating member 10 there is at least one pin, but preferably two perpendicularly offset, parallel pins 8 , 11 , moving continuously as the actuating member 7 , 10 is pushed in towards the capsule (not shown) and perforating it. The perforation process can be observed through an inspection window (not shown). In the capsule holder 5 there is one or at least two tubular pin passages 18 and 19 which are aligned axially in accordance with the direction of movement of the pin or pins 8 , 11 . On the one hand these ensure that the pin or pins 8 , 11 are correctly aimed at the capsule (not shown) and on the other hand they provide additional guidance of the actuating member 7 , 10 . However, the essential guiding is done by two guide arms 15 arranged laterally. The guide arms 15 also have the task of holding the actuating member 7 , 10 under spring bias. For this purpose the guide arms 15 are provided at their end remote from the main body with end stops which abut on the guide sleeves of the capsule holder 5 in the resting position of the actuating member 7 , 10 . The guide sleeves are located on the outside of the capsule holder 5 . Between the guide arms 15 is arranged a helical spring 9 which extends parallel to the pin or pins 8 , 11 in its axial direction, the helical spring 9 being matched to the length of the guide arms 15 such that the actuating member 7 , 10 is under tension even in the resting position. The individual assemblies made up of the lower part 6 , plate 3 , mouthpiece 2 and cover 1 are connected by means of hinge recesses and a spindle 4 and are all movable or pivotable relative to one another about this spindle. The pins used may be any pins known to the skilled man. They may be solid or hollow pins. Preferably, solid pins are used. In particular, the upper pin (facing the mouthpiece) may be a triangular pin with a triangular point. The lower pin may be a standard pin with a standard point, as laid down in the German DIN standard, for example. Alternatively the upper pin may be a standard pin with a standard point and the lower pin may be a triangular pin with a triangular point. As a second alternative it is possible to use two triangular pins with triangular points or two standard pins with standard points. The capsules used may be any of the capsules known in the art for powder inhalers (such as (hard) gelatine, plastic or metal capsules). A plastic capsule, in particular, may be used in the inhaler according to the invention, as disclosed in WO 00/07572, EP 1 100 474. The inhaler may have an inspection window. However, this is not essential for it to function in the intended manner. Similarly, all the components of the inhaler may be modified by methods known to the skilled man and according to the possibilities availability in plastics technology. Possible modifications include, for example, reinforcing or altering the wall thickness. However, these possibilities are not absolutely essential to the operation of the inhaler. The inhaler may also be coated on its inside or outside by methods known in the art. It may be used for the inhalation of all kinds of powdered medicaments which it is therapeutically advisable to administer by inhalation. The compounds listed below may be used in the device according to the invention on their own or in combination. In the compounds mentioned below, W is a pharmacologically active substance and is selected (for example) from among the betamimetics, anticholinergics, corticosteroids, PDE4-inhibitors, LTD4-antagonists, EGFR-inhibitors, dopamine agonists, H1-antihistamines, PAF-antagonists and PI3-kinase inhibitors. Moreover, double or triple combinations of W may be combined and used in the device according to the invention. Combinations of W might be, for example: W denotes a betamimetic, combined with an anticholinergic, corticosteroid, PDE4-inhibitor, EGFR-inhibitor or LTD4-antagonist, W denotes an anticholinergic, combined with a betamimetic, corticosteroid, PDE4-inhibitor, EGFR-inhibitor or LTD4-antagonist, W denotes a corticosteroid, combined with a PDE4-inhibitor, EGFR-inhibitor or LTD4-antagonist W denotes a PDE4-inhibitor, combined with an EGFR-inhibitor or LTD4-antagonist W denotes an EGFR-inhibitor, combined with an LTD4-antagonist. The compounds used as betamimetics are preferably compounds selected from among albuterol, arformoterol, bambuterol, bitolterol, broxaterol, carbuterol, clenbuterol, fenoterol, formoterol, hexoprenaline, ibuterol, isoetharine, isoprenaline, levosalbutamol, mabuterol, meluadrine, metaproterenol, orciprenaline, pirbuterol, procaterol, reproterol, rimiterol, ritodrine, salmefamol, salmeterol, soterenol, sulphonterol, terbutaline, tiaramide, tolubuterol, zinterol, CHF-1035, HOKU-81, KUL-1248 and 3-(4-{6-[2-hydroxy-2-(4-hydroxy-3-hydroxymethyl-phenyl)-ethylamino]-hexyloxy}-butyl)-benzyl-sulphonamide 5-[2-(5.6-diethyl-indan-2-ylamino)-1-hydroxy-ethyl]-8-hydroxy-1H-quinolin-2-one 4-hydroxy-7-[2-{[2-{[3-(2-phenylethoxy)propyl]sulphonyl}ethyl]-amino}ethyl]-2(3H)-benzothiazolone 1-(2-fluoro-4-hydroxyphenyl)-2-[4-(1-benzimidazolyl)-2-methyl-2-butylamino]ethanol 1-[3-(4-methoxybenzyl-amino)-4-hydroxyphenyl]-2-[4-(1-benzimidazolyl)-2-methyl-2-butylamino]ethanol 1-[2H-5-hydroxy-3-oxo-4H-1,4-benzoxazin-8-yl]-2-[3-(4-N,N-dimethylaminophenyl)-2-methyl-2-propylamino]ethanol 1-[2H-5-hydroxy-3-oxo-4H-1,4-benzoxazin-8-yl]-2-[3-(4-methoxyphenyl)-2-methyl-2-propylamino]ethanol 1-[2H-5-hydroxy-3-oxo-4H-1,4-benzoxazin-8-yl]-2-[3-(4-n-butyloxyphenyl)-2-methyl-2-propylamino]ethanol 1-[2H-5-hydroxy-3-oxo-4H-1,4-benzoxazin-8-yl]-2-{4-[3-(4-methoxyphenyl)-1,2,4-triazol-3-yl]-2-methyl-2-butylamino}ethanol 5-hydroxy-8-(1-hydroxy-2-isopropylaminobutyl)-2H-1,4-benzoxazin-3-(4H)-one 1-(4-amino-3-chloro-5-trifluoromethylphenyl)-2-tert.-butylamino)ethanol 6-hydroxy-8-{1-hydroxy-2-[2-(4-methoxy-phenyl)-1,1-dimethyl-ethylamino]-ethyl}-4H-benzo[1,4]oxazin-3-one 6-hydroxy-8-{1-hydroxy-2-[2-(ethyl 4-phenoxy-acetate)-1,1-dimethyl-ethylamino]-ethyl}-4H-benzo[1,4]oxazin-3-one 6-hydroxy-8-{1-hydroxy-2-[2-(4-phenoxy-acetic acid)-1,1-dimethyl-ethylamino]-ethyl}-4H-benzo[1,4]oxazin-3-one 8-{2-[1,1-dimethyl-2-(2.4.6-trimethylphenyl)-ethylamino]-1-hydroxy-ethyl}-6-hydroxy-4H-benzo[1,4]oxazin-3-one 6-hydroxy-8-{1-hydroxy-2-[2-(4-hydroxy-phenyl)-1,1-dimethyl-ethylamino]-ethyl}-4H-benzo[1,4]oxazin-3-one 6-hydroxy-8-{1-hydroxy-2-[2-(4-isopropyl-phenyl)-1.1-dimethyl-ethylamino]-ethyl}-4H-benzo[1,4]oxazin-3-one 8-{2-[2-(4-ethyl-phenyl)-1,1-dimethyl-ethylamino]-1-hydroxy-ethyl}-6-hydroxy-4H-benzo[1,4]oxazin-3-one 8-{2-[2-(4-ethoxy-phenyl)-1,1-dimethyl-ethylamino]-1-hydroxy-ethyl}-6-hydroxy-4H-benzo[1,4]oxazin-3-one 4-(4-{2-[2-hydroxy-2-(6-hydroxy-3-oxo-3.4-dihydro-2H-benzo[1,4]oxazin-8-yl)-ethylamino]-2-methyl-propyl}-phenoxy)-butyric acid 8-{2-[2-(3.4-difluoro-phenyl)-1,1-dimethyl-ethylamino]-1-hydroxy-ethyl}-6-hydroxy-4H-benzo[1,4]oxazin-3-one 1-(4-ethoxy-carbonylamino-3-cyano-5-fluorophenyl)-2-(tert-butylamino)ethanol 2-hydroxy-5-(1-hydroxy-2-{2-[4-(2-hydroxy-2-phenyl-ethylamino)-phenyl]-ethylamino}-ethyl)-benzaldehyde N-[2-hydroxy-5-(1-hydroxy-2-{2-[4-(2-hydroxy-2-phenyl-ethylamino)-phenyl]-ethylamino}-ethyl)-phenyl]-formamide 8-hydroxy-5-(1-hydroxy-2-{2-[4-(6-methoxy-biphenyl-3-ylamino)-phenyl]-ethylamino}-ethyl)-1H-quinolin-2-one 8-hydroxy-5-[1-hydroxy-2-(6-phenethylamino-hexylamino)-ethyl]-1H-quinolin-2-one 5-[2-(2-{4-[4-(2-amino-2-methyl-propoxy)-phenylamino]-phenyl}-ethylamino)-1-hydroxy-ethyl]-8-hydroxy-1H-quinolin-2-one [3-(4-{6-[2-hydroxy-2-(4-hydroxy-3-hydroxymethyl-phenyl)-ethylamino]-hexyloxy}-butyl)-5-methyl-phenyl]-urea 4-(2-{6-[2-(2.6-dichloro-benzyloxy)-ethoxy]-hexylamino}-1-hydroxy-ethyl)-2-hydroxymethyl-phenol 3-(4-{6-[2-hydroxy-2-(4-hydroxy-3-hydroxymethyl-phenyl)-ethylamino]-hexyloxy}-butyl)-benzylsulphonamide 3-(3-{7-[2-hydroxy-2-(4-hydroxy-3-hydroxymethyl-phenyl)-ethylamino]-heptyloxy}-propyl)-benzylsulphonamide 4-(2-{6-[4-(3-cyclopentanesulphonyl-phenyl)-butoxy]-hexylamino}-1-hydroxy-ethyl)-2-hydroxymethyl-phenol N-Adamantan-2-yl-2-(3-{2-[2-hydroxy-2-(4-hydroxy-3-hydroxymethyl-phenyl)-ethylamino]-propyl}-phenyl)-acetamide optionally in the form of the racemates, enantiomers, diastereomers thereof and optionally in the form of the pharmacologically acceptable acid addition salts, solvates or hydrates thereof. According to the invention the acid addition salts of the betamimetics are preferably selected from among the hydrochloride, hydrobromide, hydriodide, hydrosulphate, hydrophosphate, hydromethanesulphonate, hydronitrate, hydromaleate, hydroacetate, hydrocitrate, hydrofumarate, hydrotartrate, hydroxalate, hydrosuccinate, hydrobenzoate and hydro-p-toluenesulphonate. The anticholinergics used are preferably compounds selected from among the tiotropium salts, preferably the bromide salt, oxitropium salts, preferably the bromide salt, flutropium salts, preferably the bromide salt, ipratropium salts, preferably the bromide salt, glycopyrronium salts, preferably the bromide salt, trospium salts, preferably the chloride salt, tolterodine. In the above-mentioned salts the cations are the pharmacologically active constituents. As anions the above-mentioned salts may preferably contain the chloride, bromide, iodide, sulphate, phosphate, methanesulphonate, nitrate, maleate, acetate, citrate, fumarate, tartrate, oxalate, succinate, benzoate or p-toluenesulphonate, while chloride, bromide, iodide, sulphate, methanesulphonate or p-toluenesulphonate are preferred as counter-ions. Of all the salts the chlorides, bromides, iodides and methanesulphonates are particularly preferred. Other preferred anticholinergics are selected from among the salts of formula AC-1 wherein X − denotes an anion with a single negative charge, preferably an anion selected from among the fluoride, chloride, bromide, iodide, sulphate, phosphate, methanesulphonate, nitrate, maleate, acetate, citrate, fumarate, tartrate, oxalate, succinate, benzoate and p-toluenesulphonate, preferably an anion with a single negative charge, particularly preferably an anion selected from among the fluoride, chloride, bromide, methanesulphonate and p-toluenesulphonate, particularly preferably bromide, optionally in the form of the racemates, enantiomers or hydrates thereof. Of particular importance are those pharmaceutical combinations which contain the enantiomers of formula AC-1-en wherein X − may have the above-mentioned meanings. Other preferred anticholinergics are selected from the salts of formula AC-2 wherein R denotes either methyl or ethyl and wherein X − may have the above-mentioned meanings. In an alternative embodiment the compound of formula AC-2 may also be present in the form of the free base AC-2-base. Other specified compounds are: tropenol 2,2-diphenylpropionate methobromide, scopine 2,2-diphenylpropionate methobromide, scopine 2-fluoro-2,2-diphenylacetate methobromide, tropenol 2-fluoro-2,2-diphenylacetate methobromide; tropenol 3,3′,4,4′-tetrafluorobenzilate methobromide, scopine 3,3′,4,4′-tetrafluorobenzilate methobromide, tropenol 4,4′-difluorobenzilate methobromide, scopine 4,4′-difluorobenzilate methobromide, tropenol 3,3′-difluorobenzilate methobromide, scopine 3,3′-difluorobenzilate methobromide; tropenol 9-hydroxy-fluorene-9-carboxylate methobromide; tropenol 9-fluoro-fluorene-9-carboxylate methobromide; scopine 9-hydroxy-fluorene-9-carboxylate methobromide; scopine 9-fluoro-fluorene-9-carboxylate methobromide; tropenol 9-methyl-fluorene-9-carboxylate methobromide; scopine 9-methyl-fluorene-9-carboxylate methobromide; cyclopropyltropine benzilate methobromide; cyclopropyltropine 2,2-diphenylpropionate methobromide; cyclopropyltropine 9-hydroxy-xanthene-9-carboxylate methobromide; cyclopropyltropine 9-methyl-fluorene-9-carboxylate methobromide; cyclopropyltropine 9-methyl-xanthene-9-carboxylate methobromide; cyclopropyltropine 9-hydroxy-fluorene-9-carboxylate methobromide; cyclopropyltropine methyl 4,4′-difluorobenzilate methobromide. tropenol 9-hydroxy-xanthene-9-carboxylate methobromide; scopine 9-hydroxy-xanthene-9-carboxylate methobromide; tropenol 9-methyl-xanthene-9-carboxylate-methobromide; scopine 9-methyl-xanthene-9-carboxylate-methobromide; tropenol 9-ethyl-xanthene-9-carboxylate methobromide; tropenol 9-difluoromethyl-xanthene-9-carboxylate methobromide; scopine 9-hydroxymethyl-xanthene-9-carboxylate methobromide, The above-mentioned compounds may also be used as salts within the scope of the present invention, wherein instead of the methobromide the salts metho-X are used, wherein X may have the meanings given hereinbefore for X − . As corticosteroids it is preferable to use compounds selected from among beclomethasone, betamethasone, budesonide, butixocort, ciclesonide, deflazacort, dexamethasone, etiprednol, flunisolide, fluticasone, loteprednol, mometasone, prednisolone, prednisone, rofleponide, triamcinolone, RPR-106541, NS-126, ST-26 and (S)-fluoromethyl 6,9-difluoro-17-[(2-furanylcarbonyl)oxy]-11-hydroxy-16-methyl-3-oxo-androsta-1,4-diene-17-carbothionate (S)-(2-oxo-tetrahydro-furan-3S-yl) 6,9-difluoro-11-hydroxy-16-methyl-3-oxo-17-propionyloxy-androsta-1,4-diene-17-carbothionate, cyanomethyl 6{acute over (α)},9{acute over (α)}-difluoro-11β-hydroxy-16{acute over (α)}-methyl-3-oxo-17 {acute over (α)}-(2,2,3,3-tetramethylcyclopropylcarbonyl)oxy-androsta-1,4-diene-17β-carboxylate optionally in the form of the racemates, enantiomers or diastereomers thereof and optionally in the form of the salts and derivatives thereof, the solvates and/or hydrates thereof. Any reference to steroids includes a reference to any salts or derivatives, hydrates or solvates thereof which may exist. Examples of possible salts and derivatives of the steroids may be: alkali metal salts, such as for example sodium or potassium salts, sulphobenzoates, phosphates, isonicotinates, acetates, dichloroacetates, propionates, dihydrogen phosphates, palmitates, pivalates or furoates. PDE4-inhibitors which may be used are preferably compounds selected from among enprofyllin, theophyllin, roflumilast, ariflo (cilomilast), tofimilast, pumafentrin, lirimilast, arofyllin, atizoram, D-4418, Bay-198004, BY343, CP-325.366, D-4396 (Sch-351591), AWD-12-281 (GW-842470), NCS-613, CDP-840, D-4418, PD-168787, T-440, T-2585, V-11294A, C1-1018, CDC-801, CDC-3052, D-22888, YM-58997, Z-15370 and N-(3,5-dichloro-1-oxo-pyridin-4-yl)-4-difluoromethoxy-3-cyclopropylmethoxybenzamide (−)p-[(4aR*,10bS*)-9-ethoxy-1,2,3,4,4a,10b-hexahydro-8-methoxy-2-methylbenzo[s][1,6]naphthyridin-6-yl]-N,N-diisopropylbenzamide (R)-(+)-1-(4-bromobenzyl)-4-[(3-cyclopentyloxy)-4-methoxyphenyl]-2-pyrrolidone 3-(cyclopentyloxy-4-methoxyphenyl)-1-(4-N′-[N-2-cyano-S-methyl-isothioureido]benzyl)-2-pyrrolidone cis[4-cyano-4-(3-cyclopentyloxy-4-methoxyphenyl)cyclohexane-1-carboxylic acid] 2-carbomethoxy-4-cyano-4-(3-cyclopropylmethoxy-4-difluoromethoxy-phenyl)cyclohexan-1-one cis[4-cyano-4-(3-cyclopropylmethoxy-4-difluoromethoxyphenyl)cyclohexan-1-ol] (R)-(+)-ethyl[4-(3-cyclopentyloxy-4-methoxyphenyl)pyrrolidin-2-ylidene]acetate (S)-(−)-ethyl[4-(3-cyclopentyloxy-4-methoxyphenyl)pyrrolidin-2-ylidene]acetate 9-cyclopentyl-5,6-dihydro-7-ethyl-3-(2-thienyl)-9H-pyrazolo[3.4-c]-1,2,4-triazolo[4.3-a]pyridine 9-cyclopentyl-5,6-dihydro-7-ethyl-3-(tert-butyl)-9H-pyrazolo[3.4-c]-1,2,4-triazolo[4.3-a]pyridine optionally in the form of the racemates, enantiomers or diastereomers thereof and optionally in the form of the pharmacologically acceptable acid addition salts thereof, the solvates and/or hydrates thereof. According to the invention the acid addition salts of the PDE4 inhibitors are preferably selected from among the hydrochloride, hydrobromide, hydriodide, hydrosulphate, hydrophosphate, hydromethanesulphonate, hydronitrate, hydromaleate, hydroacetate, hydrocitrate, hydrofumarate, hydrotartrate, hydroxalate, hydrosuccinate, hydrobenzoate and hydro-p-toluenesulphonate. The LTD4-antagonists used are preferably compounds selected from among montelukast, pranlukast, zafirlukast, MCC-847 (ZD-3523), MN-001, MEN-91507 (LM-1507), VUF-5078, VUF-K-8707, L-733321 and 1-(((R)-(3-(2-(6,7-difluoro-2-quinolinyl)ethenyl)phenyl)-3-(2-(2-hydroxy-2-propyl)phenyl)thio)methylcyclopropane-acetic acid, 1-(((1(R)-3(3-(2-(2,3-dichlorothieno[3,2-b]pyridin-5-yl)-(E)-ethenyl)phenyl)-3-(2-(1-hydroxy-1-methylethyl)phenyl)propyl)thio)methyl)cyclopropaneacetic acid [2-[[2-(4-tert-butyl-2-thiazolyl)-5-benzofuranyl]oxymethyl]phenyl]acetic acid optionally in the form of the racemates, enantiomers or diastereomers thereof and optionally in the form of the pharmacologically acceptable acid addition salts, solvates and/or hydrates thereof. According to the invention these acid addition salts are preferably selected from among the hydrochloride, hydrobromide, hydroiodide, hydrosulphate, hydrophosphate, hydromethanesulphonate, hydronitrate, hydromaleate, hydroacetate, hydrocitrate, hydrofumarate, hydrotartrate, hydroxalate, hydrosuccinate, hydrobenzoate and hydro-p-toluenesulphonate. By salts or derivatives which the LTD4-antagonists may optionally be capable of forming are meant, for example: alkali metal salts, such as for example sodium or potassium salts, alkaline earth metal salts, sulphobenzoates, phosphates, isonicotinates, acetates, propionates, dihydrogen phosphates, palmitates, pivalates or furoates. EGFR-inhibitors which may be used are preferably compounds selected from among cetuximab, trastuzumab, ABX-EGF, Mab ICR-62 and 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(morpholin-4-yl)-1-oxo-2-buten-1-yl]-amino-}-7-cyclopropylmethoxy-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N,N-diethylamino)-1-oxo-2-buten-1-yl]-amino-}-7-cyclopropylmethoxy-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N,N-dimethylamino)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxy-quinazoline 4-[(R)-(1-phenyl-ethyl)amino]-6-{[4-(morpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopentyloxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{[4((R)-6-methyl-2-oxo-morpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{[4((R)-6-methyl-2-oxo-morpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-[(S)-(tetrahydrofuran-3-yl)oxy]-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{[4((R)-2-methoxymethyl-6-oxo-morpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[2((S)-6-methyl-2-oxo-morpholin-4-yl)-ethoxy]-7-methoxy-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-({4-[N-(2-methoxy-ethyl)-N-methyl-amino]-1-oxo-2-buten-1-yl}amino)-7-cyclopropylmethoxy-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N,N-dimethylamino)-1-oxo-2-buten-1-yl]amino}-7-cyclopentyloxy-quinazoline 4-[(R)-(1-phenyl-ethyl)amino]-6-{[4-(N,N-bis-(2-methoxy-ethyl)-amino)-1-oxo-2-buten-1-yl]amino}-7-cyclopropylmethoxy-quinazoline 4-[(R)-(1-phenyl-ethyl)amino]-6-({4-[N-(2-methoxy-ethyl)-N-ethyl-amino]-1-oxo-2-buten-1-yl}amino)-7-cyclopropylmethoxy-quinazoline 4-[(R)-(1-phenyl-ethyl)amino]-6-({4-[N-(2-methoxy-ethyl)-N-methyl-amino]-1-oxo-2-buten-1-yl}amino)-7-cyclopropylmethoxy-quinazoline 4-[(R)-(1-phenyl-ethyl)amino]-6-({4-[N-(tetrahydropyran-4-yl)-N-methyl-amino]-1-oxo-2-buten-1-yl}amino)-7-cyclopropylmethoxy-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N,N-dimethylamino)-1-oxo-2-buten-1-yl]amino}-7-((R)-tetrahydrofuran-3-yloxy)-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N,N-dimethylamino)-1-oxo-2-buten-1-yl]amino}-7-((S)-tetrahydrofuran-3-yloxy)-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-({4-[N-(2-methoxy-ethyl)-N-methyl-amino]-1-oxo-2-buten-1-yl}amino)-7-cyclopentyloxy-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N-cyclopropyl-N-methyl-amino)-1-oxo-2-buten-1-yl]amino}-7-cyclopentyloxy-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N,N-dimethylamino)-1-oxo-2-buten-1-yl]amino}-7-[(R)-(tetrahydrofuran-2-yl)methoxy]-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N,N-dimethylamino)-1-oxo-2-buten-1-yl]amino}-7-[(S)-(tetrahydrofuran-2-yl)methoxy]-quinazoline 4-[(3-ethynyl-phenyl)amino]-6.7-bis-(2-methoxy-ethoxy)-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-7-[3-(morpholin-4-yl)-propyloxy]-6-[(vinyl-carbonyl)amino]-quinazoline 4-[(R)-(1-phenyl-ethyl)amino]-6-(4-hydroxy-phenyl)-7H-pyrrolo[2,3-d]pyrimidine 3-cyano-4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(N,N-dimethylamino)-1-oxo-2-buten-1-yl]amino}-7-ethoxy-quinoline 4-{[3-chloro-4-(3-fluoro-benzyloxy)-phenyl]amino}-6-(5-{[(2-methanesulphonyl-ethyl)amino]methyl}-furan-2-yl)quinazoline 4-[(R)-(1-phenyl-ethyl)amino]-6-{[4((R)-6-methyl-2-oxo-morpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-7-methoxy-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-{[4-(morpholin-4-yl)-1-oxo-2-buten-1-yl]-amino}-7-[(tetrahydrofuran-2-yl)methoxy]-quinazoline 4-[(3-chloro-4-fluorophenyl)amino]-6-({4-[N,N-bis-(2-methoxy-ethyl)-amino]-1-oxo-2-buten-1-yl}amino)-7-[(tetrahydrofuran-2-yl)methoxy]-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-{[4-(5.5-dimethyl-2-oxo-morpholin-4-yl)-1-oxo-2-buten-1-yl]amino}-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[2-(2.2-dimethyl-6-oxo-morpholin-4-yl)-ethoxy]-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[2-(2.2-dimethyl-6-oxo-morpholin-4-yl)-ethoxy]-7-[(R)-(tetrahydrofuran-2-yl)methoxy]-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-7-[2-(2.2-dimethyl-6-oxo-morpholin-4-yl)-ethoxy]-6-[(S)-(tetrahydrofuran-2-yl)methoxy]-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{2-[4-(2-oxo-morpholin-4-yl)-piperidin-1-yl]-ethoxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[1-(tert.-butyloxycarbonyl)-piperidin-4-yloxy]-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(trans-4-amino-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(trans-4-methanesulphonylamino-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(tetrahydropyran-3-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-methyl-piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(morpholin-4-yl)carbonyl]-piperidin-4-yl-oxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(methoxymethyl)carbonyl]-piperidin-4-yl-oxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(piperidin-3-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[1-(2-acetylamino-ethyl)-piperidin-4-yloxy]-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(tetrahydropyran-4-yloxy)-7-ethoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-((S)-tetrahydrofuran-3-yloxy)-7-hydroxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(tetrahydropyran-4-yloxy)-7-(2-methoxy-ethoxy)-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{trans-4-[(dimethylamino)sulphonylamino]-cyclohexan-1-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{trans-4-[(morpholin-4-yl)carbonylamino]-cyclohexan-1-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{trans-4-[(morpholin-4-yl)sulphonylamino]-cyclohexan-1-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(tetrahydropyran-4-yloxy)-7-(2-acetylamino-ethoxy)-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(tetrahydropyran-4-yloxy)-7-(2-methanesulphonylamino-ethoxy)-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(piperidin-1-yl)carbonyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-aminocarbonylmethyl-piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(cis-4-{N-[(tetrahydropyran-4-yl)carbonyl]-N-methyl-amino}-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(cis-4-{N-[(morpholin-4-yl)carbonyl]-N-methyl-amino}-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(cis-4-{N-[(morpholin-4-yl)sulphonyl]-N-methyl-amino}-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(trans-4-ethansulphonylamino-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-methanesulphonyl-piperidin-4-yloxy)-7-ethoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-methanesulphonyl-piperidin-4-yloxy)-7-(2-methoxy-ethoxy)-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[1-(2-methoxy-acetyl)-piperidin-4-yloxy]-7-(2-methoxy-ethoxy)-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(cis-4-acetylamino-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-[1-(tert.-butyloxycarbonyl)-piperidin-4-yloxy]-7-methoxy-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-(tetrahydropyran-4-yloxy]-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(cis-4-{N-[(piperidin-1-yl)carbonyl]-N-methyl-amino}-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(cis-4-{N-[(4-methyl-piperazin-1-yl)carbonyl]-N-methyl-amino}-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{cis-4-[(morpholin-4-yl)carbonylamino]-cyclohexan-1-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[2-(2-oxopyrrolidin-1-yl)ethyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(morpholin-4-yl)carbonyl]-piperidin-4-yloxy}-7-(2-methoxy-ethoxy)-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-(1-acetyl-piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-(1-methyl-piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-(1-methanesulphonyl-piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-methyl-piperidin-4-yloxy)-7(2-methoxy-ethoxy)-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-isopropyloxycarbonyl-piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(cis-4-methylamino-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{cis-4-[N-(2-methoxy-acetyl)-N-methyl-amino]-cyclohexan-1-yloxy}-7-methoxy-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-(piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-[1-(2-methoxy-acetyl)-piperidin-4-yloxy]-7-methoxy-quinazoline 4-[(3-ethynyl-phenyl)amino]-6-{1-[(morpholin-4-yl)carbonyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(cis-2,6-dimethyl-morpholin-4-yl)carbonyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(2-methyl-morpholin-4-yl)carbonyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(S,S)-(2-oxa-5-aza-bicyclo[2,2,1]hept-5-yl)carbonyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(N-methyl-N-2-methoxyethyl-amino)carbonyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-ethyl-piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(2-methoxyethyl)carbonyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-{1-[(3-methoxypropyl-amino)-carbonyl]-piperidin-4-yloxy}-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[cis-4-(N-methanesulphonyl-N-methyl-amino)-cyclohexan-1-yloxy]-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[cis-4-(N-acetyl-N-methyl-amino)-cyclohexan-1-yloxy]-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(trans-4-methylamino-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[trans-4-(N-methanesulphonyl-N-methyl-amino)-cyclohexan-1-yloxy]-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(trans-4-dimethylamino-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(trans-4-{N-[(morpholin-4-yl)carbonyl]-N-methyl-amino}-cyclohexan-1-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-[2-(2.2-dimethyl-6-oxo-morpholin-4-yl)-ethoxy]-7-[(S)-(tetrahydrofuran-2-yl)methoxy]-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-methanesulphonyl-piperidin-4-yloxy)-7-methoxy-quinazoline 4-[(3-chloro-4-fluoro-phenyl)amino]-6-(1-cyano-piperidin-4-yloxy)-7-methoxy-quinazoline optionally in the form of the racemates, enantiomers, diastereomers thereof and optionally in the form of the pharmacologically acceptable acid addition salts, solvates or hydrates thereof. According to the invention these acid addition salts are preferably selected from among the hydrochloride, hydrobromide, hydriodide, hydrosulphate, hydrophosphate, hydromethanesulphonate, hydronitrate, hydromaleate, hydroacetate, hydrocitrate, hydrofumarate, hydrotartrate, hydroxalate, hydrosuccinate, hydrobenzoate and hydro-p-toluenesulphonate. The dopamine agonists used are preferably compounds selected from among bromocriptin, cabergoline, alpha-dihydroergocryptine, lisuride, pergolide, pramipexol, roxindol, ropinirol, talipexol, tergurid and viozan, optionally in the form of the racemates, enantiomers, diastereomers thereof and optionally in the form of the pharmacologically acceptable acid addition salts, solvates or hydrates thereof. According to the invention these acid addition salts are preferably selected from among the hydrochloride, hydrobromide, hydriodide, hydrosulphate, hydrophosphate, hydromethanesulphonate, hydronitrate, hydromaleate, hydroacetate, hydrocitrate, hydrofumarate, hydrotartrate, hydrooxalate, hydrosuccinate, hydrobenzoate and hydro-p-toluenesulphonate. H1-Antihistamines which may be used are preferably compounds selected from among epinastine, cetirizine, azelastine, fexofenadine, levocabastine, loratadine, mizolastine, ketotifen, emedastine, dimetindene, clemastine, bamipine, cexchlorpheniramine, pheniramine, doxylamine, chlorophenoxamine, dimenhydrinate, diphenhydramine, promethazine, ebastine, desloratidine and meclozine, optionally in the form of the racemates, enantiomers, diastereomers thereof and optionally in the form of the pharmacologically acceptable acid addition salts, solvates or hydrates thereof. According to the invention these acid addition salts are preferably selected from among the hydrochloride, hydrobromide, hydriodide, hydrosulphate, hydrophosphate, hydromethanesulphonate, hydronitrate, hydromaleate, hydroacetate, hydrocitrate, hydrofumarate, hydrotartrate, hydroxalate, hydrosuccinate, hydrobenzoate and hydro-p-toluenesulphonate. The pharmaceutically active substances, substance formulations or substance mixtures used may be any inhalable compounds, including, for example, inhalable macromolecules, as disclosed in EP 1 003 478. Preferably, substances, substance formulations or substance mixtures that are used by inhalation may be used to treat respiratory complaints. In addition, the compounds may come from the groups of ergot alkaloid derivatives, the triptans, the CGRP-inhibitors, the phosphodiesterase-V inhibitors, optionally in the form of the racemates, enantiomers or diastereomers thereof, optionally in the form of the pharmacologically acceptable acid addition salts, the solvates and/or hydrates thereof. Examples of ergot alkaloid derivatives are dihydroergotamine and ergotamine. LIST OF REFERENCE NUMERALS 1 cover 2 mouthpiece 3 plate 4 spindle 5 capsule holder 6 lower part 7 outer actuating member 8 pin 9 helical spring 10 inner actuating member 11 pin 12 screen housing 13 screening mesh 14 closure element 15 guide arms(s) 16 recess
An inhaler for inhaling powdered medicaments from capsules, having: a lower part which is cup-shaped, a plate latched to the lower part to close off the lower part, a capsule holder arranged on the underside of the plate, a mouthpiece that can be latched to the top of plate, and an actuating member for interacting with at least one pin for piercing a capsule in the capsule holder, where the actuating member includes a larger outer actuating member and a smaller inner actuating member, the outer actuating member forms a user-operated push-button, the inner actuating member contacts and holds the pin below a suspension element of the outer actuating member from the plate, and the point of application of force by the user onto push-button is lower than the inner actuating member.
0
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] This invention relates to human body composition and, more particularly, to a system for measuring a user's body fat percentage taking into consideration hydration levels. [0003] 2. Background Art [0004] Individuals and businesses worldwide are becoming increasingly interested in maintaining human health. From a business perspective, healthy employees are generally more productive and reliable. Preventable illnesses that result in employee down time are placing a greater strain on productivity requirements and the healthcare obligations of businesses for their employees. This problem is in addition to that of “covering” for employees during short or extended absences. [0005] From an individual standpoint, good health contributes not only to longevity, but a more productive and enjoyable life. [0006] With the increasing emphasis on health maintenance, technology has been evolving that allows individuals to more effectively monitor critical health parameters, among which is body fat percentage, a key indicator of overall health level. A multitude of instruments have been devised based upon bioimpedance technology, which relies upon the ability to measure resistance to a low level electrical signal introduced into the body at one location and received at another. [0007] The assignee herein has developed a line of technology including bioimpedance instrumentation wherein an electrical signal is introduced through the user's one hand and received through the user's other hand. Exemplary technology is shown in applicant's pending application Ser. No. 10/882,139 entitled “Method and System for Evaluating A Cost For Health Care Coverage For An Entity”, the disclosure of which is incorporated herein by reference. [0008] Generally, resistance is measured in ohms, with the applicant's commercial products having an ohms bridge allowing from 100-1100 ohms. The higher the ohms, the higher is the resistance. An ohms reading is then incorporated into an individual profile including age, weight, gender, height, and athletic activity. A person may be categorized and measurements derived therefor based upon whether the person is, for example, sedentary, inactive, active, athletic, a professional athlete, a bodybuilder, etc. [0009] The low level electrical signals in this type of instrumentation pass through the body through any conductive material. In the human body, the most conductive route is water, that is contained within lean muscle, bone marrow, blood, main organs such as the bladder, etc. Water is not contained within fat. [0010] Resistance measurement in the human body will also be affected by the level of hydration. If a user is underhydrated, the ohms reading/resistance will be higher. When this resistance value is processed through a bioimpedance device, the calculated body fat percentage will be artificially elevated, potentially as much as five percent or higher. [0011] As this technology evolves, it is becoming more and more important that, for any meaningful reliance on calculated body fat percentage values, the accuracy be maintained so that there is a limited percentage error. The failure to take into account underhydration or dehydration may result in body fat percentage measurements that are significantly inaccurate and that may vary from one measurement to the next based upon fluctuation in hydration for the user. [0012] The industry continues to seek out instrumentation that is affordable yet accurate to the point that health attributes can be accurately quantified and monitored to assist lifestyle selections that will improve and/or maintain users' overall health. SUMMARY OF THE INVENTION [0013] In one form, the invention is directed to a system for measuring percentage of body fat for a user. The system includes: structure for measuring body hydration and generating a signal representing a measured hydration value; structure for selectively changing the measured hydration value to an adjusted hydration value based upon a first parameter to thereby reflect more accurately an actual hydration value for the user and generating a signal representing the adjusted hydration value; and structure for measuring body fat percentage using the signal representing: a) the measured hydration value; or b) the adjusted hydration value in the event that the structure for selectively changing the measured hydration value changes the measured hydration value based upon the first parameter. [0014] In one form, the structure for selectively changing the measured hydration value includes structure for automatically changing the measured hydration value to an adjusted hydration value based upon the first parameter. [0015] In one form, the first parameter is a preset minimum hydration value and the structure for selectively changing the measured hydration value includes structure for changing the measured hydration value to the preset minimum hydration value in the event that the measured hydration value is below the preset minimum hydration value. [0016] In one form, the structure for measuring body hydration includes structure for notifying the user that the user is not properly hydrated in the event that the measured hydration value is below the preset minimum hydration value. [0017] In one form, the preset minimum hydration value is based upon a conventional adequate hydration value derived from a general population analysis. [0018] In one form, the preset minimum hydration value is a baseline hydration value derived from a plurality of prior hydration measurements used by the structure for measuring body fat percentage for the user. [0019] In one form, the baseline hydration value is derived by using at least two prior hydration values for the user used by the structure for measuring body fat percentage. [0020] In one form, the two prior hydration values are successive hydration values used by the structure for measuring body fat percentage. [0021] In one form, the baseline hydration value is derived by averaging a plurality of prior hydration values used by the structure for measuring body fat percentage. [0022] In one form, the baseline hydration value is derived by averaging at least two and less than all prior hydration values from a collection of prior hydration values used by the structure for measuring body fat percentage in the collection of prior hydration values. [0023] In one form, the system further includes a display for identifying user body fat percentage as measured by the structure for measuring body fat in a human readable form. [0024] In one form, the structure for measuring body fat percentage generates a signal in non-human readable form representing measured body fat percentage and the system further includes a conversion structure for changing the signal representing body fat percentage from non-human readable form into a human readable form. [0025] In one form, the structure for measuring hydration, structure for measuring body fat, and display are at a first location and the conversion structure is at a second, remote location. [0026] In one form, the structure for measuring hydration, structure for measuring body fat, and display are all at the same location. [0027] In one form, the signal representing measured body fat percentage is conveyed to the conversion structure over one of a local area network or the internet. [0028] In one form, the structure for measuring hydration, structure for measuring body fat, and display are combined into an instrument at the first location. [0029] In one form, the first parameter is a preset minimum hydration value and the structure for measuring body hydration includes structure for notifying a user that the user is not properly hydrated as indicated by the fact that a measured hydration value is below the preset minimum hydration value and thereafter sending a signal to the structure for measuring body fat percentage only after the structure for measuring body hydration has generated a signal representing a second measured hydration value and after the user has been notified that the user is not properly hydrated. [0030] In one form, the structure for selectively changing the measured hydration value includes structure for generating a signal representing the measured hydration value used by the structure for measuring body fat percentage in the event that the measured hydration value exceeds the baseline hydration value. [0031] In one form, the structure for measuring body fat percentage includes structure for measuring body fat percentage based upon a measured electrical resistance. [0032] In one form, the preset minimum hydration value is on the order of 75%. BRIEF DESCRIPTION OF THE DRAWINGS [0033] FIG. 1 is a schematic representation of a conventional system for measuring percentage of body fat for a user; [0034] FIG. 2 is a schematic representation of the inventive system for measuring percentage of body fat for a user; [0035] FIG. 3 is a flow diagram representation of a process for measuring body fat percentage for a user with the system in FIG. 2 based upon a first hydration value; [0036] FIG. 4 is a flow diagram representation as in FIG. 3 based upon a second hydration measurement value; [0037] FIG. 5 is a flow diagram representation as in FIG. 3 based upon a third hydration measurement value; [0038] FIG. 6 is a flow diagram representation as in FIG. 3 based upon a fourth hydration measurement value; [0039] FIG. 7 is a schematic representation of a means on the system in FIG. 2 for measuring hydration and including a means for generating instructions to a user to hydrate under appropriate conditions; [0040] FIG. 8 is a schematic representation of a means for measuring body fat on the system in FIG. 2 that produces a signal representative of the calculated body fat percentage that is communicated to a conversion means to allow display of a fat percentage value; and [0041] FIG. 9 is a schematic representation of the inventive system as operated on a local area network or over the internet. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0042] In FIG. 1 , a conventional system for measuring percentage of body fat for a user is shown at 10 . The system 10 consists of a means for measuring hydration at 12 , using well-known technology. The means 12 generates a signal 14 that is processed by a means for measuring body fat 16 , that in turn produces a signal 18 representing the user's body fat percentage. That signal 18 is directed to a point of use 20 , that might be a display or another device configured to further process or store signals. [0043] In FIG. 2 , a system for measuring percentage of body fat for a user, according to the invention, is shown schematically at 22 . The system 22 consists of a means for measuring hydration at 24 , which incorporates a means for selectively changing measured hydration values at 26 . As explained in greater detail below, the means 26 may be operable automatically to change a measured hydration value to an adjusted hydration value based upon a particular parameter, as also described below. [0044] The means 24 generates a signal 28 that is representative of either the measured or adjusted hydration value. The signal 28 is directed to a means for measuring body fat 30 . The means 30 processes the signal 28 , and other input data for the user, and generates a signal 32 representing a percentage body fat measurement for the user. The signal 32 is directed to a point of use 34 , that might be a display at the user site or a display at a remote location. Alternatively, the point of use 34 might be a device wherein the signal 32 is further processed, converted, stored, or otherwise manipulated. [0045] The system 22 and its components are shown schematically since the precise configuration of each is not critical to the present invention. As noted above, exemplary usable technology is disclosed in applicant's pending application Ser. No. 10/882,139, entitled “Method and System for Evaluating A Cost for Health Care Coverage for an Entity”, which is incorporated herein by reference. The schematic showing of these components is intended to encompass virtually every conceivable variation of the basic technology that is required to perform as herein described. Those skilled in the art could devise myriad variations of these components with different capabilities, yet all with the ability to perform the basic functions contemplated by the invention. [0046] The function and significance of the means 26 will now be described. Medical studies and researchers have shown that the average percentage of water within lean body mass is 75%. Hydration ranges can generally be classified as follows: Optimum—80%-85%; Good—75%-80%; Adequate—70%-75%; Marginal—65%-70%; Inadequate—60%-65%; and Poor—below 60%. [0053] When the hydration of lean mass is below 75%, false high readings of body fat may become significant. [0054] As shown in flow diagram form in FIG. 3 , using the system 22 , a first hydration measurement is taken using the means 24 , as shown at block 36 . As shown at block 38 , the means 24 , through the means 26 , determines whether the first measured hydration value meets an established parameter. While the parameter may vary, one exemplary parameter is a pre-set minimum hydration value, which for purposes of example will be 75% or another value based upon recognized adequate hydration values derived from a general population analysis. If it is determined that a first measured hydration value is at or above 75%, that value will be used by the means 30 to calculate the user's body fat percentage, as shown at block 40 . [0055] If the first measured hydration value is below 75%, the user's body fat measurement will be calculated through the means 30 using an adjusted hydration value of 75%, as shown at block 42 . Additionally, the system 22 is configured to notify the user of inadequate hydration as evidenced by the first measured hydration value, as shown at block 44 . This notification may be generated by the means 24 , or otherwise. [0056] As shown in FIG. 4 , a subsequent second hydration measurement is taken using the apparatus 22 , as shown at block 46 . The system 22 compares the second measured hydration value to the same or a different parameter, as indicated at block 48 . With the 75% hydration rate used, if the second measured hydration value is at or greater than 75%, that value is used to calculate body fat through the means 30 , as indicated at block 50 . At the same time, the apparatus 22 is configured to establish a first baseline hydration value that averages the first two hydration values that are processed by the means 30 in calculating body fat, as shown at block 52 . [0057] If the second measured hydration value is not at 75% or greater, the system 22 notifies the user of inadequate hydration, as shown at block 54 . As shown at block 56 , the second hydration measurement is repeated after hydration. As shown at block 58 if, after hydration, the second hydration measurement does not reach or exceed 75%, the user is so notified, as indicated at block 54 and the cycle repeats until a hydration level of 75% or greater is measured. At that point, the second hydration measurement value can be processed by the means 30 , as shown at block 50 . [0058] FIG. 4 depicts two different options for apparatus operation. That is, if the second measured hydration value is lower than the established parameter, a user can be forced to hydrate to eventually generate a reading that is a more accurate reflection of body hydration. As a further alternative, as shown at block 60 , the body fat percentage can be calculated using an adjusted hydration value, such as the aforementioned 75% value. [0059] In FIG. 5 , system operation is shown for taking a third hydration measurement using the apparatus 22 , as shown at block 64 . As shown at block 66 , it is determined whether the third measured hydration value meets a parameter, which may be the 75% hydration level or the first baseline hydration value that results from averaging as shown in FIG. 4 . [0060] If the third measured hydration value does not meet the parameter, as shown at block 68 , the user is notified of inadequate hydration. As shown at block 70 , the third hydration measurement step may be repeated after hydration. As shown at block 72 , if, after hydration, the third hydration measurement value does not meet the established parameter, the user may be notified of inadequate hydration as at block 68 and the cycle repeated until the parameter is met. Once the parameter is met, as shown at block 73 , the system may determine whether the parameter using the first baseline hydration value is met. If not, as shown at block 74 , the system may calculate the body fat percentage using the second baseline hydration value. As shown at block 75 , the user is also notified of inadequate hydration. [0061] If the measured hydration value meets the parameter, as shown at block 76 , body fat percentage is calculated using the third measured hydration value. As shown at block 78 , the system also establishes a second baseline value using the average of three hydration values that are actually measured, or more preferably processed by the means 30 in prior measurements. [0062] As a further alternative, in the event that the third measured hydration value does not meet the parameters noted at block 66 , as shown at block 80 , the body fat percentage may be calculated using an adjusted third hydration measurement value, which may be 75%, or another value. At the same time, as noted at block 82 , the user is notified that he/she is inadequately hydrated. [0063] In FIG. 6 , a flow diagram representation of system operation is shown for taking a subsequent fourth hydration measurement. The blocks in FIG. 6 , that correspond to those in FIG. 5 , are numbered using the same numbers with a “′” designation. The primary distinction between what is shown in FIGS. 5 and 6 is that in block 78 ′, a third baseline value is established for use as a further parameter and preferably uses less than all of the collection of four prior measurement values. As an example, the first hydration measurement value may be eliminated from the averaging. While this is preferred, any of the four measured hydration values might be eliminated so that only three of the four values are averaged for the recalculated baseline. [0064] As shown in FIG. 7 , the means for measuring hydration may include a means 88 for generating instructions to hydrate as the apparatus 22 is utilized as described above. The instructions may be generated by other system components. [0065] As shown in FIG. 8 , the means for measuring body fat 30 generates the signal 32 that may be in untranslated form and thus not human readable. A separate conversion means 90 may be provided for converting the signal 32 to a human readable form or another form for subsequent use and/or processing. In the event that the conversion means 90 converts the signal to a human readable form, the translated signal 92 from the conversion means 90 may be made available to a user or another party, as through a display 94 . [0066] It should be understood that the precise configuration of the components and their integration is not limited to any specific structure or manner. The aforementioned components could be separate or united into a single instrument. [0067] As one additional variation, as shown in FIG. 9 , the inventive system, as shown generically at 96 , may have an instrument 98 with a means at 100 for measuring and generating a signal 102 representing a percentage of body fat that is calculated using the aforementioned concept of selectively adjusting measured hydration values. [0068] In this embodiment, the signal 102 is transmitted over a network 104 . The network 104 may be a local area network or the internet. [0069] The signal 102 is conveyed to a conversion means/server 106 where appropriate processing may be performed. As an example, the processing may be a conversion of a non-human readable signal to human readable form. Alternatively, the body fat percentage value may be coordinated with a user profile including age, weight, gender, height and lifestyle quantification, as noted above. This feedback may be provided to the user at the instrument location 98 and/or at another location. At the server 106 , the data may be stored for future use and comparison purposes. The comparison may involve the user's own data and/or data representative of the general population. [0070] The foregoing disclosure of specific embodiments is intended to be illustrative of the broad concepts comprehended by the invention.
A system for measuring percentage of body fat for a user. The system has: structure for measuring body hydration and generating a signal representing a measured hydration value; structure for selectively changing the measured hydration value to an adjusted hydration value based upon a first parameter to thereby reflect more accurately an actual hydration value for the user and generating a signal representing the adjusted hydration value; and structure for measuring body fat percentage using the signal representing: a) the measured hydration value; or b) the adjusted hydration value in the event that the structure for selectively changing the measured hydration value changes the measured hydration value based upon the first parameter.
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CROSS REFERENCE TO RELATED APPLICATIONS This application is a national phase of PCT application No. PCT/EP2012/076326, filed Dec. 20, 2012, which claims priority to IT patent application No. MI2011A002327, filed Dec. 20, 2011, all of which are incorporated herein by reference thereto. FIELD OF THE INVENTION The present invention relates to a cementitious composition for forming mortars or concretes having reduced tendency to react with alkali. PRIOR ART In the concretes and mortars field, the alkali-aggregate reaction (AAR) is an end product degradation phenomenon associated with a chemical reaction between reactive silica contained in certain types of aggregate and the cement matrix. It is generally accepted that the alkali-aggregate reaction can take place when the following series of conditions occur simultaneously: i. Presence of sufficient moisture in the concrete (permanently or temporarily) ii. Presence in the aggregates of a sufficient content of species reactive to alkalis (primarily reactive silica) iii. Presence of a sufficient content of alkali to the cement paste placed in contact with the aggregates. The AAR phenomenon is generally difficult to control since the physicochemical mechanisms that govern the evolution thereof have very slow kinetics. The negative effect on the works can also be seen many years after the execution thereof, through the development of a network of cracks in concrete. The mechanical characteristics of the concrete can consequently be degraded and/or the functionality of the work may be lost. The mechanism of action of the AAR comprises an initial step of increasing the alkalinity of the solution following the dissolution of sodium, potassium and calcium ions from different sources. In a subsequent step, the Si—O bonds in the silica exposed on the surface of the aggregate are hydrated to form a gel containing H 2 SiO 4 2− , H 3 SiO 4 − ions and cations such as K+, Na+, Ca 2+ in varying proportions. This gel coating the surface of the aggregate exposed to attack tends to absorb water molecules and to expand, locally generating tractive forces in the cement matrix, which can fracture where sufficient resistance to traction has not been developed. More in particular, the hydroxyl ions generated from hydration of the alkali act as primer of the chemical reaction, thus the establishment of a high pH can generally be considered a favourable condition for the reaction itself. The occurrence of AAR can lead to undesired phenomena in the works, such as: widespread cracking discolouration around the cracks exudation of gel from the cracks misalignment of adjacent sections joint closures localized explosion phenomena To limit the occurrence of the AAR phenomenon, one can intervene on the basic mechanisms of the phenomenon by attempting to exclude at least one of the conditions (i, ii, iii) above. More in particular, point (i) being strongly dependent on the conditions of product exposure and point (ii) being inherent to the origin of the aggregates, modifying the effects thereof is often difficult or impractical. As concerns point (iii), certain possible strategies for reducing the risk of AAR occurrence are: I. use of components for concrete having a limited alkali content II. use of materials with latent hydraulic or pozzolanic activity mixed with the concrete (pozzolanas, fly ash, dross, microsilica, metakaolin, etc.). III. use of inhibitor additives, which is the case of the present invention. SUMMARY OF THE INVENTION According to the present invention, a cementitious composition is proposed, that is for forming mortars or concretes having reduced tendency to react with alkali, characterized in that it comprises as an additive at least a compound of general formula: [R—N—(CH 2 —COOH) n ] x   (I) R being an aliphatic or aromatic hydrocarbon chain, n=2 or 3 and x=1 or 2. The following are preferred compounds of general formula (I): CH 3 —N—(CH 2 —COOH) 2 (CH 2 ) m —(N—(CH 2 —COOH) 2 ) 2 , con m≧2 C 6 H 5 —N—(CH 2 —COOH) 2 C 6 H 10 —(N—(CH 2 —COOH) 2 ) 2 One overall preferred compound of general formula (I) is ethylene diamine tetraacetic acid, or EDTA, of formula: (CH 2 —COOH) 2 —N—(CH 2 ) 2 —N—(CH 2 —COOH) 2 The present invention also has as object a composition comprising at least one hydraulic binder, water and, optionally, one or more aggregates, and/or one or more mineral additions, and/or fibres for cements, and/or one or more additives, preferably comprising at least one of the compounds of general formula (I) in an amount by weight ranging from 0.01% and 1% by weight with respect to the binder, as inhibitor of AAR. In one embodiment, this composition comprises EDTA in an amount by weight ranging from 0.2% to 0.4% by weight with respect to the binder. Preferably, it comprises EDTA in amount by weight equal to 0.28% by weight. The present invention also has as object an addition for a cementitious composition for forming mortars or concretes having reduced tendency to react with alkali, characterized in that it comprises at least one of said compounds of general formula: [R—N—(CH 2 —COOH) n ] x   (I) R being an aliphatic or aromatic hydrocarbon chain, n=2 or 3 and x=1 or 2. The present invention also has as object the use of at least one compound of general formula: [R—N—(CH 2 —COOH) n ] x   (I) R being an aliphatic or aromatic hydrocarbon chain, n=2 or 3 and x=1 or 2. as an additive for a cementitious mixture for forming mortars or concretes in order to reduce the tendency to react with alkali of mortar or concrete. The term hydraulic means a material in powder form, in dry state, which when mixed with water, provides plastic mixtures that are able to solidify and harden. Cements means in particular those included in European EN 197-1 standard. The cementitious compositions in question are divided into pastes, i.e. compositions free of inert aggregates, and conglomerates, i.e. compositions containing at least one inert aggregate. The conglomerates are in turn divided in mortars, containing fine aggregates such as for example sand, and concretes, containing both fine aggregates and coarse aggregates such as gravel, pebbles and crushed aggregate selected for example from those classified according to the European EN 12620 standard. The present invention is directed at mortars and concretes in particular. Mineral addition means any type of finely subdivided inorganic material that can be added to the concrete to impart improved mechanical resistance and durability characteristics. The additions can be inert, pozzolanic or can have latent hydraulic activity, for example selected from those permitted by European EN 206-1 standard. For example, a concrete compliant with European EN 206-1 standard, having an addition in excess of 10 kg/m 3 is object of the invention. According to the present invention, at least one compound of formula (I), for example EDTA, is introduced as an additive to the cementitious mixture, for example to form concrete, directly into the mixer or preventively dissolved in the mixing water or on the addition thereof. The amount of EDTA added to the cementitious mixture is preferably between 0.01% and 1% by weight of hydraulic binder. More preferably, the dose of EDTA is between 0.2% and 0.4% by weight of binder. Even more preferably, the dose of EDTA is equal to 0.28% by weight of binder. In the present invention binder means the sum of cement and addition. A cement of the present invention is in particular selected according to European EN 197-1 standard. An addition is in particular selected according to European EN 206-1 standard. A cementitious mixture according to the present invention may comprise additions with latent hydraulic or pozzolanic activity, such as fly ash, microsilica, finely ground granulated blast furnace slag. As hydraulic binders said cements according to European EN 197-1 standard are preferred. DETAILED DESCRIPTION OF THE INVENTION Characteristics and advantages of the present invention are described in grater detail in the following examples, provided by way of a non-limiting example of the present invention. EXAMPLES In the described examples, EDTA was used for the preparation of mortar mixtures according to the invention, dissolving it in the mixing water in the mixer. Aggregate containing reactive silica and that is therefore susceptible to AAR was used; the reactive species content was 25% on average. NaOH was introduced to the mixtures as an alkali source, dissolved in the mixing water in the content of 1% by weight expressed as Na 2 O referring to the binder. Mortar specimens were prepared having 4 cm×4 cm×16 cm dimensions were prepared. The determination of performance was performed by measuring the deformation of the specimens, 24 hours from casting, under the following conditions: in a 1N of NaOH solution at 80° C., onerous both due to the high temperature and due to the continuous supply of alkali during exposure. in water at 60° C., onerous on account of the acceleration of the speed of the AAR due to the high temperature exposure. Example 1 The effect of EDTA in modifying AAR was evaluated in mortar mixtures containing fly ash, as shown in Table 1, using strongly accelerating conditions of exposure (NaOH 1N at 80° C.). or performance of the tests, the following proportions of mixture were adopted using a cement CEM II/A-LL 42.5 R: water-binder ratio equal to 0.55—binder weight—NaOH dissolved in the mixing water in a proportion of 1% by weight expressed as weight of Na 2 O relating to the binder, understood as the sum of the cement and pozzolanic addition. EDTA was added to one of the two mixtures in a proportion of 0.28% by weight of binder, equal to a value of 0.07% by weight referring to the mortar. A second mixture wherein EDTA was not added is shown as reference. It can be observed that using EDTA, the expansions were significantly reduced, the desired technical effect thereby being achieved. TABLE 1 Deformation (expansion) Maturation in NaOH 1N at 80° C. [μm/m] 7 days 14 days 28 days 90 days Reference 581 931 1313 2144 EDTA 0.07% 331 463 731 1200 (present invention) Example 2 The positive effect of EDTA in reducing AAR was verified from tests on mortar mixtures containing fly ash, as shown in Table 2, using accelerating conditions of exposure (water at 60° C.). The following mixture proportions, using CEM II/A-LL 42.5 R, were adopted for performance of the tests: water/binder ratio equal to 0.55 aggregate/binder ratio equal to 2.25 fly ash in a proportion of 20% by weight of binder NaOH dissolved in the mixing water in a proportion of 1% by weight expressed as weight of Na 2 O referring to the binder. EDTA was introduced into one of the two mixtures in a proportion of 0.28% by weight of binder, equal to 0.07% by weight referring to the mortar. A second mixture wherein EDTA was not added is shown as reference. It can be observed the expansions were significantly reduced using EDTA. TABLE 2 Deformation (expansion) Maturation in water at 60° C. [μm/m] 7 days 14 days 28 days 90 days Reference 210 150 191 263 EDTA 0.07% 110 63 47 113 (present invention) Example 3 The positive effect of EDTA in reducing AAR was verified by tests on mortar mixtures containing powdered glass as addition. The physicochemical characteristics of the powdered glass in question are shown in Table 3 and Table 4. TABLE 3 reactive SiO 2 [%] 52.88 SiO 2 [%] 69.0 Al 2 O 3 [%] 2.70 Fe 2 O 3 [%] 0.36 CaO [%] 8.84 MgO [%] 1.44 Na 2 O [%] 15.6 K 2 O [%] 0.84 TABLE 4 BET m 2 /g 0.59 Density - ρ g/cm 3 2.540 Laser - Sv (specific surface) m 2 /cm 3 0.99 Laser - xp (average diameter) μm 16.7 Laser - n (amplitude) — 1.23 The following mixture proportions were adopted for performance of the tests: fly ash in a proportion of 20% by weight of binder aggregate/binder ratio equal to 1.88 water/binder ratio equal to 0.49 NaOH dissolved in the mixing water in a proportion of 1% by weight expressed as weight of Na 2 O referring to the binder. Binder means the sum of cement and powdered glass. EDTA is added to one of the two mixtures in a proportion of 0.28% by weight of binder, equal to 0.1% by weight of mortar. A second mixture wherein EDTA was not added is shown as reference. Table 5 shows the results of tests of the expansion tests in mortar under strongly accelerating conditions of exposure of the AAR (NaOH 1N at 80° C.). It can be observed that by using EDTA the expansions were significantly reduced as follows. TABLE 5 Deformation (expansion) Maturation in NaOH 1N at 80° C. [μm/m] 7 days 14 days 28 days 90 days 126 days Reference 3363 4131 5119 7456 8844 EDTA 0.1% 2494 3394 3638 4638 4644 (present invention) Example 4 The present example shows that, although EDTA is an acid, its use as an additive for concrete according to the present invention has not shown abatement of the mechanical characteristics arising from negative interactions with a strongly basic cementitious matrix. Table 6 records the determinations of dynamic elastic modulus of the same specimens for which the expansions were recorded in the preceding Table 1 and Table 2. It can be derived from Table 6 that it there has been no decrease in elastic modulus in the time, but that there has been, on the contrary, an increase between 30 and 50%, between 1 and 90 days, in all examined cases. TABLE 6 Dynamic Dynamic Specimens the elastic elastic expansions of modulus modulus which are shown (1 day) (90 days) in [MPa] [MPa] % increase Table 1 Reference 16691 22110 28 EDTA 17077 26191 42 Table 2 Reference 15745 28170 57 EDTA 17417 29545 52 Table 5 Reference 15269 17528 14 EDTA 15913 21895 32 Example 5 (Comparative) The effect of the use of a disodium salt of the EDTA instead of the EDTA in a cement mixture is studied in the present invention. Table 7 shows the test expansion data on mortar under strongly accelerating conditions of exposure (NaOH 1N at 80° C.). The following mixture proportions were adopted for performance of the tests: aggregate/cement ratio equal to 1.88 water/cement ratio equal to 0.49 NaOH dissolved in the mixing water in a proportion of 1% by weight expressed as weight of Na 2 O referring to the binder. Na-EDTA added in a proportion of 0.5% and 2% on cement, respectively equal to 0.1% and 0.3% by weight of mortar. The behaviour of a mixture used as reference wherein Na-EDTA has not been used, is also recorded. Table 7 shows only a mild effect reduction effect of the expansions with respect to the reference, probably to be attributed to the two non-complexing functional groups present in the disodium salt molecule of the EDTA. The present example highlights that the use of a salt of EDTA, in this case a disodium salt, does not produce appreciable effects on the reduction of the expansions. In addition, the use of high sodium salt contents has led to undesirable variations of the rheology and of the mechanical characteristics of the mixtures. More in particular, the higher dose of Na-EDTA (0.3%) caused a strong reduction to 1 day of the elastic modulus with respect to the reference. The use of a salt of EDTA must therefore be considered excluded from the scope of the present invention. TABLE 7 Deformation (expansion) [μm/m] Dynamic Dynamic Use of (Maturation in NaOH Rheology elastic elastic disodium 1N at 80° C.) (Spreading) modulus modulus salt of 7 14 28 [mm] [MPa] [MPa] the EDTA days days days UNI 7044 (1 day) (7 days) Reference 3650 6006 8919 115 18461 19424 Na-EDTA 3344 5381 8106 131 18420 20215 (0.1%) (outside the present invention) Na-EDTA 4488 5975 8894 180 7809 18315 (0.3%) (outside the present invention)
The invention has as object a cementitious composition for forming mortars or concretes having reduced tendency to react with alkali, characterized in that it comprises as additive at least a compound of general formula: [R—N—(CH 2 —COOH) n ] x   (I) R being an aliphatic or aromatic hydrocarbon chain, n=2 or 3 and x=1 or 2.
2
BACKGROUND OF THE INVENTION The present invention relates to a map display system for guiding a vehicle such as a car. Various suggestions have been made about a map display system of this type in the prior art. An example is disclosed in Japanese Patent Laid-Open Publication No. 164583/84 invented by the present applicant. In this system, map pattern data providing the basis of display of roads and the like on a display screen and character data providing names of municipalities, roads and the like are both stored as code data, so that with the driving of the vehicle, map patterns and descriptive characters are indicated on the display screen automatically or by the operation of the driver. Indication of all character data included in a given map area on display makes it difficult to see the map as a great number of display data characters are involved. For this reason, there is needed some display limitation. SUMMARY OF THE INVENTION The object of the present invention is to provide a map display system in which character data are provided as a data base independent of data for preparing a map, so that characters are displayed always in the same size regardless of the scale of the map which may be enlarged or reduced by a map display designation on the one hand, and the characters are made easily recognizable on the other hand. That is the interval between characters is kept constant. In order to achieve the above-mentioned object, according to the present invention, there is provided, as shown schematically in FIG. 1, a map display system comprising map data memory means for storing map-forming data required for display of each display area and character data corresponding to each of said areas; display area designation means for reading the map-forming data corresponding to a specified display area from said map data memory means and producing a display area instruction; display character designation means for selecting only the character data corresponding to defined components constructing the specific display area designated by said display area designation means and producing a display character instruction; and display means for displaying the map of the specified display area in response to the display area instruction from said display area designation means and displaying characters in response to the display character instruction from said display character designation means in said display area. A map display system further comprises character form control means for maintaining the size of the characters displayed on the display means and the interval between characters to a fixed level regardless of the display scale of the display area. A map display system further comprises number-of-characters control means for changing the number of characters displayed on the character display means in accordance with the scale of the display area. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram showing a configuration of the present invention. FIG. 2 is a block diagram showing an embodiment of the present invention. FIG. 3 shows a data configuration of character data. FIGS. 4 and 5 are flowcharts for explaining the processing operation of a CPU. FIGS. 6 to 11 are diagrams showing forms of map and display screens for explaining the transfer of screen display forms. FIG. 12 is a flowchart showing displays of display data according to type codes and designation codes of descriptive data. DESCRIPTION OF THE PREFERRED EMBODIMENTS A configuration of an embodiment of the map display system according to the present invention is shown in FIG. 2. In this map display system, a system 1 includes a well-known microcomputer having a CPU 1a, a ROM 1b, a RAM 1c, an input port 1d and a common bus 1e, and a CRT controller 1f. The system further comprises input means including a direction sensor 2 for detecting the direction in which the vehicle is running, a distance sensor 3 for detecting the distance covered by the vehicle, a control panel 4 operated by the driver, and a reader 5b with a replaceable magnetic disc 5a, which input means are electrically connected to the system proper, and output means including at least a CRT display 6 electrically connected thereto for displaying map patterns such as roads and characters. The direction sensor 2 includes an annular permalloy core, an excitation coil and two coils intersecting each other at right angles, and produces a direction signal for detecting the vehicle running direction against the earth's magnetism on the basis of the output voltage of the two coils. The distance sensor 3 detects the revolutions of a speed meter cable indirectly as an electrical signal through a reed switch, a magnetically sensitive element or a photoelectric cell, or detects the revolutions of the output shaft of the transmission as an electrical signal in a similar manner, thereby producing a distance signal used for computing the distance covered by the vehicle. The control panel 4 includes at least a switch (not shown) for supplying and interrupting power to the map display system from a battery mounted on the vehicle, enlargement and reduction keys (not shown) which are operated by the driver for designating an enlarged or reduced display of the map, and a display key (not shown) which is operated by the driver for designating the display of a description on the screen of the CRT display 6. The magnetic disc 5a stores map patterns as pattern data and character data corresponding to appropriate geographic points on the map as code data. Assume that characters "ABC City", "DEFG", "HIJKL" and "MNO" are to be displayed, for example. As shown in FIG. 3, each of the character data is made up of a set of data elements including a display character code, an X coordinate of the position, a Y coordinate of the position, a pilot code display scale, a single-character display scale, a double-character display scale, a three-character display scale, . . . . . , a n-character display scale. The ROM 1b of the system proper has a program stored therein by which the CPU 1a executes the processes shown in the flowchart of FIG. 4. The CPU 1a repeatedly executes the processes (1) to (12) described below. (1) Whether or not the enlargement key is turned on (step 101 in FIG. 4) is decided. (2) If it is decided that the enlargement key is turned on, the enlargement process is executed (step 102). The specific operation of the enlargement process will be described later. (3) After execution of this enlargement process, or if it is decided that the enlargement key is not turned on by the step 101, then it is decided whether or not the reduction key has been turned on (step 103). (4) If it is decided that the reduction key has been turned on, the reduction process is executed (step 104). (5) After execution of the reduction process or if it is decides at step 103 that the reduction key has not been turned on, then the direction signal from the direction sensor 2 and the distance signal from the distance sensor 3 are received to compute the present position of the vehicle in a well-known manner (step 105). (6) The present position obtained by the above computation is compared with the geographic point corresponding to the descriptive data, that is, the descriptive point thereby to decide whether or not the present position coincides with the descriptive point (step 106). (7a) If it is decided that the present position does not coincide with the descriptive point, the process is passed to the computation of the present position (step 105). (7b) If it is decided that the present position coincides with the descriptive point, on the other hand, the description based on the descriptive data corresponding to this descriptive point is displayed on the screen of the CRT display 6 through the CRT controller 1f or the description on display on the screen of the CRT display 6 is erased (step 107). (8) It is decided whether or not the abovementioned description is the one required to be stored in the RAM 1c, such as a radio broadcasting station with the receiving frequency thereof or a telephone number of JAF (step 108). (9) If it is decided that the description is the one to be stored, the particular descriptive data is stored in the RAM 1c (step 109), and the description, after being displayed for several seconds on the screen of the CRT display 6 through the CRT controller 1f, is erased (step 110). (10) After the end of the process of the step 110, or after it is decided at step 109 that the description involved is not the one required to be stored such as "Narrow road" or "Beware of falling stone", then it is decided whether or not the display key has been turned on by a signal from the display key on the control panel 4 (step 111). (11) If it is decided that the display key has been turned on, the description based on the descriptive data stored in the RAM 1c is displayed on the screen of the CRT display 6 through the CRT controller 1f (step 112). (12) After execution of, the process of the step 112, or if in the step 111 it is decided that the display key has not been turned on, then process is passed to the step 101 for deciding whether the enlargement key has been turned on or not. Essential parts of the aforementioned enlargement processes are specifically shown in FIG. 5. These processes will be explained below. (1) A display scale coincident with the scale designated by the enlargement key operation is determined (step 1021). In other words, it is decided whether or not the designated scale coincides with the pilot code display scale, the one-character display scale, the two-character display scale, the three-character display scale, . . . . . or the n-character display scale, or it does not coincide with any of the display scales. This step 1021 is executed only for one of a plurality of display characters once each time of process. (2a) If the designated scale fails to coincide with any of the display scales, the positional coordinate (x, y) determined in advance in correspondence with the display character is transferred to the display screen, and the mark "X" or "Δ" is attached to the coordinate position (step 1022). (2b) When the designated scale coincides with the pilot code display scale, on the other hand, the pilot code is displayed at the display coordinate position in the same manner as above (step 1023). At the same time, a correspondence table is displayed at the upper right corner of the screen as viewed from the operator (step 1024). This correspondence table is displayed in such a form as "a: ABC City" if the display characters are "ABC City" and the pilot code is "a", for example. (2c) If the designated scale coincides with the i-character display scale, such as the double-character display scale, for instance, it is decided whether these two characters coincide with all the display characters (step 1025). Assuming that the display characters are "ABC City", for instance, the characters involved are seven in all, and therefore it is decided that they fail to coincide with each other, so that the display color is changed (step 1026). This display color change is a process for changing the color of the characters to be displayed next. After this display color change or the step 1025 decides that all the characters coincide, the characters to be displayed are displayed in color at the display coordinate position (step 1027). (3) After the process of (2a), (2b) or (2c) above, it is decided whether or not the process has been completed for all the display characters (step 1028), and if all the data is not completely processed, the step 1021 is executed again for the next display characters. If all the data is completely processed, by contrast, this routine is left. In parallel to this enlargement process, the form of display screen described below is achieved according to the designated scale. Specifically, in the case of a map comprising patterns and characters as shown in FIG. 6, assume that the designated scale is minimum, that is, display of the whole map is designated. In view of the fact that roads are so densely located that a character display thereof is not legible, only the marks "X" and "Δ" are attached at the display positions based on the coordinate (x, y) as shown in FIG. 7. In the case of a designated scale a rank higher, the pilot code "a" is displayed only for ABC City, together with the correspondence table "a: ABC City" at the upper right corner at the same time as shown in FIG. 8. Further, on the other hand, "AB" alone of "ABC City", "DE" alone of "DEFG" and "HIJ" alone of "HIJK" are displayed as shown in FIG. 9, while at the same time displaying the whole of "MNO". If the designated scale is a greater rank, the whole of "ABC City" and "HIJKL" and "DEF" alone of "DEFG" are displayed as shown in FIG. 10. As can be seen from these figures, the interval between adjacent characters remains the same regardless of the scale of the map. Now, explanation will be made of the manner in which the display form of the screen of the CRT display 6 undergoes a change with the progress of the vehicle with reference to the steps 105 to 112 in the flowchart of FIG. 4 described above. The roads displayed on the screen of the CRT display 6 have descriptive points (P 2 , P 3 , P 4 , . . . ) for displaying service data of various types, so that sentences of the descriptive data are displayed on the screen of the CRT display 6 when the vehicle passes each descriptive point. (1) When the vehicle having passed the point P1 shown in FIG. 11 reaches the descriptive point P2, the data "Beware of falling rock" is displayed at a part of the screen, such as at the lower part thereof. (2) Subsequently when the vehicle having passed the point where he was warned against falling rock reaches the descriptive point P3, the display "Beware of falling rock" is erased. (3) Subsequently when the vehicle reaches the descriptive point P4, the telephone number of JAF (corresponding to AAA) such as "JAF ΔΔ- 0000" is displayed for several seconds. (4) Subsequently when the vehicle reaches the descriptive point P7 through the points P5 and P6, the receiving frequency such as "A broadcasting station xxxxx KHz" is displayed for several seconds. (5) After that, when the vehicle reaches the descriptive point P9 through the point P8, the receiving frequency "B broadcasting station 0000 KHz" is displayed for several seconds. (6) Then, when the vehicle reaches the descriptive point P13 through the points P10, P11 and P12, "Narrow road" is displayed at a part of the screen. (7) After that, when the vehicle reaches the descriptive point P14 through the narrow road, the display "Narrow road" is erased. As described above, in the case where a vehicle makes progress as shown in FIG. 11, the display form of the screen changes as specified from (1) to (7) with the progress of the vehicle. However, if the display key of the JAF telephone number or other key is operated after the vehicle has passed the descriptive point P4, for instance, the telephone number of JAF or the related data, as the case may be, is displayed by the operation of the display keys. The steps 106 to 112 in the flowchart of FIG. 4 will be explained more in detail below. As shown in Table 1, the display data, designation codes and type codes are stored in the magnetic disc 5a in correspondence with the coordinate data of the respective descriptive points (P 2 , P 3 , P 4 , . . . ). TABLE 1______________________________________DESCRIPTIVE POINT DATAPosition ofdescriptive Type Designationpoint Display data code code______________________________________P2 (x.sub.p2, y.sub.p2) Beware of falling 1 1 rockP3 (x.sub.p3, y.sub.p3) "Beware of falling 1 2 rock" cancelledP4 (x.sub.p4, y.sub.p4) JAF ΔΔ-OOOO 2 3P7 (x.sub.p7, y.sub.p7) A broadcasting sta- 3 3 tion xxxx KHzP9 (x.sub.p9, y.sub.p9) B broadcasting sta- 3 3 tion xxxxx KHz. . . .. . . .. . . .P13 (x.sub.p13, y.sub.p13) Narrow road 1 1P14 (x.sub.p14, y.sub.p14) "Narrow road" 1 2 cancelled______________________________________ DESIGNATION CODES: 1: Data displayed while a caution instruction is issued. 2: Data for designating the cancellation of the data on display. Displaye for several seconds. 3: Data displayed for several seconds and stored the RAM data. This data becomes an object of operation display. TYPE CODES: 1: Caution data 2: JAF data 3: Broadcasting station data The descriptive data shown in Table 1 are processed in accordance with the flow chart shown in FIG. 12. In the flowchart of FIG. 12, the display data is displayed and stored in the RAM 1c in accordance with the designation code and the type code of each descriptive data. The caution data with the type code of "1", for instance, is not required to be displayed after the vehicle has passed the particular point, and therefore is not stored in the RAM 1c. As to the JAF data or the broadcasting station data with the type code of "2, 3", however, they are stored in the RAM 1c, since the telephone number of JAF or the receivable frequency of the broadcasting stations is necessary in case of emergency even after the particular descriptive point has been passed. When the user operates the display keys, therefore, the descriptive data is read out and displayed from the RAM even after the particular descriptive point has been passed. Storage addresses corresponding to each descriptive data are predetermined in the RAM, and they are rewritten as the latest data each time the descriptive points are passed. In the case where the data in the RAM is displayed at step 112, only that data with the type code of "2" or "3" is picked up from Table 1 and displayed. The display keys may be adapted for displaying each type code each time of operation thereof.
In a map display system, map-forming data necessary for display of a display area and character data representing display areas are stored in a map data memory. A display area commander reads map-forming data indicating a specified display area out of the map data memory, and produces a display area instruction. A display character commander selects character data for a given point of the specified display area designated by the display area designation commander, and produces a display character instruction. On the basis of the display area instruction from the display area commander and the display character instruction from the display character commander, a map of the specified display area and characters in the specified display area are displayed on a display.
6
CROSS REFERENCE TO RELATED APPLICATION [0001] This application claims priority to U.S. Ser. No. 61/885,792, titled SWITCHABLE CAMERA SYSTEM FOR A FIREARM, filed on Oct. 2, 2013, the disclosure of which is hereby incorporated by reference in its entirety. BACKGROUND [0002] Military and law enforcement personnel often enter and search unknown operating environments, such as homes or buildings. In some situations, the unknown operating environment may include dangerous adversaries, such as armed criminals or enemy combatants. In many cases, military and law enforcement will search these environments with a firearm for protection and to help in apprehending the adversary or otherwise achieving a defined objective. [0003] Searching these unknown operating environments can be dangerous for military or law enforcement personnel. This danger is amplified at potential ambush points where the military or law enforcement personnel's view of the environment may be obstructed by, for example, a wall or ceiling. Examples of ambush points include corners, doorways, and entrances to attics. In these situations, military and law enforcement personnel have few options to check for an adversary hidden by the obstruction. SUMMARY [0004] In general terms, this disclosure is directed to a switchable camera system for a firearm. In one possible configuration and by non-limiting example, the camera system allows the user to see into potential ambush points (e.g., around corners and above surfaces) before entering the ambush point and risking attack. [0005] One aspect is a camera system for a firearm comprising: a camera assembly including a plurality of cameras fixedly oriented in a plurality of different directions, the plurality of cameras configured to generate a plurality of image signals; a display assembly including a display panel; a mounting fixture secured to the camera assembly, the mounting fixture configured to be removably attached to a firearm; and a switch configured to select between the plurality of cameras to display one of the plurality of image signals on the display panel. [0006] Another aspect is a camera and firearm assembly comprising: a firearm; a camera assembly secured to the firearm and including at least three cameras, each of the cameras generating a video signal; a switch, the switch being configured to select one of the video signals; and a display panel secured to the firearm and configured to display the selected one of the video signals. [0007] Yet another aspect is a method of improving situational awareness for a user of a firearm, the method comprising: activating a firearm-mounted camera system including a display panel and a plurality of cameras fixedly oriented in a plurality of different directions, the cameras being positioned about the forward end of a firearm; receiving a switch input from a user selecting one of the cameras; generating an image of a portion of an environment with the selected one of the cameras; and displaying the image of the portion of the environment on the display panel to alert the user to conditions in the portion of the environment. [0008] Another aspect is a camera system for a firearm comprising: a camera assembly including a plurality of cameras oriented in different directions, the plurality of cameras generating a plurality of images; a display panel including a display device; a mounting fixture secured to the camera assembly, the mounting fixture configured to be removably attached to a firearm; and a switch configured to select between the plurality of cameras to present one of the respective images on the display device. [0009] Yet another aspect is a camera and firearm assembly comprising: a firearm; a camera assembly secured to the firearm and including at least two cameras, each of the cameras generating a video signal; a switch, the switch being configured to select one of the video signals; and a display panel secured to the firearm and configured to display the selected one of the video signals. [0010] Another aspect is a method of approaching a potential ambush point comprising: approaching the end of an obstruction; positioning a camera assembly of a firearm-mounted camera system beyond the obstruction; viewing a screen of the firearm-mounted camera system; and looking for a visible representation on the screen of an object of interest. [0011] A further aspect is a method of improving situational awareness for a user of a firearm, the method comprising: activating a firearm-mounted camera system including a display device and a plurality of cameras oriented in different directions, the cameras being positioned about the forward end of a firearm; receiving a switch input from a user selecting one of the cameras; detecting an image of an object with the selected one of the cameras; and displaying the image of the object on the display device to alert the user to the presence of the object. DESCRIPTION OF THE DRAWINGS [0012] Aspects of the disclosure may be more completely understood in consideration of the following detailed description of various embodiments of the disclosure in connection with the accompanying drawings. [0013] FIG. 1 is a diagram depicting an example operating environment in which a firearm-mounted camera system can be used. [0014] FIG. 2 is a perspective view of the example firearm-mounted camera system of FIG. 1 . [0015] FIG. 3 is a schematic diagram of an example camera assembly of a firearm-mounted camera system. [0016] FIG. 4 is a side view of the enclosure of the camera assembly of the example firearm-mounted camera system of FIG. 1 . [0017] FIG. 5 is a view of the camera assembly of the firearm-mounted camera system of FIG. 1 . [0018] FIG. 6 is a close-up view of the mounting fixture of the camera assembly of the example firearm-mounted camera system of FIG. 1 . [0019] FIG. 7 is a schematic diagram of an example switching mechanism of a firearm-mounted camera system. [0020] FIG. 8 is a side view of the switching mechanism of the example firearm-mounted camera system of FIG. 1 . [0021] FIG. 9 is a down-barrel, perspective view of the example firearm-mounted camera system of FIG. 1 , similar to the typical view from the perspective of a user. [0022] FIG. 10 is a side view of an example display assembly of the example firearm-mounted camera system of FIG. 1 rotated by approximately 90 degrees in an open position. [0023] FIG. 11 is a side view of the display assembly of the example firearm-mounted camera system of FIG. 1 in a closed position. [0024] FIG. 12 is a side view of the display assembly of the example firearm-mounted camera system of FIG. 1 rotated by approximately 180 degrees in an open position. [0025] FIG. 13 is a front, perspective view of the display assembly of the example firearm-mounted camera system of FIG. 1 . [0026] FIG. 14 is a diagram depicting another example operating environment in which a firearm-mounted camera system can be used. [0027] FIG. 15 is a diagram depicting another example operating environment in which a firearm-mounted camera system can be used to fire around an obstruction. [0028] FIG. 16 is perspective view of another example firearm-mounted camera system. [0029] FIG. 17 is a rear, perspective view of the housing of the switching mechanism of the firearm-mounted camera system of FIG. 16 . [0030] FIG. 18 is a top, cross-sectional view of the housing of the switching mechanism of the firearm-mounted camera system of FIG. 16 . DETAILED DESCRIPTION [0031] The example embodiments described in the following disclosure are provided by way of illustration only and should not be construed as limiting. Various modifications and changes may be made to the example embodiments described below without departing from the true spirit and scope of the disclosure. [0032] The present disclosure relates generally to a switchable camera system for a firearm. The camera system is switchable because it includes multiple cameras and a switch to select among them. In some embodiments, for example, the camera system allows the user to see into potential ambush points (e.g., around corners and above surfaces) before entering the ambush point and risking attack. Additionally, the camera system allows the user to search under and inside possible hide locations, such as inside a boat, dumpster, or car, for a potentially dangerous person or animal. [0033] FIGS. 1 and 2 depict an example firearm-mounted camera system 100 . FIG. 1 is a diagram depicting an example operating environment 50 in which a firearm-mounted camera system 100 can be used. FIG. 2 is a perspective view of the example firearm-mounted camera system 100 . [0034] The example operating environment of FIG. 1 includes a portion 52 of a building, a user U of the firearm-mounted camera system 100 , and an object O of interest. [0035] In this example, the portion 52 of the building includes a passageway 54 , a passageway 56 , and an obstruction 58 . The user U is located in passageway 54 , while the object O of interest, such as an armed adversary, is located in passageway 56 . The object O of interest is obstructed from the view of user U by an obstruction 58 . In this example, the obstruction includes a wall 60 that terminates at a corner 62 . To improve situational awareness, it is desirable for the user U to know whether or not an object O of interest is present behind the obstruction 58 to permit the user U to react accordingly. [0036] The firearm-mounted camera system 100 includes a firearm 80 and a camera system 102 . [0037] The firearm 80 is a type of weapon arranged and configured to fire a projectile. Examples of the firearm 80 include handguns and long guns, such as rifles or shotguns. The firearm 80 can be of a variety of different actions, including manual, semi-automatic, or fully automatic. The firearm 80 can be a tactical firearm with a pistol grip, rail mount, bayonet mount, or flashlight mount, or one that can be configured as such. Examples include AR-type rifles, like the AR-15, manufactured by Colt's Manufacturing Company, LLC, of Hartford, Conn., M16 rifle, M4 Carbine manufactured by Colt's Manufacturing Company, LLC of Hartford, Conn. and variants, M14 rifle manufactured by Springfield Armory, Inc. of Geneseo, Ill. and variants, such as the G3 manufactured by Heckler & Koch GmbH, of Oberndorf am Neckar, Germany, the MP5 manufactured by Heckler & Koch GmbH, of Oberndorf am Neckar, Germany, and the Uzi manufactured by Israel Military Industries, of Ramat HaSharon, Israel, or semi-automatic or pump-action shotguns. [0038] In some embodiments, the camera system 102 includes a camera assembly 104 , a switching mechanism 106 , and a display assembly 108 . The camera system 102 is configured to be mounted to the firearm 80 . [0039] The camera assembly 104 includes at least one camera 110 . The camera 110 operates to detect light representing an image and convert the detected light into electrical signals. Some embodiments include multiple cameras 110 , such as three cameras 110 A, 110 B, and 110 C that each face in different directions. Examples of the camera assembly 104 are illustrated and described in more detail herein with reference to FIGS. 3-6 . [0040] The switching mechanism 106 is provided to perform receiving input from the user U, and upon receipt of the input, to perform one or more switching operations. For example, when multiple cameras 110 A, 110 B, and 110 C are present, the switching mechanism 106 can be used to select between the various cameras 110 A, 110 B, and 110 C. Examples of the switching mechanism 106 are illustrated and described in more detail herein with reference to FIGS. 7-8 . [0041] The display assembly 108 generates a visible representation 112 of the image captured by one or more of the cameras 110 of the camera system 100 . The graphical depiction A in FIG. 1 illustrates the view from the perspective of the user U in the illustrated scenario. Examples of the display assembly 108 are described in more detail herein with reference to FIGS. 9-13 . [0042] When the firearm-mounted camera system 100 is utilized in the manner shown in FIG. 1 , the user approaches the end of the obstruction at the corner 62 , and positions the firearm 80 so that the camera 110 of the camera assembly 104 mounted thereon extends past the corner 62 . Upon doing so, the image detected by the camera 110 is displayed as the visible representation 112 by the display assembly 108 to the user U. An image of the object O of interest is also detected by the camera 110 and included in the visible representation 112 to alert the user U to the presence of the object O. In this way, the situational awareness of the user U is improved to permit the user to react appropriately. [0043] FIG. 3 is a schematic diagram of an example camera assembly 104 . In some embodiments, camera assembly 104 includes enclosure 300 , interior volume 302 , and camera 110 . In some embodiments, camera assembly 104 includes multiple cameras 110 A, 110 B, and 110 C. In some embodiments, camera assembly 104 also includes infrared emitters 304 A and 304 B. [0044] Enclosure 300 is a hollow, cylindrical shell formed from plastic, metal, rubber, or any other suitable material in some embodiments. In some embodiments the enclosure 300 forms a head assembly of the camera assembly 104 . Enclosure 300 defines an interior volume 302 . Enclosure 300 includes at least one optical path, such as an aperture, through which camera 110 is directed. In some embodiments, Enclosure 300 includes additional optical paths through which additional cameras may be directed. Additionally, in some embodiments, enclosure 300 includes one or more infrared paths, such as the areas defined by apertures, through which infrared emitters, such as infrared emitters 304 A or 304 B, are directed. [0045] Interior volume 302 is the volume surrounded by and defined by the enclosure 300 . At least some of the components of the camera assembly, including camera 110 , are disposed in interior volume 302 . In some embodiments, multiple cameras, such as cameras 110 A, 110 B, and 110 C, are disposed in interior volume 302 . Additionally, in some embodiments, infrared emitters 304 A and 304 B are also disposed in interior volume 302 . The wiring assembly 306 for cameras 110 A, 110 B, and 110 C and infrared emitters 304 A and 304 B connects to these parts and extends through and out from the interior volume 302 . In some embodiments, interior volume 302 is filled with a substance, such as epoxy, to ruggedize camera assembly 104 by surrounding the wiring and components to minimize shifting and movement. [0046] Cameras 110 A, 110 B, and 110 C operate to detect light and convert the detected light into electrical signals representing the image detected from the light. These electrical signals are examples of image signals. In some embodiments, cameras 110 A, 110 B, and 110 C also operate to detect infrared light. In other embodiments, cameras 110 A, 110 B, and 110 C operate to detect both optical light and infrared light. The cameras 110 A, 110 B, and 110 C can be configured to use a variety of image capture sensors, including charge-coupled devices, complementary metal-oxide-semiconductors, or any other means of capturing images. In some embodiments, cameras 110 A, 110 B, and 110 C are digital video cameras. [0047] Cameras 110 A, 110 B, and 110 C are at least partially contained within enclosure 300 and are directed through one or more optical or infrared paths through enclosure 300 , such as an area defined by an aperture. Cameras 110 A, 110 B, and 110 C are directed in different directions relative to each other. In FIG. 3 , cameras 110 A and 110 B are directed in opposite directions, D 1 and D 2 , and are configured to aim out from the sides of a firearm. By contrast, Camera 110 C is directed in direction D 3 and configured to aim out from the front of the firearm. [0048] Infrared emitters 304 A and 304 B operate to emit electromagnetic radiation, such as near infrared light. Near-infrared light is electromagnetic radiation with a wavelength from 0.78-3 μm. Near-infrared light is not visible to the human eye. Infrared emitters 304 A and 304 B can be configured to use any technology that emits infrared light, such as a light emitting diode. [0049] Infrared emitters 304 A and 304 B are at least partially contained within enclosure 300 . Infrared emitters 304 A and 304 B are directed towards one or more infrared paths through enclosure 300 , such as the area defined by an aperture, which directs infrared light out to the environment proximate to camera assembly 104 . This infrared light is not detected by the human eye, but is detected by cameras 110 A, 110 B, and 110 C in some embodiments. In some embodiments, an additional infrared emitter is included and directed towards the front of the firearm. Other embodiments include additional infrared emitters to illuminate a wide field of view with infrared light. In this manner, camera assembly 104 provides covert, night-vision capabilities. [0050] Although, the example camera assembly 104 of FIG. 3 includes three cameras, some embodiments may include more or fewer than three cameras. Similarly, some embodiments may include more or fewer than the two infrared emitters included in the example embodiment of camera assembly 104 shown in FIG. 3 . [0051] FIG. 4 is a side view of enclosure 300 of the example camera assembly 104 . Enclosure 300 includes base 400 , cover 402 , fasteners 404 and 406 , optical path 408 , and infrared path 410 . [0052] Base 400 is hollow and cylindrical with a closed bottom surface and an opening on top. Base 400 is formed from plastic, metal, rubber, or any other suitable material. [0053] Cover 402 is configured to fit on top of base 400 and seal it. Cover 402 is formed from plastic, metal, rubber, or any other suitable material. In some embodiments, cover 402 is formed from the same material as base 400 . However, in other embodiments, base 400 and cover 402 are formed from different materials. [0054] Fasteners 404 and 406 operate to secure cover 402 to base 400 . Examples of fasteners 404 and 406 include screws and bolts. However, in some embodiments, other means of securing cover 400 to enclosure 300 are used. [0055] Optical path 408 is a portion of the surface of base 400 that operates to permit the passage of optical light. Examples of optical path 408 include the areas defined by apertures, lens, plane glass, and optical filters. In some embodiments, base 400 includes optical path 408 through which camera 110 A is directed and receives optical light. In other embodiments, base 400 includes additional optical paths through which additional cameras are directed. Additionally, in some embodiments, optical path 408 operates to permit passage of infrared light as well as optical light. [0056] Infrared path 410 is a portion of the surface of base 400 that operates to permit the passage of infrared light. Examples of infrared path 410 include the areas defined by apertures, lens, plane glass, and optical filters. In some embodiments, base 400 includes infrared path 410 through which infrared emitter 304 A is directed and emits infrared light. In other embodiments, base 400 includes additional infrared paths through which additional infrared emitters are directed. [0057] FIG. 5 is a view of an example camera assembly 104 mounted on an example firearm 80 . Camera assembly 104 includes enclosure 300 , beam 500 , and mounting fixture 502 . In some embodiments, camera assembly 104 also includes cable 506 . [0058] Enclosure 300 contains camera 110 A and is described in detail in FIGS. 3 and 4 . [0059] Beam 500 is a hollow beam or cylinder constructed from a rigid material, such as metal, plastic, or a composite. Beam 500 is secured at a first end to enclosure 300 and at a second end to mounting fixture 502 . In some embodiments, beam 500 is disposed in a direction generally parallel to the barrel 84 of firearm 80 . In some embodiments, a direction generally parallel to the barrel 84 is a direction that is within one, five, or fifteen degrees of the direction of the barrel 84 . Beam 500 positions enclosure 300 near muzzle 82 of firearm 80 . In some embodiments, enclosure 300 is set back behind the muzzle 82 by a distance 504 to minimize the effect of muzzle flash and muzzle blast on enclosure 300 when firearm 80 is discharged. In yet other embodiments, the beam 500 is not included. Instead, the enclosure 300 is secured directly to the mounting fixture. [0060] Because enclosure 300 is positioned near muzzle 82 of firearm 80 , the user may use camera assembly 104 to see around obstructions while extending only a small portion of firearm 80 beyond the obstruction. Accordingly, this minimizes the risk that the firearm or user's hand will be grabbed by an adversary who is hiding beyond the obstruction. [0061] Mounting fixture 502 is an apparatus that attaches camera assembly 104 to firearm 80 . In some embodiments, mounting fixture 502 is configured to attach to a picatinny rail 86 , such as with a thumbscrew or a hex screw. In other embodiments, mounting fixture 502 is configured to be removably attached to firearm 80 via other mechanisms, such as a bayonet mount. In yet another embodiment, mounting fixture 502 is permanently secured to firearm 80 . [0062] Cable 506 is a cable that operates to carry signals representing images to switching mechanism 106 . In some embodiments, cable 506 is an electrical cable. In some embodiments, cable 506 also operates to carry power and control signals from switching mechanism 106 to camera assembly 104 . In other embodiments, cable 506 is an optical fiber cable. In some embodiments, cable 506 is partially or completely contained in beam 500 . Other embodiments do not include cable 506 at all. In these embodiments, signals representing images may be transmitted to switching mechanism 106 by wireless radio frequency communication or optical beam. [0063] FIG. 6 is a close-up view of the mounting fixture 502 of an example camera assembly 104 secured to a firearm 80 . Mounting fixture 502 includes lever 600 . Mounting fixture 502 is configured to mate with rail 86 when it is removably attached to firearm 80 . [0064] Lever 600 is a rigid beam that pivots about a fixed point. Lever 600 operates to secure the mounting fixture 502 to rail 86 . Lever 600 is sized to be rotated by hand. As lever 600 is rotated in a first direction, D 4 , fixture 502 is released from rail 86 . Conversely, as lever 600 is rotated in a direction opposite of D 4 , fixture 502 is secured to rail 86 . In other embodiments, mounting fixture 502 is configured to be removably attached to firearm 80 with a thumbscrew or hex screw, rather than a lever. [0065] FIG. 7 is a schematic diagram of switching mechanism 106 of an example camera system 102 . Switching mechanism 106 is in electrical communication with the camera assembly 104 and the display assembly 108 . In some embodiments, switching mechanism 106 controls the power signals for camera assembly 104 and display assembly 108 . In some embodiments, switching mechanism 106 receives electrical signals representing images from camera assembly 104 . Further, in some embodiments, switching mechanism 106 transmits electrical signals representing images to display assembly 108 . [0066] In some embodiments, switching mechanism 106 includes control board 700 , camera switch 702 , power switch 704 , and power supply 706 . [0067] Control board 700 is an electronic apparatus that receives and transmits electrical signals. Examples of control boards include printed circuit boards, analog signal processors, digital signal processors, and other processing devices. Control board 700 may also be implemented through any other reasonable means of providing control function. In some embodiments, control board 700 includes a processor 708 , memory 710 , and accelerometer 712 . [0068] In some embodiments, control board 700 operates to enable or disable all or some of camera assembly 104 and display assembly 108 . In some embodiments, control board 700 operates to direct electronic signals representing images received from camera assembly 104 to display assembly 108 . In some embodiments, the processor of control board 700 encodes and stores images received from camera assembly 104 into its memory. [0069] In some embodiments, camera switch 702 is an electromechanical device having multiple states, each state opening or closing an electrical circuit. In some embodiments, camera switch 702 is configured to be mechanically manipulated by hand to switch between states. Camera switch 702 is in electrical communication with control board 700 . Based on the current state of camera switch 702 , control board 700 operates to select which camera signal from camera assembly 104 is transmitted to display assembly 107 . In some embodiments, control board 700 disables or enables one or more cameras of camera assembly 104 based on the state of camera switch 702 . Further, in some embodiments, control board 700 disables or enables one or more infrared emitters of camera assembly 104 based on the state of camera switch 702 . [0070] In some embodiments, camera switch 702 has three physical positions. Each physical position corresponds to one of the cameras in camera assembly 104 . In other embodiments, camera switch 702 may have fewer physical positions than the number of cameras in camera assembly 104 . In these embodiments, the switch indicates to control board 700 to loop to the next camera signal received from camera assembly 104 . In some embodiments, camera switch 702 is implemented as a potentiometer, similar to a joystick. In these embodiments, a camera is selected by actuating the potentiometer. When the potentiometer is not actuated, a default camera will be selected. Alternatively, in some embodiments, the camera system 102 may be disabled when the potentiometer is not actuated. In other embodiments, camera switch 702 is implemented with one or more buttons or touch sensors. When one of the buttons or touch sensors is activated, a specific camera is selected. Still other embodiments are possible. [0071] In this manner, control board 700 and camera switch 702 operate to allow the user of camera system 102 to select the image that is displayed on display assembly 108 from the images received by the cameras in camera assembly 104 . [0072] In some embodiments, processor 708 reorients the selected image received by the cameras in camera assembly 104 based on the orientation of the firearm 80 sensed by accelerometer 712 . In this manner, the image displayed on display assembly 108 is oriented so that up is at the top of the screen regardless of the orientation of firearm 80 . The image reorientation process is illustrated in FIG. 14 . In some embodiments, the orientation of the firearm is detected using gyroscope technology, such as a vibrating structure gyroscope. Still other orientation-sensing technologies may be used. [0073] In some embodiments, processor 708 stores some or all of the images received by the cameras in camera assembly 104 to memory 710 . The images stored in memory 710 can be used for record-keeping, evidentiary, or other purposes. [0074] Power switch 704 is an electromechanical device configured to turn the camera system 102 on or off. In some embodiments, power switch 704 will have two physical states. The first state completing a circuit and allowing a current to flow; the second state breaking the circuit and preventing the current from flowing. In some embodiments, power switch 704 is a push button switch in which the push button switch toggles (or switches) from a first state to a second state when it is pushed a first time, and toggles (or switches) back to the first state when it is pushed a second time. In other embodiments, power switch 704 may flip or slide from one state to another. [0075] Power supply 706 provides electrical energy to camera system 102 . In some embodiments, power supply 706 is a battery. In some embodiments, power supply 706 is in electrical communication with power switch 704 . In those embodiments, in one state, power switch 704 completely deprives camera system 102 of power. In other embodiments, power supply 706 is in direct electrical communication with control board 700 . In those embodiments, the signal from power switch 704 directs the control board to provide power to display assembly 108 and camera assembly 104 . [0076] FIG. 8 is a side view of switching mechanism 106 mounted to firearm 80 . In some embodiments, switching mechanism 106 includes foregrip 800 and mounting fixture 802 . [0077] In some embodiments, foregrip 800 is a hollow cylinder formed from a rigid material, such as metal or plastic. In some embodiments, foregrip 800 contains power supply 706 and control board 700 . Further, in some embodiments, power switch 704 and camera switch 702 are secured to the exterior of foregrip 800 . In some embodiments, foregrip 800 includes an access panel to replace or charge the batteries of power supply 706 . In some embodiments, foregrip 800 is configured to perform at least two functions. First, foregrip 800 provides physical protection to the components of switching mechanism 106 . Second, foregrip 800 provides a convenient location for the user to hold and control firearm 80 while keeping his or her hand in close proximity to camera switch 702 and power switch 704 . Because conveniently located camera switch 702 allows the user to select images for display from camera assembly 104 , the user may quickly move from one obstruction to the next without delaying to reconfigure camera system 102 . [0078] Mounting fixture 802 is an apparatus that attaches switching mechanism 106 to firearm 80 . In some embodiments, mounting fixture 802 is configured to attach to picatinny rails. The mounting fixture 802 may be configured to mount to the picatinny rails at an angle. In other embodiments, mounting fixture 802 is configured to be removably attached to firearm 80 via other mechanisms. In yet another embodiment, mounting fixture 802 is permanently secured to firearm 80 . [0079] In some embodiments, mounting fixture 802 is integral with foregrip 800 . In other embodiments, mounting fixture 802 is secured to foregrip 800 with a fastener or by another means. [0080] FIG. 9 is a down-barrel, perspective view of the example firearm-mounted camera system 100 , similar to the typical view from the perspective of a user U. In this view, display assembly 108 of camera system 102 is shown as mounted on firearm 80 and held by user U. [0081] Display assembly 108 includes screen 900 , hinge 902 , pivot point 904 , and cable 906 . Additionally, in some embodiments display assembly 108 includes the power supply 706 and control board 700 . [0082] In some embodiments, screen 900 is a liquid crystal display. In other embodiments, screen 900 is a light-emitting diode display. Still other embodiments of screen 900 are possible as well. Screen 900 operates to receive an electrical signal representing an image and display that image. [0083] In some embodiments, hinge 902 is a barrel hinge. Hinge 902 is configured to allow display assembly 108 and screen 900 to be rotated in a direction D 5 towards or in the opposite direction away from the user (direction D 5 is also illustrated in FIG. 11 ). When screen 900 is fully rotated towards the user, it faces the body of firearm 80 and does not significantly interfere with the view of user U. Display assembly 108 can also be rotated away from the user so that screen 900 faces out in the direction of the side of firearm 80 and may be viewed from the side of firearm 80 . In this manner, user U may quickly configure camera system 102 to be used or hidden from view without delay for physical attachment or removal of components. [0084] Pivot point 904 is a mechanical joint that operates to allow screen 900 to be rotated up in direction D 6 or down in the opposite direction. In combination with hinge 902 , pivot point 904 operates to allow user U to adjust the orientation of screen 900 to optimize viewing and minimize interference with user U's field of view. [0085] Cable 906 is a cable that operates to carry signals representing images to screen 900 . In some embodiments, cable 906 is an electrical cable. In some embodiments, cable 906 also operates to carry power and control signals to screen 900 or other components of display assembly 108 . In other embodiments, cable 906 is an optical fiber cable. Other embodiments do not include cable 906 at all. In these embodiments, signals representing images may be transmitted to screen 900 by wireless radio frequency communication or optical beam. [0086] FIG. 10 is a side view of an example display assembly 108 of a firearm-mounted camera system 100 . Display assembly 108 includes mounting fixture 1000 . [0087] Mounting fixture 1000 is an apparatus that attaches display assembly 108 to firearm 80 . In some embodiments, mounting fixture 1000 is configured to attach to picatinny rails. The mounting fixture 1000 may be configured to mount to the picatinny rails at an angle. In other embodiments, mounting fixture 1000 is configured to be removably attached to firearm 80 via other mechanisms. In yet another embodiment, mounting fixture 1000 is permanently secured to firearm 80 . [0088] Mounting fixture 1000 is secured to hinge 902 . In some embodiments, mounting fixture 1000 is integral with hinge 902 . In other embodiments, mounting fixture 1000 is secured to hinge 902 with a screw, bolt, or other appropriate fastener. [0089] FIG. 11 is a side view of display assembly 108 of an example firearm-mounted camera system 100 . In this figure, display assembly 108 is rotated in direction D 5 about hinge 902 into a fully closed position. In a fully closed position, the screen of display assembly 108 faces and abuts the side of firearm 80 . In this position, the screen and display assembly 108 minimally interfere with the field of view and situational awareness of the user of firearm 80 . [0090] FIG. 12 is another side view of display assembly 108 of an example firearm-mounted camera system 100 . In this view, the display assembly 108 is rotated about hinge 902 into a fully open position. In this position, screen 900 may be viewed from the side of firearm 80 . [0091] FIG. 13 is a front, perspective view of display assembly 108 of an example firearm-mounted camera system 100 . In this figure, display assembly 108 is rotated to a standard open position about hinge 902 . In this figure, display assembly 108 is rotated around pivot point 904 to tilt up. [0092] FIG. 14 depicts an example firearm-mounted camera system 100 . FIG. 14 is a diagram depicting an example operating environment 50 in which a firearm-mounted camera system 100 can be used. The example operating environment of FIG. 14 includes a portion 52 of a building and an object O of interest. [0093] In this example, the portion 52 of the building includes a room 66 , attic 68 , and obstruction 58 . Attic 68 is above room 66 . In this example, the obstruction includes a ceiling 64 that separates room 66 from attic 68 . In this example, ceiling 64 also includes an open access panel 70 permitting access from room 66 to attic 68 . [0094] The user U is located in room 66 . The object O of interest, such as an armed adversary, is in attic 68 and is obstructed from the view of user U by ceiling 64 . To improve situational awareness, it is desirable for the user to know whether or not an object O of interest is present in the attic 68 to permit the user to react accordingly. The graphical depiction B in FIG. 14 illustrates the view from the perspective of the user U in the illustrated scenario. [0095] When the firearm-mounted camera system 100 is utilized in the manner shown in FIG. 14 , the user approaches the open access panel 70 and positions the firearm-mounted camera system 100 so that the camera 110 of camera assembly 104 extends above ceiling 64 . Upon doing so, the image detected by the camera 110 is displayed as the visual representation 114 B on display assembly 108 . An image of the object O of interest is also detected by the camera 110 and included in the visual representation 114 B. Visual representation 114 B shows the image detected by the camera after it has been reoriented based on the orientation of the gun as detected by the accelerometer. For illustrative purposes, graphical depiction B also includes internal representation 114 A, which shows the image detected by the camera before it is reoriented. In this way, the user is alerted to the presence of the object O and may react accordingly. [0096] FIG. 15 is a diagram depicting an example operating environment 50 in which a firearm-mounted camera system 100 can be used to fire around an obstruction 58 . The example operating environment of FIG. 15 includes a portion 52 of a building, a user U of the firearm-mounted camera system 100 , and an object O of interest. [0097] In this example, the portion 52 of the building includes a passageway 54 , passageway 56 , and obstruction 58 . The user U is located in passageway 54 , while the object O of interest, such as an armed adversary, is located in passageway 56 . The object O of interest is obstructed from the view of user U by an obstruction 58 . In this example, the obstruction includes a wall 60 that terminates at a corner 62 . [0098] When the firearm-mounted camera system 100 is utilized in the manner shown in FIG. 15 , the user U approaches the end of the obstruction at corner 62 and positions the firearm-mounted camera system 100 so that the muzzle 82 is extended past the corner 62 and pointed into passageway 56 . In this figure, display assembly 108 is rotated about hinge 902 into the fully open position so that screen 900 may be viewed from the side of the firearm. User U is holding the firearm from the side and, accordingly, may view screen 900 . In this manner, user U may aim and, if necessary, fire firearm 80 around a corner without stepping into passage 56 . [0099] FIG. 16 is perspective view of an example firearm-mounted camera system 100 . As has been previously described, the firearm-mounted camera system 100 includes firearm 80 and a camera system 102 . [0100] In this embodiment, camera system 102 does not include a foregrip. Instead, camera system 102 is mounted on top of firearm 80 . In other embodiments, camera system 102 is mounted on the side of firearm 80 . Another alternative is that camera system 102 is mounted at an angle between one of the sides and the bottom or the top of firearm 80 . In this manner, camera system 102 does not occupy the bottom of firearm 80 , and the bottom of firearm 80 may be used to support other accessories, such as a grenade launcher. [0101] As has been previously described, the camera system 102 includes camera assembly 104 , switching mechanism 106 , and display assembly 108 . In this embodiment, switching mechanism 106 includes housing 1600 , frame 1602 , aperture 1604 , and camera switch 702 . [0102] Housing 1600 is a hollow shell formed from plastic, metal, rubber, or any other suitable material and is configured to contain power supply 706 and control board 700 . In some embodiments, housing 1600 contains additional elements. Housing 1600 is described in more detail in FIGS. 17-18 . [0103] Frame 1602 is a U-shaped structure. Frame 1602 is secured to housing 1600 and together housing 1600 and frame 1602 form aperture 1604 . In some embodiments, frame 1602 is formed from three hollow beams that have square-shaped cross sections. In some embodiments, the hollow beams meet at a ninety-degree angle. In other embodiments, frame 1602 is formed from a single hollow beam that is bent or curved. In some embodiments, the hollow beams have a round or oval cross section. Frame 1602 is formed from hollow beams so that wires may run through frame 1602 to beam 500 to connect camera assembly 104 to switching mechanism 106 . [0104] Aperture 1604 is an opening through which front sight 88 of firearm 80 may protrude. In this manner, camera system 102 does not interfere with the operation of front sight 88 . [0105] In the embodiment shown, camera switch 702 is implemented as multiple momentary switches. For example, the embodiment shown in FIG. 16 includes two momentary switches, momentary switch 1606 on the right side of firearm 80 and another momentary switch on the left side of firearm 80 (not shown). Momentary switch 1606 is engaged only while it is being actuated (e.g., touched, pressed down, etc.). Momentary switch 1606 is mounted on the right side of firearm 80 . Momentary switch 1606 is electronically connected to control board 700 via switch cable 1608 . Although not shown, a second momentary switch is mounted on the left side of firearm 80 and is also electronically connected to control board 700 via a switch cable. [0106] As described above with respect to FIG. 7 , control board 700 and camera switch 702 operate to allow the user of camera system 102 to select the image or images to be displayed on display assembly 108 from the images received by the cameras in camera assembly 104 . In some embodiments, the control board displays two or more images simultaneously (e.g., by splitting the screen between images). For example, in some embodiments, multiple images are shown when multiple momentary switches are actuated concurrently. [0107] Camera assembly 104 has already been described in detail in FIGS. 3-5 . In the embodiment shown in FIG. 16 , beam 500 of camera assembly 104 is secured to frame 1602 . Camera assembly 104 is further secured to firearm 80 with securing assembly 1610 . Securing assembly 1610 includes a first ring 1612 and a second ring 1614 . First ring 1612 is coupled to second ring 1614 . First ring 1612 is secured around the distal end of beam 500 . Second ring 1614 fits over the end of barrel 84 of firearm 80 (similar to a bayonet). In some embodiments, the inner diameter of second ring 1614 is larger than the outer diameter of barrel 84 so that securing assembly 1610 may be slipped over the end of barrel 84 . In some embodiments, first ring 1612 and second ring 1614 are formed from a rigid material and include a tightening mechanism. In other embodiments, first ring 1612 and second ring 1614 are formed from a material with elastic properties. Other embodiments are possible as well. [0108] Display assembly 108 has already been described in detail in FIGS. 9-13 . Display assembly 108 is electronically connected to switching mechanism 106 by cable 906 . In other embodiments, display assembly 108 communicates with switching mechanism 106 by wireless radio frequency communication or optical communication via beam or fiber. [0109] FIG. 17 is a rear, perspective view of housing 1600 of an embodiment of switching mechanism 106 . In some embodiments, switching mechanism 106 includes mounting fixture 802 , battery tube access caps 1616 a - b , left switch connector port 1618 , right switch connector port 1620 , and video connector port 1622 . [0110] In this embodiment, mounting fixture 802 is an indentation in the bottom surface of housing 1600 that is configured to couple with a rail mount on a firearm. In some embodiments, mounting fixture 802 is configured to couple directly to a firearm. In yet other embodiments, mounting fixture 802 is configured to couple to another type of mount for a firearm. Further, in some embodiments, housing 1600 is integrally formed with firearm 80 . Yet other embodiments are possible as well. [0111] Battery tube access caps 1616 a - b are flat, round caps that are configured to couple with housing 1600 to seal access to the interior of housing 1600 . In some embodiments, battery tube access caps 1616 a - b have threads and are configured to be twisted on or off. In other embodiments, battery tube access caps 1616 a - b are configured to be pushed on and pulled off. Other embodiments are possible as well. Battery tube access caps 1616 a - b provide access to the interior of housing 1600 so that batteries may be replaced. Although the embodiment shown in FIG. 17 includes two battery tube access caps, other embodiments with more or fewer battery access caps are possible as well. [0112] Left switch connector port 1618 is a port in housing 1600 that is configured to receive the plug of a cable that is connected to a switch on the left side of the firearm. Right switch connector port 1620 is a port in housing 1600 that is configured to receive the plug of a cable that is connected to a switch on the right side of the firearm. Video connector port 1622 is a port in housing 1600 that is configured to receive the plug of a cable that is connected to display assembly 108 . In some embodiments, left switch connector port 1618 , right switch connector port 1620 , and video connector port 1622 are electronically connected to control board 700 . [0113] FIG. 18 is a top, cross-sectional view of an embodiment of switching mechanism 106 . Switching mechanism 106 includes power supply 706 . [0114] In this embodiment, power supply 706 includes batteries 1624 a - b . Batteries 1624 a - b are devices that convert stored chemical energy into electrical energy. In some embodiments, batteries 1624 a - b are rechargeable batteries (e.g., nickel metal hydride, lithium ion, etc.). In some other embodiments, power supply 706 may include more or fewer batteries. Further in some embodiments, power supply 706 may not include batteries at all. [0115] In some embodiments, switching mechanism 106 is connected to cable 506 . In some embodiments, cable 506 is connected to control board 700 and to camera assembly 104 . In some embodiments, cable 506 operates to direct electronic signals representing images received from camera assembly 104 to control board 700 . In some embodiments, cable 506 further operates to direct electronic control signals from control board 700 to camera assembly 104 . Further, in some embodiments, cable 506 operates to carry power from control board 700 or power supply 706 to camera assembly 104 . Cable 506 is routed through housing 1600 and into channel 1628 of frame 1602 . Channel 1628 is formed in the hollow space inside of the beam or beams that comprise frame 1602 . In this manner, cable 506 is routed around aperture 1604 and front sight 88 . [0116] Although the subject matter has been described in language specific to structural features and/or methodological acts, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as example forms of implementing the claims.
Systems, apparatuses, and methods for improving situational awareness for a user of a firearm are disclosed. An example camera system for a firearm includes a camera assembly, display panel, a mounting fixture, and switching mechanism. An example camera assembly includes a plurality of cameras fixedly oriented in a plurality of different directions. An example mounting fixture is secured to the camera assembly and configured to be removably attached to a firearm. An example switch is configured to select between the plurality of cameras to cause an image from the selected camera to be displayed on the display panel. An example method includes activating a firearm-mounted camera system, receiving a switch input from a user selecting a camera, generating an image of a portion of an environment with the selected camera, and displaying the image on a display panel to alert the user to conditions in the portion of the environment.
5
BACKGROUND OF THE INVENTION The present invention relates to stream data applications where a sequentially accessed buffer is used, and in particular to buffer systems employing memory management to prevent loss of still required or “leftover” buffer contents as a result of overwriting. The present invention also pertains to management of a prioritized buffer for stream data organized in fixed size packets or cells, as may be employed in wireless multimedia applications. Wireless voice communications such as provided today by cellular systems have already become indispensable, and it is clear that future wireless communications will carry multimedia traffic, rather than merely voice. ATM (asynchronous transfer mode) technology has been developed over wired networks to carry high-speed data traffic with different data rates, different quality-of-service (QoS) requirements (for example, data reliability, delay considerations, etc.), different connection or connectionless paradigms, etc. for multimedia communications. It is then natural to assume that in the future wireless ATM-based (WATM) service will be provided at the consumer end of a wired network. Existing efforts towards building a wireless local-area network (LAN) are focused around emerging standards of IEEE 802.11 in the United States and HIPERLAN in Europe. While these standards are almost mature, their development did not take into consideration ATM-based service requirements of QoS guarantees for both real-time and data traffic. Essentially, these requirements come about by multiplexing video, audio, and data services (multimedia) in the same medium. Audio data does not require the packet-error reliability required of data services, but cannot tolerate excessive delay. Video data can in general suffer more delay than audio; however it is intolerant to delay jitter. These delay and packet-error rate considerations forced ATM to adopt a connection-oriented service. It also forced error-control to be done end-to-end, instead of implementing error-control between every two nodes within the specified connection (error-control is a method of ensuring reliability of packets at a node, whereby a packet error is detected, and then a packet retransmission request is sent to the transmitting node). Such a strategy was feasible with the wired fiber-optic networks, which has a very small packet error rate. Wireless networks do not in general provide such low-error rates. Delay considerations are also important for ATM service. A wired ATM network will simply block any services for which it cannot guarantee the required QoS. Typically wireless networks do not allow such a feature; the delay actually can increase exponentially in an overloaded network. Such a channel-access protocol is indeed specified in IEEE 802.11 and HIPERLAN. The services that are supported over ATM have one of the following characteristics with regards to the time-varying feature of the data rate of service; also listed are the QoS parameters which are expected to be sustained by the network: Constant Bit Rate (CBR): Specify Bit Rate Variable Bit Rate (VBR)—RT: Specify Sustained Cell Rate, Max Burst Size, Bounded Delay Variable Bit Rate (VBR)—NORT: Specify Sustained Cell Rate, Max Burst Size Available Bit Rate (ABR): Best Effort Service—No Bandwidth Guarantees Except for a Minimum Rate Negotiation Unspecified Bit Rate (UBR): ABR without any Guaranteed Rate Clearly, an important issue in designing a WATM system is that the Medium Access Control (MAC) protocol, which specifies the method of access to the wireless channel among multiple users, must satisfy the basic requirements of ATM. One method of implementing a MAC protocol is to use Time-Division Multiple Access (TDMA), wherein TDMA frames are divided into slots, each of which is assigned to an unique user. In general, this assignment can either be fixed, resulting in classical TDMA, or could be variable, resulting in reservation-based TDMA (R-TDMA). In R-TDMA, a sub-framing occurs in terms of different “phases” of the TDMA frame consisting typically of a “control” phase where reservations are asked and assigned, and a “data” phase, where transmission slots are used. To accommodate ATM QoS, the MAC protocol could implement R-TDMA utilizing a sequence of Control-Data Frames (CDFs), each CDF consisting of a control phase followed by a data phase. During the control phase, multiple wireless terminals specify a number of ATM slots required for their use. Once this request is successful, a certain number of ATM slots will be reserved for a particular wireless terminal and the wireless terminal can then transmit its designated packets in a specified sequence during the data phase. To implement R-TDMA, the MAC layer needs a single prioritized buffer. Two issues are important to the MAC layer buffer control. First, incoming cells from the upper layer have to be sorted according to their ATM QoS specifications, i.e. ATM cells which have more immediate requirement must be sent earlier. Second, the MAC layer must support power saving, i.e., the MAC layer should be active only when required. The prioritized buffer implementation presents a problem in buffer management, as memory fragmentation can result. For example, assume first that the buffer is empty. Then assume that 5 ATM cells occupied sequential addresses in memory. Because of QoS considerations, assume that ATM cells 2 and 4 were transmitted during the current CDF, leaving gaps in the buffer and resulting in a memory fragmentation problem. Since the buffer size cannot be infinite, a method must be found to reuse these gaps. Generally, the fragmentation problem could be solved in software executed by the processor, i.e., a processor-based embedded system is used to manage defragmentation of the prioritized buffer. A simple technique could recopy all the “leftover” packets within the buffer to the head of the buffer. However, such a solution, although programmable, can be quite expensive with respect to the processor's resources. For bursty sources, it is possible that there may be a significant number of leftover packets within the buffer, and moving all of those packets is a significant overhead. Note that this creates two problems, namely that a significant amount of processor time could be used for memory defragmentation, and also that an upper bound to the amount of time that a processor needs for memory defragmentation is large causing problems in how the scheduling of processor tasks are to be undertaken. Another solution with reference to the above architecture is to copy all the leftover ATM cells from the “input” buffer to another place, for example an additional buffer, and implement memory defragmentation in a controlled way using processor software, i.e., copy the leftover packets in the prioritized buffer to appropriate spaces within the additional buffer. This alleviates the problem significantly as compared to the method described above, as leftover packets occurring only during the current CDF must be moved every time. However, the problem in this technique is memory duplication and also the processor essentially implements two memory copy commands for every byte that is transmitted, namely one from the prioritized buffer to the additional buffer, and another from the additional buffer to the physical layer FIFO. SUMMARY OF THE INVENTION It is an object of the present invention to provide a sequentially accessible buffer including memory management means arranged to defragment the buffer, which management of defragmentation is implemented in a manner that the processor is not loaded with the problem of either relocating or “writing-around” leftover packets. It is a further object of the present invention that such management of defragmentation is implemented in a simple and yet extremely controlled way which maximizes the buffer utilization, and minimizes the processor interaction with the defragmentation. In the case of a WATM terminal, minimizing processor interaction with the defragmentation enables better power-saving. These and other aspects of the present invention are satisfied by providing a buffer comprising an addressable memory system which is divided into sequential equal-sized pages for storing respective data packets having the same number of bytes. (When the data packets are ATM cells, each is 53-bytes in length.) The invention is characterized in that the memory system further comprises first memory locations for storing tags associated with the respective pages, each tag indicating whether the associated page is empty or full; and address generation means responsive to data states derived from the stored tags, respectively, for developing a succession of addresses of memory locations in the memory system which control sequential writing into the buffer of bytes contained in data packets, the addresses in said succession jumping over addresses within pages which are full, thereby bypassing and avoiding overwriting pages which are full. While the tags are generated by the processor, the data states derived from the stored tags, and the succession of addresses of memory locations are generated without further processor intervention. The present invention is further characterized in that the address generation means comprises means responsive to said data states for forming first address components or pointers indicative of pages which are empty; means for forming second address components indicative of byte positions within packets; and means for combining the first and second address components. The succession of addresses of memory locations may be formed by simply concatenating page number and byte number. A further aspect of the present invention is that the memory system comprises second memory locations for storing said data states; and means for deriving said data states from the stored tags, respectively, in a manner that a stored data state is preserved when a corresponding tag indicates that a corresponding page is full. The data states which control the formation of the succession of addresses of memory locations are thus derived from the tags written by the processor in a manner which avoids conflict between the processor's updating of tags and the generation of addresses in response to requirements dictated by the MAC layer. Additional aspects of the present invention are that a variable number of the data packets are received or are to be transmitted within R-TDMA frames, each of which includes a data phase containing a plurality of time slots for containing data packets, and a control phase for reserving time slots, and further that the data packets correspond to respective types of services having respective quality of service requirements, and the memory system is a prioritized buffer for containing data packets sorted in accordance with the respective quality of service requirements of the type of traffic to which the packets correspond. Other objects, features and advantages of the present invention will become apparent upon perusal of the following detailed description when taken in conjunction with the appended drawing, wherein: BRIEF DESCRIPTION OF THE DRAWING FIG. 1 shows the organization of a Control Data Phase (CDF); FIG. 2 generally illustrates a prioritized buffer within the MAC layer; FIG. 3 shows the MAC subsystem in accordance with the present invention, including memory defragmentation circuitry; FIG. 4 shows a block diagram implementation of the memory defragmentation circuitry of FIG. 3, to implement a “write-around” method; and FIG. 5 shows the memory defragmentation circuitry of FIG. 4 in greater detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is described as part of a WATM terminal, as an example. However, it should be understood that the invention can be used in any case where a technique is needed to bypass occupied locations in a sequentially accessed buffer whose contents are still required, but may be overwritten and lost (typically in stream data applications). Referring first to FIG. 1 of the drawing, the organization of a Control-Data Frame (CDF) is shown to consist of a control phase followed by a data phase. During the control phase, multiple wireless terminals specify a number of ATM slots required for their use. Once this request is successful, a certain number of ATM slots will be reserved for a particular wireless terminal and the wireless terminal can then transmit its designated packets in a specified sequence during the data phase. For the purpose of illustration, only the time axis is considered, where time is divided into slots, each of which equals the length of a control packet or a data packet plus some guard time. As an example, a typical embedded system implementation for wireless ATM is described. FIG. 2 generally shows a prioritized buffer 10 for all ATM cells and a buffer server 12 , all within the MAC layer 14 . FIG. 3 describes the hardware for the MAC subsystem which is very programmable to accommodate improvements in the MAC protocol. The MAC layer hardware design provides a buffered data path between an ATM-MAC interface to the ATM and a MAC-PHY interface to the physical layers PHY that allows for MAC layer scheduling and management functions to take place with a minimum of incurred delay or packet loss. The download data path from the ATM-MAC interface to the MAC-PHY interface includes: an input FIFO 20 to accommodate the data rate in accordance with the UTOPIA European standard and to cushion the ATM data flow so that memory defragmentation can be achieved; a prioritized buffer 22 which is composed of dual port, random access via one port, sequential access via the other, memories (SARAMs, not shown) in which scheduling takes place; and an output FIFO 24 to accommodate the physical layer data rate and also to allow for insertion of MAC overhead parameters. Stream data enters buffer 22 via its sequential port to be operated on via its RAM port by the processor or MPU 34 , and then passed on to the next layer, again via its sequential port. The upload data path is also a SARAM upload buffer 26 that collects packets, allows RAM access to MAC layer data, and continues sequential access to the ATM layer. A DPRAM mailbox 28 is provided for mailbox functions between MAC and ATM layers to pass parameters and status information. Programmable devices (PLDs) 30 and 32 , control the interfaces, the data paths and the time keeping functions. The processor or MPU 34 is coded to perform all scheduling and management functions. Preferably, a common hardware design is provided for use in a base station or in a wireless terminal. Two sets of operating code will be resident in EEPROM 36 . By switch selection one of the two sets of code will be called into SRAM 38 on power up to configure as either a base station (BS) or as a wireless terminal (WT). PLDs 30 and 32 are provided to augment the operations of MPU 34 . PLD 30 contains the address latches and chip select decodes that implement the memory map, command and status registers for processor interaction, and the signal set to interface with the ATM layer via Utopia. PLD 32 complements the processor with the timestamp counter and the implementation of phases of the CDF. Additionally, PLD 32 contains the physical layer interface signal set, and the command and status registers to interact with MPU 34 . MPU 34 is preferably a MIPS RISC processor of the R3000 class, for example IDT79R3041. EEPROM 36 is preferably 128k in size and holds boot code, a monitor, and two sets of operating code (BS and WT). 128k of SRAM 38 is also preferably 128k in size; it provides storage for dynamic parameters and general work space. To solve the memory fragmentation problem, the processor MPU 34 must first stop the flow of ATM packets from FIFO 20 into buffer 22 , and then remove the gaps in the memory. FIG. 4 shows as a block diagram the circuitry for implementation of memory defragmentation by a “write-around” method. In this Figure, ATM cells are assumed (53-byte packets) and the buffer is assumed to be composed of 154 ATM cells which is approximately 8K of memory. This Figure describes the additional hardware which controls the “prioritized buffer” address counter in FIG. 3 . The buffer is organized along packet boundaries or pages for convenience of operation and minimizing the logic to implement it. MPU 34 , which executes the algorithms on the buffer, maintains a table of pointers to each packet boundary, and, therefore, knows the location of all leftover packets. A tag register 40 is provided, which has as many bits as there are packet boundaries in buffer 22 . Each bit tags a boundary or page as either occupied with a leftover, or free for use, zero being free and one being taken. After each algorithm execution, MPU 34 refreshes tag register 40 by writing ones to those locations still occupied and resetting the remainder to zero. As previously stated, buffer 22 is implemented as a dual port ram, one port being randomly accessed by MPU 34 while the other port is sequentially accessed by an address or byte counter 42 , driven by the clock CL of the input stream data source. The counter 42 is decoded by decoder 44 to mark packet boundaries or ends of ATM cells in buffer memory 22 , each referred to hereafter as “END OF CELL”, as well as other predetermined byte counts within a cell or packet referred to hereafter as “LOAD TAGS” and “PRESET MARK”. Upon decode of END OF CELL, a marker, or token bit, in a page register 46 is advanced to a position corresponding to the next empty fragment, or page, in buffer 22 . A shadow register 48 is provided to track the progress of the marker bit in page register 46 . Shadow register 48 fills with ones as packets fill the pages of buffer 22 . MPU 34 reads the contents of shadow register 48 to determine how many packets are in buffer 22 . After scheduling tasks are completed MPU 34 then writes to tag register 40 as previously described. Shadow register 48 keeps constant pace with incoming packets so as to avoid conflicts with updates to tag register 40 by MPU 34 . The updates to tag register 40 are transferred to shadow register 48 conflict free. The marker bit in page register 46 is then caused to be set to the lowest free page in buffer 22 . The sequential addresses for addressing buffer 22 are formed as a sum by an adder 48 of two components, namely a free page starting address and a fixed length packet byte count output from byte counter 42 , there being 53 bytes in a cell or packet for ATM. Each free page starting address is generated from a multiplexedarray of page addresses (preferably implemented as a gate array) in response to the position of the marker bit in page register 46 . The END OF CELL decode from byte counter 42 is used to advance the marker bit position in page register 46 , and the PRESET MARK and LOAD TAGS decodes from byte counter 42 update the shadow register and execute the tag updates. FIG. 5 illustrates the details of the interactions between page register 46 (composed of D flip-flops 46 . 0 , 46 . 1 , . . . 46 . 153 ), shadow register 48 (composed of D flip-flops or memory locations 48 . 0 , 48 . 1 , . . . 48 . 153 ) and tag register 40 (composed of D flip-flops or memory locations 40 . 0 , 40 . 1 , . . . 40 . 153 ). Tag register 40 may be written to by MPU 34 independently of any other operations via respective MPU BUS inputs to the D inputs and an MPU WRITE input to the toggle input of the respective flip-flops 40 . 0 , 40 . 1 , . . . 40 . 153 . To transfer the update of tag register 40 to shadow register 48 conflict-free a command bit is set in response to the decode PRESET MARK and transferred in response to the decode LOAD TAGS so as not to interfere with shadow or marker bit movements. Page register 46 and shadow register 48 interact through a network of AND gates 50 . 0 , 50 . 1 , . . . 50 . 153 , and 52 . 0 , 52 . 1 , . . . 52 . 152 (not shown) which provide a logic one on the D input of the flip-flop of page register 46 at a position corresponding to the lowest free or empty page. AND gate 50 . 0 feeds the D input of flip-flop 46 . 0 and receives a first input which is a constant logic one provided by connection to power supply voltage VCC, and a second input which is the NOT Q output of flip-flop 48 . 0 , whereas subsequent AND gates 50 . 1 . . . 50 . 153 in the series also feed the D inputs of the corresponding gates 46 . 1 . . . 46 . 153 , and receive the second input which is the NOT Q output of the corresponding flip-flops 48 . 1 . . . 48 . 153 . However the first inputs received by AND gates 50 . 1 . . . 50 . 153 are the outputs of gates 52 . 0 . . . 52 . 152 (not shown). AND gate 52 . 0 also receives a first input which is a constant logic one provided by connection to power supply voltage VCC, and receives a second input which is the Q output of flip-flop 48 . 0 , whereas subsequent AND gates 52 . 1 . . . 52 . 152 (not shown) in the series also receive the second input which is the Q output of the corresponding flip-flops 48 . 1 . . . 48 . 2 . However, the first inputs received by AND gates 52 . 1 . . . 52 . 152 (not shown) are the outputs of the immediately prior gates 52 . 0 . . . 52 . 151 (not shown). Further NAND gates 54 . 0 , 54 . 1 , . . . 54 . 153 feed preset inputs of flip-flops 48 . 0 , 48 . 1 , . . . 48 . 153 , respectively, and receive first inputs which are the Q outputs of flip-flops 46 . 0 , 46 . 1 , . . . 46 . 153 , respectively, and a second input which is the PRESET MARK decode produced by decoder 44 . On powering up, the page register zero location or position maintained by flip-flop 46 . 0 is preset to a logic one via NAND gate 54 . 0 while all other locations in all three registers are cleared to logic zero. Thus, page zero is initially active, while all others are initially inactive. A packet arriving from the stream data source causes the shadow register zero position maintained by flip-flop 48 . 0 to be set during its byte one interval in response to the LOAD TAGS decode, indicating this page is filled. Logic one is passed to page register position one maintained by flip-flop 46 . 1 . This position is now enabled to be set while all other page positions are conditioned to be cleared by the END OF CELL decode produced by decoder 44 in response to the currently arriving packet. It can be seen from the logic in FIG. 5 that if shadow register position one maintained by flip-flop 48 . 1 were set, the logic one originally derived from VCC would be passed on to the next page register position, bypassing or jumping over position one. If several successive positions in the shadow register were set, that the logic one would be passed on to the next position where the shadow register is at zero. This is the mechanism for writing around occupied locations in the buffer memory that contain leftover packets. In this scheme MPU 34 reads the status of shadow register 48 to determine occupied positions. Tag register 40 is provided to operate on shadow register 48 . A one written to a position in tag register 40 will preserve the current state of its companion in shadow register 48 while a zero will clear that position. Clearing indicates reuse of the position is possible while preserving indicates the content of the page is still needed. All updates occur during specific times during a packet reception (indicated by the various decodes from decoder 44 ) so that setup for the next packet is conflict free. It should be appreciated that the objects of the invention have been satisfied by providing management of buffer defragmentation is implemented in a manner that processor MPU 34 is not loaded with the problem of either. relocating or “writing-around” leftover packets. While the present invention has been described in particular detail, it should also be appreciated that numerous modifications are possible within the intended spirit and scope of the invention.
A prioritized buffer for the Medium Access Control (MAC) layer for multimedia applications, in particular wireless Asynchronous Transfer Mode (ATM) in which reservation based TDMA is performed on the basis of control data frames (CDFs), is formed by an addressable memory system which is divided into sequential equal-sized pages for storing respective data packets or ATM cells having the same number of bytes. The memory system includes a tag register for storing tags associated with the respective pages, each tag indicating whether the associated page is empty or full, a shadow register for storing conflict-free updates from the tag register, and a page register for storing pointers to the lowest free or unoccupied page. Sequential buffer addresses of memory locations in the memory system, which control sequential writing into the buffer of bytes contained in data packets, are generated from summing a first address component responsive to the contents of the page register and a second address component which is a byte count of a current packet being received from a stream data source. A succession of byte addresses is produced which jumps over addresses within pages which are full, thereby bypassing and avoiding overwriting pages which are full.
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FIELD OF THE INVENTION [0001] The present invention provides a natural composition comprising Coleus forskohlii extract and Bacillus subtilis BS139 (the storage ID is NRRL NO. B-50347). The user could achieve the goal of weight loss healthily while taking the natural composition. Meanwhile, the user could evaluate the metabolite rate to achieve the goal of weight loss. BACKGROUND OF THE INVENTION [0002] Obesity is the most important health problem in the modern society and is the most serious modern civil disease. There are lots of factors could cause obesity, such as body activities decrease, malnutrition, excessive starches and sugars intake, or excessive fat intake, etc. Wherein excessive fat intake is the most important factor. Moreover, people now changing their diet style and prefer to eat at outside, so that people often over intake unnecessary fat. Even some people select the food carefully, the invisible fats in all kinds of fresh food and artificial food is therefore unavoidable. Besides, people usually live with a busy work life, and become comfortable and relaxed state after work at home, this would cause fat accumulation in the body easily in the long run and losing weight would become more difficult to cause healthy body at risk. [0003] Studies show that there is about 75-80% people in a civilized society population would be overweight or obese in their lifetime. Obesity would not only cause appearance defects, and also induce psychological and social obstacles and further affect the work ability; besides, it is easy to cause some physiologically symptoms, such as edema, cardiac hypertrophy, fatty liver, cholelithiasis and urolithiasis, musculoskeletal disorders, gynecologic cancers such as breast cancer or uterine cancer, gout and hyperuricemi, hyperlipidemia, angina, diabetes, hypertension, stroke or infarction and so on. According to the latest statistics from the Ministry of Health and Welfare (Taipei City, Taiwan R.O.C.), overweight or obese of adult men has reached 51% in our country, and, overweight or obese of adult women also reached 36%. In primary school, the ratio of overweight or obese in children is, 29% for boy and 21.0% for girl. Similarly, according to the latest statistics from WHO, 39% of adults aged 18 years and over were overweight and 13% were obese in worldwide. These data shows that the rate of overweight and obesity continues to rise. In addition, in the top ten causes of death, eight of the top ten causes of death are associated with obesity, such as cancer, heart disease, cerebrovascular disease, diabetes, chronic lower respiratory diseases, hypertension, chronic liver disease and cirrhosis, chronic kidney disease, etc. Therefore, it is important to maintain a healthy body weight for a personal goal to most people. [0004] There are all kinds of dazzling, strange ways to lose weight, but some of them are not healthy ways to lose weight. The best way is to rely on regular exercises and changing diet. However, people are often lack of patience in losing weight, so that his/her biggest problem is that he/she cannot keep exercise and often cannot refuse to delicious foods. That is why the weight losing product is the best choice for the people who want to lose weight. Some common weight losing products, such as weight losing drug approved by the Ministry of Health and Welfare—phenyl propanolamine could promote the body metabolic rate, increase calorie consumption and reduce appetite, etc., and could also cause weight loss effectively in a short time. However the accompanied side effects such as palpitations, vomiting, insomnia and other side effects would happen, some people would have severe anorexia. Although the users achieve the goal of weight loss successfully, he/she would also lose his or her health. [0005] In other words, most people would only focus on reducing the body “weight” instead of reducing the body “fat” when they carry on losing weight. That is, after losing weight, the whole body fat even the abdominal fat might not be changed. However, only the lower triglyceride level represents the effectiveness of losing weight. Therefore, providing a safe, healthy weight losing function agent without effecting the daily life, to improve existing method is an urgent mission for people who is overweight and who wants to maintain a health, low body fat percentage. SUMMARY OF THE INVENTION [0006] According to above description, the present invention provides a natural composition comprising Coleus forskohlii extract and Bacillus subtilis BS139. The user could achieve the goal of losing weight healthily while taking the natural composition. Meanwhile, the user could evaluate the metabolite rate to achieve the goal of losing weight. [0007] The present invention provides a composition for reducing fat accumulation, which comprises Coleus forskohlii extract and Bacillus subtilis BS139, wherein the Bacillus subtilis BS139 is stored in Agricultural Research Service (NRRL), the storage ID is NRRL NO. B-50347. The present invention composition for reducing fat accumulation is composed by Coleus forskohlii extract and Bacillus subtilis BS139 with a specific ratio. [0008] The Bacillus subtilis of the present invention is stored in Agricultural Research Service (NRRL), the address is: Jamie L. Whitten Building 1400 Independence Ave., S. W. Washington D.C., 20250, the storage number is NRRL NO. B-50347, and the classification name is Bacillus subtilis and the storage time is Feb. 1, 2010. [0009] In one example of the present invention, the content of Coleus forskohlii extract is 0.01 wt % to 0.05 wt %, and the content of Bacillus subtilis BS139 is 0.02 wt % to 0.08 wt %. [0010] In one example of the present invention, the natural composition could reduce 20% to 40% rate of body weight gain in an animal or a human body. [0011] In one example of the present invention, the natural composition could reduce 10% to 80% weight of abdominal fat in an animal or a human body effectively. [0012] In one example of the present invention, the natural composition could reduce 5% to 12% Triglyceride in an animal or a human body effectively. [0013] In one example of the present invention, the natural composition could reduce 15% to 25% caloric intake rate in an animal or a human body effectively. [0014] In one example of the present invention, the natural composition is applied to a pharmaceutical product, health food, health-care food, food or animal feed. [0015] The present invention also provide a preparation method of a pharmaceutical composition for treating obesity by a plant extract, wherein the plant extract comprising: effective amount of 0.01 wt % to 0.05 wt % Coleus forskohlii extract and effective amount of 0.02 wt % to 0.08 wt % Bacillus subtilis BS139, wherein the Bacillus subtilis BS139 is stored in Agricultural Research Service (NRRL), the storage ID is NRRL NO.B-50347. BRIEF DESCRIPTION OF THE DRAWINGS [0016] FIG. 1 Illustration of the weight change of female rats after feeding the different feeds in different days. [0017] FIG. 2 Illustration of the weight change of female rats after feeding the different feeds in different weeks. [0018] FIG. 3 Illustration of the feed intake of female rats after feeding the different feeds in different weeks. [0019] FIG. 4 Illustration of the feed efficiencies of female rats after feeding the different feeds. DETAILED DESCRIPTION OF THE INVENTION [0020] Experimental Animal and Feeding Environment [0021] Eighteen 5-weeks old Wistar female rats were used as experimental animals, each rat was 160 g and was kept in the rodent animal feeding room of Agricultural Technology Research Institute (Hsinchu City, Taiwan R.O.C). The temperature of the rodent animal feeding room was controlled in 23° C. (20-26° C.) and the light cycle was 12-hours lighted. The experimental rats were kept in cages, which were sterilized by high temperature and high pressure; besides, the feeding water was provided with water bottles, which were also sterilized by high pressure. [0022] The Construction of Different Groups of Wistar Female Rats Feeding with Different Feeds [0023] Two rats were kept in one cage, and the animal numbers, cage numbers were labeled. The six-week experiment was followed by 7-days habitual period. The rats were randomly into 3 groups: control group, oil-added feed group, oil-added and drug treated feed group. There were 3 cages in total, and there were 6 rats in each group. The rats in the control group were feed with imported granular rodent feed (Lab Diet® 5001 Rodent Diet). The rats in oil-added feed group was feed with 10% soybean oil containing high-fat feed, wherein the high-fat feed was prepared by adding 10% soybean oil after smashing the imported granular rodent feed and shaping into a lump. The high-fat feed was prepared two days before feeding, so as to avoid the problem of oil oxidation. The rats in the oil-added and drug treated feed group were feed with high-fat feed, and the Coleus forskohlii extract and Bacillus subtilis BS139 were then added. The main nutritious ingredients in the feeds were listed as Table 1, wherein all the data in the table were average values. [0000] TABLE 1 Main nutritious ingredient in the feeds Granular rodent feed group (Lab Diet ® 5001 Oil-added Group Rodent Diet) feed group Total Calories (kcal/kg) 4,070 4,560 Total Proteins (%) 23.7 21.8 Total Fat (%) 5.2 14.4 Total Calcium (%) 0.94 0.86 Total Phosphorous (%) 0.68 0.60 [0024] Experiment Analysis [0025] The rats were weighted in the beginning of the experiment (Day 1) and every week respectively, and the weekly feed consumption of each rats were recorded. The daily clinical symptoms were observed during experiment, and whether the clinical symptoms or death were existed in each animal was recorded. The tail vein blood was collected in the end of experiment (Day 42), and the glucose level, triglyceride level, aspartate aminotransferase (AST) level, and alanine aminotransferase (ALT) level of each rats were tested by Automated Clinical Chemistry Analyzer (Kodak Ektachem DT-II System, Rochester, N.Y., USA). Then the rats were sacrificed for pathological observation, and the tissue weight was recorded. Example 1. The Intake Amounts of Feeds and Calories [0026] Please refer to the Table 2, the feed intake amounts were slightly different between different groups during experiment period, but there was no statistical difference (P>0.05), wherein the values in Table 2 were average values. [0000] TABLE 2 The intake amounts of feeds (g/rat/week) and calories (kcal/rat) Total Total calories feed intake amount Week Week Week Week Week Week intake (calculated groups 1 2 3 4 5 6 amount value) Control group 151 185 185 209 204 198 1,132 4,607 Oil-added feed 138 134 210 224 244 218 1,168 5,326 group oil-added and drug 177 134 192 194 262 183 1,142 5,207 treated feed group [0027] To compare the rodent feed group with control group, the oil-added feed group was feed with 10% soybean oil containing high-fat feed. In the oil-added feed group, the feed intake amount was 8.6% lower than control group during week 1, the amount was even 27.6% lower than control group during week 2; however the feed intake amount was higher than control group afterward, the amount was increased 7-19% during week 3 and week 6. The feed intake amount of the oil-added feed group was decreased during week 1 and week 2, which seemed to be affected by the added oil; however, after two weeks habituation, the feed intake amounts during following 4 weeks were higher than control group. During experiment period, the total feed intake amount of oil-added group was similar to the total feed intake amount of control group; however, the total calories intake amount was 15.6% higher than control group, which was matched with the purpose of high-fat feed to increase the rat's calories intake amount. [0028] The rats in the oil-added and drug treated feed group were then feed with Coleus forskohlii extract and Bacillus subtilis BS139, and the intake amount was measured, the test result of intake amount change in this group is not consistent with the test result of oil-added group. During week 1, the rat's feed intake amount of oil-added and drug treated feed group was 17.2% higher than the control group, and was 28.3% higher than the oil-added feed group. During week 2, the rat's feed intake amount of oil-added and drug treated feed group was similar to the rats in oil-added feed group, but 27.6% lower than the rats in control group. Then, during the week 5, the rat's feed intake amount of oil-added and drug treated feed group was 28.4 higher than the rats in control group. During week 4 and week 6, the rat's feed intake amount of oil-added and drug treated feed group was both 7% lower than the rats in control group. The added Coleus forskohlii extract and Bacillus subtilis BS139 seem to inhibit the rat's feed intake amount after one week (that is, week 2, 4, 6). During the whole experiment period, the rat feed intake amount of oil-added and drug treated feed group was similar to rats in control group, however, the total calories intake amount was 13% higher than the rats in control group but 2.6% lower than the rats in the oil-added feed group. Example 2: Growth Curve and Weight Changes [0029] Please refer to the FIG. 1 , all the rats in different groups were similar to each other in weight, which is about 117 g in the beginning; however, all the rats in different groups gain weight as more feed days. The rats in the control gain weight gradually slow down as more feed days, and the growth curve of the oil-added feed group was different with the control group. It's noteworthy that the rat's weight of the oil-added and drug treated feed group was lower than control group and oil-added feed group from day 21, the difference between the oil-added and drug treated feed group and control group, oil-added feed group was increase as more feed days but the increase of the difference was not equidistant. [0030] Please refer to the Table 3, all the data in the Table 3 were average values, the superscripts showed the significant differences in the same row. Wherein the P value of a and b was smaller than 0.05, the P value of a and c was smaller than 0.01, and the P value of a and d was smaller than 0.001. [0000] TABLE 3 Weekly Weight gain (g/rat) Total Week Week Week Week Week Week weight Group 1 2 3 4 5 6 gain Control 24.2 a 22.2 a 16.5 a 16.5 7.7 3.2 90.2 a group Oil-added  8.0 b 42.3 d 20.2 a 12.5 7.8 7.7 98.5 a feed group oil-added 14.3 ab 35.2 cd  5.2 c 10.3 4.7 5.2 74.8 b and drug treated feed group [0031] The rats in the control group gained weight over 22 g during week 1 and 2, gained weight about 16.5 g during week 3 and 4, gained 7.7 g during week 5, and gained only 3.2 g during week 6. The rats in oil-added feed group gained only 8 g during week 1, which is significantly lower than control group (P<0.05). On the other hand, the gained weight in oil-added feed group was significantly higher than control group during week 2, which is 42.3 g (P<0.001). Then, the weekly weight gain in control group and oil-added feed group was no significant difference between two groups during week 3-6. The weight gain in oil-added and drug treated feed group was no difference to the other two groups during week 1, but the weight gain in oil-added and drug treated feed group was significantly higher than control group during week 2, which is 35.2 g (P<0.01). During week 3, the rats in oil-added and drug treated feed group only gain 5.2 g, which was significantly lower than control group and oil-added feed group (P<0.01). Then, the weekly rate of weight gain in oil-added and drug treated feed group was no difference to the other groups in statics, but the values of weight gain in oil-added and drug treated feed group was lower than in control group and oil-added feed group during week 4-6. During the experiment period, the total weight gain in control group and oil-added feed group was 90.2 g and 98.5 g respectively. In contrast, the oil-added and drug treated feed group only gain 74.8 g, which was significantly lower than the other groups (P<0.05). The result showed that the weight curve of oil-added and drug treated feed group was lower than the control group and oil-added feed group since week 3, which prove that the feed of the composition of 0.01 wt % to 0.05 wt % Coleus forskohlii extract and 0.02 wt % to 0.08 wt % Bacillus subtilis BS139 could help reduce weight gain. [0032] Please refer to FIG. 2 and FIG. 3 , the rat in the group of high-fat feed, the amount of feed intake could be reduced due to accommodation in early stage, so as to reduce the weight gain of the rat (week 1). However, the amount of feed intake in oil-added and drug treated feed group was 17% higher than the control group, but the weight gain was 40% lower than the control group, which represented that the added Coleus forskohlii extract and Bacillus subtilis BS139 composition seemed to have the function of inhibit the weight gain. Except for week 2, similar result was observed during week 3, 4, 5 and 6. In comparison with control group, the amount of feed intake in oil-added and drug treated feed group was 3.8% higher, but the weight gain was 68.5% lower during week 3; the amount of feed intake in oil-added and drug treated feed group was 28.4% higher, but the weight gain was 38.7% lower during week 5. In comparison with oil-added group, the amount of feed intake in oil-added and drug treated feed group was 8.6% higher, but the weight gain was 74.3% lower during week 3. Furtherly, the amount of feed intake in oil-added and drug treated feed group was 7.4% higher, but the weight gain was 39.7% lower during week 5. The result showed that the amount of feed intake was increased in the oil-added and drug treated feed group, but the increase rate of weight gain was lower than control group and oil-added feed group. That is, the composition of 0.01 wt % to 0.05 wt % Coleus forskohlii extract and 0.02 wt % to 0.08 wt % Bacillus subtilis BS139 in the present invention could reduce 20% to 40% rate of body weight gain in an animal or a human body. Example 3. Tissue Weight [0033] All the animals were healthy and not dead, nor observed any clinical symptoms during experiment period. Please refer to Table 4, all the data in the Table 4 were average values, the superscripts showed the significant differences of statics in the same row. Wherein the P value of a and b was smaller than 0.05, the P value of a and c was smaller than 0.01. The heart and kidney weight was no difference between all the groups after animal sacrificed. However, the abdominal fat weight of oil-added feed group was 58.5% higher (P<0.05) than control group; but the abdominal fat weight of oil-added and drug treated feed group was 44.5% lower (P<0.01) than oil-added feed group, and was 12.1% lower (P>0.05) than control group, while the rats in oil-added and drug treated feed group were also feed with high-fat feed. The Coleus forskohlii extract and Bacillus subtilis BS139 composition was added in the oil-added and drug treated feed group, which inhibit the abdominal fat accumulation under similar calories intake condition. The abdominal fat accumulation in the oil-added and drug treated feed group was significantly lower than control group and oil-added feed group, which proved that the Coleus forskohlii extract and Bacillus subtilis BS139 composition of the present invention could reduce the fat intake and reduce the fat accumulation effectively. That is, the composition of 0.01 wt % to 0.05 wt % Coleus forskohlii extract and 0.02 wt % to 0.08 wt % Bacillus subtilis BS139 in the present invention could reduce 10% to 80% weight of abdominal fat accumulation in an animal or a human body. [0000] TABLE 4 Tissue weight (g) Oil-added Control Oil-added and drug treated Tissue group feed group feed group Heart 0.86 0.88 0.90 Kidney 2.42 2.44 2.26 Abdominal fat 3.23 b 5.12 a 2.84 bc Example 4. Biochemical Profile of Blood [0034] Please refer to Table 5, all the data in the Table 5 were average values. The superscripts showed the significant differences of statics in the same row, for example, the P value of a and c was smaller than 0.01. In comparison with control group, the blood glucose level was lower (P<0.01) in the oil-add feed group, which means that the high-fat feed could reduce the blood glucose level, but the triglycerate level was slightly higher (16.5%). The blood glucose level in oil-added and drug treated feed group was lower (P<0.01) than control group; but the increase level of triglyceride (5.5%) in oil-added and drug treated feed group was 11% lower than oil-added feed group. Therefore, the added Coleus forskohlii extract and Bacillus subtilis BS139 composition could reduce the triglycerate when the rats eat more high-fat food, wherein the mechanism might not be related to glucose generation, but related to lipid metabolism and generation. That is, the composition of 0.01 wt % to 0.05 wt % Coleus forskohlii extract and 0.02 wt % to 0.08 wt % Bacillus subtilis BS139 in the present invention could reduce 5% to 12% triglyceride in blood either an animal or a human body. [0000] TABLE 5 Biochemical Profile of Blood Oil-added and drug Control Oil-added treated Item group feed group feed group Glucose (mg/dL) 232 a 146 c 151 c Triglycerate (mg./dL)  69.7  81.2  73.5 aspartate aminotransferase 160 135  93.2 (AST)   alanine  41.3  49.5  40.3 aminotransferase(ALT) [0035] Besides, the aspartate aminotransferase (AST) level and alanine aminotransferase (ALT) level were important markers to evaluate the effectiveness of liver disease treatment, which were often used to evaluate the liver cell damage level and classify the liver disease as acute or chronic. Aspartate aminotransferase (AST) abundantly existed in liver, and alanine aminotransferase (ALT) exists in heart, liver and muscle cell. When these cells were damaged, especially when hepatic cells were damaged, the activity of aspartate aminotransferase (AST) and alanine aminotransferase (ALT) of the serum would increase significantly. In this example, although the aspartate aminotransferase (AST) level in oil-added feed group was lower than control group, alanine aminotransferase (ALT) level remained high. Moreover, the alanine aminotransferase (ALT) level in oil-added feed group was slightly increased, on the other side, the alanine aminotransferase (ALT) level in oil-added and drug treated feed group showed slightly decreased. However, the differences were not much between different groups. Example 5. Feed Efficiency [0036] Please refer to FIG. 4 , the total weight gain was divided by total intake amount, so as to calculate the efficiency of feed converted into weight. The calculated result of control group was similar to oil-added feed group. The feed efficiency of oil-added and drug treated feed group was 19% lower than the other groups, which means the rats feed with the feed containing Coleus forskohlii extract and Bacillus subtilis BS139 needed to eat 19% more feed to achieve similar weight gain. Therefore, the Coleus forskohlii extract and Bacillus subtilis BS139 composition of the present invention could reduce the feed nutrition intake and reduce the reaction of feed convert into weight effectively. That is, the composition of the present invention could reduce 15% to 25% caloric intake rate in an animal or a human body effectively. [0037] According to the experiment of the present invention, the Wistar female rats feed with high-fat feed would increase weight and abdominal fat accumulation; meanwhile, the Coleus forskohlii extract and Bacillus Subtilis BS139 composition of the present invention could control the high-fat feed induced rate of weight gain (24.1%), and inhibit the lipid metabolism (triglyceride) and abdominal fat accumulation (44.5%), the inhibition level is greater than the increase level of weight gain and abdominal fat accumulation in normal feed group. Besides, after 6 weeks, there is no any clinical symptoms (severe side effects) in the rats feed with the Coleus forskohlii extract and Bacillus subtilis BS139 composition and high-fat feed. The composition of the present invention could inhibit user's weight gain, reduce the fat intake, reduce the fat accumulation, without reducing the appetite and without having any side effect, so that the user could control his/her body weight in a healthy style. As mention above, the present invention could reduce the weight gain in animal or human body, reduce triglyceride in animal or human body, reduce the food intake rate in animal or human body through specific percentage range of the composition of 0.01 wt % to 0.05 wt % Coleus forskohlii extract and 0.02 wt % to 0.08 wt % Bacillus subtilis BS139 (Storage ID: NRRL NO. B-50347). [0038] Although the present invention has been described in terms of specific exemplary embodiments and examples, it will be appreciated that the embodiments disclosed herein are for illustrative purposes only and various modifications and alterations might be made by those skilled in the art without departing from the spirit and scope of the invention as set forth in the following claims.
The present invention provides a natural composition of reducing weight gains and decreasing the accumulation of fat, comprising Bacillus subtilis BS139 (Storage ID: NRRL NO.B-50347) and Coleus forskohlii extract. Moreover, this composition can be used in the treatment of obesity, helping them healthy reduce fat accumulation, to achieve the effect of weight loss.
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BACKGROUND OF THE INVENTION This invention relates to a nutritional composition and more particularly to a nutritional composition for the management of protein intake. Protein intake, especially in human beings, has received the considerable attention of researchers, nutritionists, medical personnel and others concerned with health issues related to alimentation. Indeed, the general awareness of the public of the important links between health, longevity, morbidity and the quality of life in senescence, on the one hand, and diet, on the other hand, is reflected in the popular adage "you are what you eat". Protein intake is especially relevant in cases where a patient suffers from a malady requiring treatment with one or more therapeutic agents which may be hindered or blocked by the presence of protein. Whether a therapeutic agent will be hindered or blocked and to what extent depends on the nature of the agent and the nature of the malady. One such malady is Parkinson's disease. Parkinson's disease is an ancient disease and is now understood to be a result of a reduction, sometimes substantial, of levels of an important neurotransmitter, dopamine, as a result of the decadence of nigrostriatal dopaminergic neurons. This results in a variety of manifestations, the most common of which are movement disorders and fatigue. The movement disorders may be uncontrolled actions (including tremor) or poverty of movement such as muscular rigidity. Until the 1960's, researchers had been attempting to increase levels of dopamine in the brain in order to treat Parkinson's disease. These attempts failed due to the inability of dopamine to cross the blood brain barrier. In the 1960's, the discovery was made that levels of dopamine in the brain could be increased by the oral or parenteral administration of a substance called levodopa. Levodopa is recognized in the literature as a "large neutral amino acid" or "LNAA" (see Nutt, J. G. and Carter, J. H., "Dietary Issues in the Treatment of Parkinson's Disease", Chapter 28 in Therapy of Parkinson's Disease, edited by William C. Koller and George Paulson, (1990) Decker Press, New York) and is a hydroxyphenylalanine of the chemical formula (-)-3-(3,4-dihydroxyphenyl)-L-alanine. As used herein, "LNAA" refers to amino acids which are neutral in that they have only one carboxyl group and one amino group and which generally have a molecular weight greater than 130. Included within the group of LNAAs are phenylalanine, tryptophan, threonine, valine, isoleucine, histidine, leucine, tyrosine and methionine. It has been known for some time that the reduction of protein intake can assist in the treatment of individuals being administered an LNAA-type therapeutic agent such as levodopa. This is based on the theory that the amino acids constituting protein will compete with the therapeutic agent to cross the blood brain barrier and, thus, will reduce the amount of therapeutic agent ultimately crossing that barrier. This competition results in a lessening of the therapeutic effect of the therapeutic agent or a fluctuation in the response of the patient due to fluctuating levels of competing amino acids in the bloodstream as protein is ingested and metabolized (see Pincus, J. H. et al., Plasma levels of amino acids correlate with motor fluctuations in parkinsonism. Arch. Neurol. (1987) 44:1006-1009; Nutt, J. G., On-off phenomenon: Relation to levodopa pharmacokinetics and pharmacodynamics. Ann. Neurol. (1987) 22:535-540; Leenders, K. L. et al., Inhibition of L-18F-fluordopa uptake into human brain by amino acids demonstrated by positron emission tomography. Ann. Neurol. (1986) 20:258-262). Protein redistribution diets to date have concentrated on eliminating or reducing total protein in a given meal or meals or for a given period of the day. In the case of Parkinson's disease, some protein redistribution diets have been described as being virtually protein-free until the evening meal (see F. Bracco et al., Protein redistribution diet and antiparkinsonian response to levodopa. Eur. Neurol. (1991) 31:68-71) and as comprising eliminating daytime protein (see Karstaedt, P. J. et al., Standard and controlled-release levodopa/carbidopa in patients with fluctuating Parkinson's disease on a protein redistribution diet. Arch. Neurol. (1991) 48:402-405). Other protein redistribution diets restrict protein consumption during the day to e.g. no more than 7 grams (see Pincus, J. et al., Influence of dietary protein on motor fluctuations in Parkinson's disease. Arch. Neur. (1987) 44:270-272; Pincus, J. et al., Protein redistribution diet restores motor function in patients with dopa-resistent "off" periods. Neurology (1988) 38:481-483; Pincus, J. et al., Plasma levels of amino acids correlate with motor fluctuations in Parkinsonism. Arch. Neurol. (1987) 44:1006-1009). U.S. Pat. No. 4,690,820 discloses a high-caloric, high-fat dietary composition having a carbohydrate to protein ratio of 3:1 to 3.7:1 also deriving 45-75% of its calories from fat in the amount of 120-325 grams per liter. U.S. Pat. No. 5,206,218 discloses a method and composition for reducing post-prandial fluctuations in LNAA plasma levels wherein the composition administered has a carbohydrate to protein ratio of from about 3:1 to about 6:1, preferably 4:1. There are a number of disadvantages to the above-noted diets and compositions. A disadvantage to the severely protein-restricted or protein-free diets is that the evening meal must contain a relatively substantial amount of protein in order to satisfy the body's need for essential amino acids and to avoid consequent malnutrition. Compliance with such a regimen can be very difficult for individuals who do not have the appetite or the ability to consume such a substantial amount of protein. Additionally, the often severe onset of parkinsonian symptoms following the high intake of protein in the evening necessary for adequate nutrition is a major disadvantage. Another disadvantage also causing non-compliance is that the protein deficiency borne during the day by the patient may lead to intolerable, or at least bothersome, hunger pangs throughout the day. All of the above diets and compositions suffer from the disadvantage that there is no management of the type of protein (if any) which is administered. Existing meal replacement products, including low protein products, available on the market tend to rely on high levels of caseinates, such as sodium and calcium caseinates, and/or whey or whey extracts for the source of protein contained in such products. However, these proteins are rich in LNAAs, especially leucine and isoleucine. Accordingly, while a low protein product may be advantageous in that lower protein overall will benefit a patient needing reduced LNAA competition at the blood brain barrier, if the protein which is present in the low protein product is largely constituted by LNAAs, the maximized benefit will not be realized. SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a nutritional composition for the management of protein intake which has a first weight-to-weight ratio of carbohydrate to protein of at least about 3.5:1 where the protein component has a particular amino acid composition characterized by a second ratio of one group of amino acids to another group of amino acids. The first group of amino acids (referred to herein as "Group A") consists of glycine, serine, lysine, alanine, aspartic acid, glutamic acid, proline, arginine and hydroxyproline. The second group of amino acids (referred to herein as "Group B") consists of phenylalanine, tryptophan, threonine, valine, isoleucine, histidine, leucine, tyrosine and methionine. The weight-to-weight ratio of the Group A amino acids to Group B amino acids is from about 3:1 to about 6.5:1. Preferably, the first ratio, that of carbohydrate to protein, is from about 7:1 to about 12:1, more preferably from about 7:1 to about 8:1 and most preferably is about 7.5:1. Preferably, the second ratio (A:B) is from about 4:1 to about 5:1. Most preferably, the A:B ratio is about 4.5:1. In another aspect of the present invention, there is provided a nutritional composition which has a particular amino acid composition characterized by a ratio of a different group of amino acids (referred to herein as "Group A*") to the second group of amino acids (Group B) noted above. Group A* consists of glycine, glutamic acid, proline and hydroxyproline. The weight-to-weight ratio of the first different group to the second group (A*:B) is from about 1.5:1 to about 4.5:1 and preferably from about 2.5:1 to about 3.5:1. Most preferably, the A*:B ratio is about 3:1. A yet further aspect of the present invention is a method for facilitating the transport of LNAA-type therapeutic agents across the blood brain barrier in a mammal comprising the administration of the compositions of the present invention. In preferred embodiments, the therapeutic agent is levodopa, the mammal is a human being, and the human being is afflicted with Parkinson's Disease. In a further preferred embodiment, the composition is administered at lunchtime to the substantial exclusion of any other source of carbohydrate or protein. The compositions of the present invention provide adequate nutritional intake when consumed in the context of a proper daily diet and are satisfying, yet at the same time do not interfere, or provide minimized interference, with LNAA-type therapeutic agents. DESCRIPTION OF THE PREFERRED EMBODIMENTS The carbohydrate component of the compositions of the present invention can be selected from the many known sources of carbohydrate. Appropriate ingredients include a variety of mono-, di- and polysaccharides used as nutritive sources of carbohydrates in food products. Examples of carbohydrates which are constituted by monosaccharides and disaccharides are dextrose, lactose, maltose, fructose (in crystalline form or aqueous solution), sucrose (as crystals or in solution), invert sugar and glucose (in various syrup forms including corn syrup). The carbohydrate may also be sourced from natural foods used as sweeteners which comprise a high carbohydrate content, such as honey, fruit juices and concentrates, maple syrup and maple sugar. Examples of carbohydrates which are constituted by polysaccharides or mixtures of mono-, di- and polysaccharides are corn syrup solids, various gums, such as xanthan gum, guar gum, carrageenan gum, arabic gum, locust bean gum and tragacanth gum, maltodextrins, glucose syrups, rice syrup, psyllium, pectin, corn starch (including chemically modified and/or pregelatinized corn starch), tapioca starch, rice starch, potato starch, wheat starch, arrowroot starch and cassava starch. While non-nutritive carbohydrates such as cellulose-based ingredients (for example, microcrystalline cellulose, cellulose gum), polydextrose and sorbitol are used as food ingredients, such non-nutritive carbohydrates are not contemplated for inclusion in calculating the carbohydrate component of the compositions of the present invention. It will be understood by the skilled addressee that the carbohydrate or blend of carbohydrates selected will depend on the various attributes of the ingredients. For example, different carbohydrates will provide energy more or less quickly and a judicious selection of same can contribute to balancing the delivery of carbohydrate calories to the consumer so that the energy provided is meted out over a period of time. Impacting also on the choice of carbohydrate ingredients is the desired flavor of the finished product. Different carbohydrates have different sweetness impact; for example, very low for 10 DE maltodextrin and very high for fructose. In addition to the consideration of sweetness impact, the carbohydrate or carbohydrates must be chosen for "fit" into the flavor profile of the desired product. Finally, the carbohydrate or carbohydrates will be selected for functionality related to texture and processing characteristics of the desired nutritional composition; for example, modified corn starch will be selected for thickness in a cooked, ready-to-eat pudding, whereas starch would be excluded where the product desired is a beverage, as too much thickness would be undesirable. These and other factors in the selection of appropriate carbohydrates are within the knowledge of those skilled in the nutritional arts. The protein component of the present invention can be derived from one or more natural sources or by the direct addition of amino acids or by a judicious combination of the two. In the case of naturally-sourced proteins, the nature and content of the protein sources used in the compositions of the present invention must be carefully selected and balanced in order to provide the desired amino acid content. Preferably, a range of essential and non-essential amino acids will be provided, but in any event within the relative limits contemplated herein. Examples of naturally-sourced proteins useful in the practising of the within invention arranged in order of highest in Group A amino acids versus Group B amino acids to lowest in Group A amino acids versus Group B amino acids are collagen, gelatin, wheat, oats, corn, peas, beans (for example, soybeans) and lentils, egg (whole, yolk and white) and milk proteins. Collagen is a preferred protein for use as a component of the protein sources in the present invention as it is high in Group A amino acids versus Group B amino acids. Particularly preferred is gelatin, a collagen with shorter peptide chain lengths. When gelatin or another collagen is used as a component of the composition, and a liquid product is desired, the hydrolyzed form of same should be used to maintain the liquid consistency desired. Examples of such hydrolyzed materials which are commercially available are POLYPRO® 5000, an edible hydrolyzed collagen (available from Geo Hormel Inc., New Jersey, U.S.A.) and HYDROGEL® A, an edible hydrolyzed gelatin (available from Germantown (Canada) Inc., Toronto, Canada). It will be understood that, generally speaking, a careful blending of different protein types will be necessary to achieve some content of all or most essential amino acids while at the same time maintaining the ratios of Group A amino acids to Group B amino acids within the limits contemplated in the present invention. For example, a composition containing as the only or principal source of protein a milk protein such as whey or calcium or sodium caseinate will be much too rich in Group B amino acids. The proper balancing of such a milk protein with, for example, a collagen will result in a composition which can meet the limits of the present invention yet still provide an acceptable content of various amino acids. It is not possible or practical to provide here all the possible permutations and combinations of naturally-sourced proteins which will result in a composition in accordance with the present invention. It is within the ability of those skilled in the art having knowledge of the amino acid contents of given protein sources to devise combinations and relative quantities of such protein sources so as to achieve the ratios provided for herein. It will also be apparent to those skilled in the art that the protein component of the present compositions may be derived entirely or partly from the direct addition of amino acids (to the extent permitted by relevant food and drug regulations) in amounts relative to the carbohydrate component and each other so as to satisfy the ratios contemplated by the present invention. In the case of partial derivation of the protein component from direct amino acid addition, this may be done in order to supplement the amino acid content derived from naturally-sourced protein in order to meet the ratios contemplated. In the alternative, if direct addition is desired, such may be achieved by the addition of individual amino acids or by the synthesis of polypeptides having a composition such as will, when combined in a given amount with a given amount of carbohydrate, meet the ratios contemplated by the present invention. Methods for the in vitro synthesis of polypeptides and the biosynthesis of polypeptides by host microorganisms encoded for the expression of specifically-sequenced proteins are known. The nutritional compositions of the present invention may additionally comprise a fat component. Fats occur widely in nature and play several roles and, in particular, in humans, three important roles: structural, storage and metabolic. For this reason, generally speaking, fat is an important component of human nutrition. Fats provide energy when consumed and, in addition, act as carriers of fat-soluble vitamins. Fats are a major contributor of metabolic energy, delivering on average nine calories per gram, in comparison to an average of four calories per gram of protein or carbohydrate. The calories of fats are either stored in the body for gradual metabolism and release of energy, or used more quickly for energy, depending on the nutritional status of the consumer. To be used as an energy source, fats must be metabolized and, for this reason, supply energy more gradually than small molecules, particularly the monosaccharides (or "simple sugars"). Dietary fats include mixtures of triacylglycerols, phospholipids, cholesterol, other sterols and fat-soluble vitamins. Edible tits and oils are predominantly composed of esters of glycerol with fatty acids. These are called triacylglycerols or triglycerides. The physical and metabolic properties of these molecules are determined largely by the degree of unsaturation and chain lengths of the fatty acids. Monounsaturated fatty acids contain one double bond and polyunsaturated fatty acids contain two or more double bonds. Some fatty acids, components of fats, are essential in the human diet (that is, they are required for normal function but cannot be synthesized by the body). These fats, such as the n-6 and n-3 families of polyunsaturated fatty acids; for example, linoleic acid, are essential dietary nutrients. Fats are important contributors to the texture and flavor of food products. Mixtures of fats with higher saturated fatty acid content are solid at room temperature; for example, cocoa butter. Mixtures with a high content of unsaturated fatty acids are fluid at room temperature; for example, vegetable oil. These properties affect the selection of specific fats as food ingredients and, accordingly, the nature of the food product desired can dictate the type of fat selected. For example, high polyunsaturate-containing vegetable oil can be used exclusively in fluids such as beverages whereas higher amounts of saturated fats are needed in products with harder textures; for example, a chocolate bar-type product. During the past several decades, evidence has accumulated that heart disease and some cancers are associated with the consumption of diets high in saturated fatty acids and cholesterol. The growing awareness of the relationship between diet and disease has led to a reduction in saturated fat content in food products and dietary habits. For this reason, as components for use together with the compositions of the present invention, mono- and polyunsaturated fats are preferred, although some level of saturated fat is acceptable. As mentioned above, the blend of fats will depend, in part, on the desired characteristics of the product as well as on the desired nutritional profile. Appropriate fat sources include a variety of vegetable fats and oils as well as those from animal sources. Because of their generally lower content of saturated fats and absence of cholesterol, vegetable sources are preferred. Examples of acceptable fat components include: vegetable oils relatively higher in unsaturates such as sunflower oil, safflower oil, canola oil, soybean oil, corn oil, cottonseed oil, olive oil, peanut oil, almond oil, walnut oil and sesame oil; vegetable oils relatively higher in saturates such as cocoa butter, palm oil, palm kernel oil, coconut oil and hydrogenated vegetable oils (coating fats, etc.); animal fats relatively higher in unsaturates such as fish oils; animal fats mid-range in unsaturates such as goose, beef and pork fats; and animal fats relatively higher in saturates such as milk fat (butter fat). The blend of fat components selected for a specific composition will depend on several attributes of the ingredients. Selection will be based on physical properties of the ingredients and those desired in the finished product, as well as on flavor, texture, cost and availability. As well, relative amounts of individual fats may be selected by the person skilled in the nutritional arts based on the provision of essential fatty acids. Finally, the amount of fat will be selected based on providing an appropriate amount of caloric energy for the product; for example, in the range of 150 to 250 calories for a "snack" and in the range of 250 to 600 calories for a "meal". The compositions of the present invention may also contain added vitamins and minerals. The amount and kind of such vitamins and minerals is normally governed by local health regulatory requirements. Such requirements often specify maximum and recommended quantities or ranges of recommended quantities of vitamins and minerals both on a daily basis and, for example, where a product is intended for use as a liquid diet or as a meal replacement, on a per serving basis. It is noted that, subject to health regulatory requirements for the presence of vitamin B6, such presence is ideally minimized or eliminated where the nutritional composition is intended for use by a person being administered levodopa, since it is known that vitamin B6 interferes to some degree with levodopa uptake in the brain. The compositions of the present invention may contain other ingredients known to those skilled in the art in order to provide an organoleptically acceptable final product for consumption. For example, additional ingredients may include flavoring materials such as natural and artificial flavors and other ingredients added especially for flavor; for example, specific sweeteners, fruits, salt and flavor enhancers. Also included may be coloring materials including certified color additives and natural color additives such as beet powder, beta carotene and caramel. Spices and seasonings may also be included as well as emulsifiers and stabilizers such as hydrocolloids (for example, carrageenan, xanthan, guar and locust bean gums) and specialized fats (for example, mono- and di-glycerides). In addition, preservatives may be used such as sodium benzoate and potassium sorbate. It should be noted, however, that further ingredients as suggested above should be judiciously selected as to kind and quantity so as to maintain the final composition of the product within the limits of the ratios contemplated by the present invention. For example, if a certain additive deemed necessary for flavoring contains certain amino acids, the amount of natural or synthetic protein or directly-added amino acids may have to be adjusted in order to achieve a product of an acceptable constitution within the scope and meaning of the present invention. As well, it should be noted that many of the carbohydrate, protein and fat components discussed above will also contribute functionality in the various areas of flavoring, coloring, emulsification, stabilization and preservation. The person skilled in the art will also appreciate means by which the consistency of the present compositions may be modified and prepared so as to provide a liquid pudding-like, or solid composition. In general, product texture will be determined by the unique combination of ingredients and by processing methods. For example, in a liquid beverage, a smooth, creamy texture will result from the judicious selection of specific amounts and balance of proteins, starches, gums and fats in the formulation. As well, the viscosity, or thickness, will depend on the processes used to mix the ingredients and stabilize the suspension (the blending and homogenizing processes, respectively). Similarly, in a pudding product, the texture (creamy, smooth, spoonable, firm) will accrue to the specific ingredients used (modified starches, gums, fats, emulsifiers, etc.) and the processing steps (blending, cooking, homogenizing, cooling, etc.). The finished texture of a solid product, such as a "chocolate bar" will also depend on the ingredients and on the mixing and forming processes. The compositions of the present invention can be prepared using techniques known to those skilled in the art. For example, in the case of a liquid composition, generally speaking, dry ingredients will be premixed and added to the liquid components (excluding the oily ingredients, if any) and mixed. The oily ingredients will then be added and the mixture homogenized in, for example, a colloid mill. The resultant homogenized mixture will then be heated, canned, sterilized and cooled. Other preparation techniques for liquid compositions and for compositions of other textures, such as puddings and snack bars, are known. In the alternative, the compositions embodying the present invention may be prepared and packaged in powdered or dried form for reconstitution with water to a liquid or pudding-like texture. The advantage to such a powdered or dried form is that handling and shipping of the product is less expensive than in the case of a fully-constituted product as the product is substantially lighter. Also, properly packaged in moisture-resistant or even moisture-proof packaging, powdered or dried products will benefit from a substantially longer shelf-life. All of such compositions are contemplated as within the scope of the present invention. It is to be noted that legislators and regulators in many jurisdictions have enacted statutes and regulations governing the content and labelling of nutritional compositions and, in particular, those compositions intended as "meal replacements". Naturally, the practising of the present invention must always be within the bounds of such statutes and regulations, where applicable. In addition, as those skilled in the nutritional sciences will appreciate, the compositions of the present invention do not supply the necessary complement of essential amino acids and should accordingly be administered to a given individual in accordance with the instructions, and under the supervision, of a qualified health practitioner who will advise such individual of the type of overall diet within which the compositions of the present invention should be consumed. EXAMPLE 1 A chocolate-flavored liquid composition in accordance with the present invention was made using the following ingredients in the following weight percentages: ______________________________________ wt.%______________________________________skim milk powder 3.08hydrolysed gelatin 2.69maltodextrin 9.62dextrose 7.69sugar 6.92cocoa 1.15lecithin 0.58walnut oil 0.77fish oil (microencapsulated) 0.39fish oil (concentrated) 0.19linolenic acid 0.19micronized fiber 1.54vitamin mixture 0.15sunflower oil 3.46canola oil 3.46water 58.12 100.00______________________________________ The dry ingredients were weighed and premixed and added to the water with stirring. The oils (preblended) were then added and the mixture was homogenized. The homogenized product was heated to 185° F. and then cooled. Per 260 gram serving, the resulting nutritional composition contained 9.41 grams of protein, 64.04 grams of carbohydrate and 23.50 grams of fat. The carbohydrate to protein weight to weight ratio of the composition was 6.81:1 and the protein to fat weight to weight ratio was 0.40:1. The weight to weight ratio of Group A amino acids to Group B amino acids was 3.39:1 and the weight to weight ratio of Group A* amino acids to Group B amino acids was 2.12:1. EXAMPLE 2 A chocolate-flavored liquid composition was prepared using the method of manufacture of Example 1 containing the following ingredients in the following weight percentages: ______________________________________ wt.%______________________________________water 60.49maltodextrin 9.00dextrose 8.50sugar 6.00canola oil 4.50sunflower oil 4.50hydrolized gelatin 2.60skim milk powder 1.60cocoa powder (10/12) 1.10vitamin/mineral premix 0.95deoiled granular lecithin 0.50carrageenan 0.19salt 0.08 100.00______________________________________ Per 260 gram (235 ml.) serving, the composition thus prepared had a caloric content of 483 (2020 kJ) and contained 8 grams of protein, 62 grams of carbohydrate and a total of 25 grams of fat. The fat was comprised of 12 grams of polyunsaturates, 9.3 grams of monounsaturates, 2.3 grams of saturates and 1 milligram of cholesterol. The carbohydrate to protein weight-to-weight ratio was thus 7.75:1, and the protein to fat weight-to-weight ratio was 0.32:1. Each 260 gram (235 ml.) serving contained the following amino acids in approximately the following amounts: ______________________________________glycine 1.310 g.serine 0.300 g.lysine 0.325 g.alanine 0.577 g.aspartic acid 0.517 g.glutamic acid 0.997 g.proline 1.018 g.arginine 0.538 g.hydroxyproline 0.601 g.phenylalanine 0.208 g.tryptophan 0.034 g.threonine 0.197 g.valine 0.273 g.isoleucine 0.205 g.histidine 0.156 g.leucine 0.349 g.tyrosine 0.136 g.methionine 0.094 g.______________________________________ Thus, the weight to weight ratio of Group A to Group B amino acids was 3.74:1. The weight-to-weight ratio of Group A* to Group B amino acids was 2.38:1. EXAMPLE 3 A commercial quantity of the chocolate-flavored liquid composition of Example 2 was made (with some very minor variations in weight percentages as shown) with the ingredients in the following amounts: ______________________________________ wt.%______________________________________skim milk powder 005.008 kg. 001.59hydrolyzed gelatin 008.139 kg. 002.59maltodextrin 028.172 kg. 008.95dextrose 026.607 kg. 008.45sugar 018.781 kg. 005.97cocoa powder (10/12) 003.756 kg. 001.19salt 000.250 kg. 000.08carrageenan 000.939 kg. 000.30vitamin/mineral premix 003.000 kg. 000.95deoiled granular lecithin 001.565 kg. 000.49canola oil 014.086 kg. 004.48sunflower oil 014.086 kg. 004.48water 190.378 kg. 060.48 314.767 kg. 100.00______________________________________ The previously weighed dry ingredients were mixed and added to a stirred tank containing the water. The mixture was stirred until it was of a smooth consistency at which time the canola and sunflower oils were added. The resultant mixture was processed through a colloid mill and transferred to a 500 liter steam-heated kettle and heated to 185° F. with stirring. The liquid composition was then transferred to a filling machine where the composition was deposited in 250 ml. cans each containing 260 g. of the product (235 ml. when at room temperature). The cans were hermetically sealed and transferred to a steam retort for sterilization at 240° F. for 15-20 minutes. The cans thus sterilized were then conveyed to a water bath and cooled to room temperature for labelling and packaging in cardboard canons each containing 24 cans. 1200 cans or 50 cases of 24 cans are thus produced. EXAMPLE 4 A vanilla-flavored liquid composition was prepared using the method of manufacture of Example 1 containing the following ingredients in the following weight percentages: ______________________________________ wt.%______________________________________water 60.46dextrose 10.00maltodextrin 8.00sugar 6.00canola oil 4.50sunflower oil 4.50hydrolized gelatin 2.80skim milk powder 1.80vitamin/mineral premix 0.95deoiled granular lecithin 0.50carrageenan 0.22color (titanium dioxide) 0.20salt 0.05flavor (vanillin + ethyl vanillin) 0.02 100.00______________________________________ Per 260 gram (235 ml.) serving, the composition thus prepared had a caloric content of 483 (2020 kJ) and contained 8 grams of protein, 62 grams of carbohydrate and a total of 25 grams of fat. The fat was comprised of 12 grams of polyunsaturates, 9.3 grams of monounsaturates, 2.4 grams of saturates and 1 milligram of cholesterol. The carbohydrate to protein weight-to-weight ratio was thus 7.75:1, and the protein to fat weight-to-weight ratio was 0.32:1. Each 260 gram (235 ml.) serving contained the following amino acids in approximately the following amounts: ______________________________________glycine 1.377 g.serine 0.283 g.lysine 0.322 g.alanine 0.584 g.aspartic acid 0.501 g.glutamic acid 0.960 g.proline 1.068 g.arginine 0.543 g.hydroxyproline 0.647 g.phenylalanine 0.190 g.tryptophan 0.027 g.threonine 0.186 g.valine 0.259 g.isoleucine 0.198 g.histidine 0.155 g.leucine 0.332 g.tyrosine 0.125 g.methionine 0.093 g.______________________________________ Thus, the weight to weight ratio of Group A to Group B amino acids was 4.02:1. The weight-to-weight ratio of Group A* to Group B amino acids was 2.59:1. EXAMPLE 5 A strawberry-flavored liquid composition was prepared using the method of manufacture of Example 1 containing the following ingredients in the following weight percentages: ______________________________________ wt.%______________________________________water 60.10dextrose 10.20maltodextrin 7.50sugar 6.47canola oil 4.50sunflower oil 4.50hydrolized gelatin 2.80skim milk powder 1.80vitamin/mineral premix 0.95deoiled granular lecithin 0.50carrageenan 0.30color 0.12citric acid 0.12strawberry flavor 0.09salt 0.05 100.00______________________________________ Per 260 gram (235 ml.) serving, the composition thus prepared had a caloric content of 486 (2030 kJ) and contained 8 grams of protein, 62 grams of carbohydrate and a total of 25 grams of fat. The fat was comprised of 12 grams of polyunsaturates, 9.3 grams of monounsaturates, 2.4 grams of saturates and 1 milligram of cholesterol. The carbohydrate to protein weight-to-weight ratio was thus 7.75:1, and the protein to fat weight-to-weight ratio was 0.32:1. :Each 260 gram (235 ml.) serving contained the following amino acids in approximately the following amounts: ______________________________________glycine 1.377 g.serine 0.283 g.lysine 0.322 g.alanine 0.584 g.aspartic acid 0.501 g.glutamic acid 0.960 g.proline 1.068 g.arginine 0.543 g.hydroxyproline 0.647 g.phenylalanine 0.190 g.tryptophan 0.027 g.threonine 0.186 g.valine 0.259 g.isoleucine 0.198 g.histidine 0.155 g.leucine 0.332 g.tyrosine 0.125 g.methionine 0.093 g.______________________________________ Thus, the weight to weight ratio of Group A to Group B amino acids was 4.02:1. The weight-to-weight ratio of Group A* to Group B amino acids was 2.59:1. EXAMPLE 6 A viscous liquid nutritional composition is made containing the following ingredients: ______________________________________ wt.%______________________________________gelatin 4.000egg white powder 0.050wheat flour 0.150maltodextrin 10 DE 5.000dextrose 5.000sugar 4.000salt 0.050carrageenan PMD 0.500vitamin/mineral mix 0.800titanium dioxide 0.300vanillin 0.015ethyl vanillin 0.005lecithin 0.500canola oil 3.000sunflower oil 6.000water 70.630 100.000______________________________________ Per 260 gram serving, this composition has a protein content of 9.11 grams, a carbohydrate content of 34.86 grams, a fat content of 24.58 grams, and a caloric content of 397. Accordingly, the carbohydrate to protein weight to weight ratio is 3.82:1. The weight to weight ratio of Group A amino acids to Group B amino acids is 5.86:1 and the weight to weight ratio of Group A* amino acids to Group B amino acids is 3.87:1. EXAMPLE 7 A pudding-like nutritional composition is made containing the following ingredients: ______________________________________ wt.%______________________________________skim milk powder 0.500gelatin 3.000egg white powder 1.000wheat flour 0.500maltodextrin 10 DE 18.000dextrose 16.000sugar 12.000salt 0.100guar gum 1.000vitamin/mineral mix 0.850color 0.100flavor 0.050lecithin 1.000canola oil 4.000sunflower oil 4.000water 37.900 100.000______________________________________ Per 150 gram serving, this composition has a protein content of 5.56 grams, a carbohydrate content of 66.44 grams, a fat content of 13.38 grams, and a caloric content of 408. Accordingly, the carbohydrate to protein weight to weight ratio is 11.94:1. The weight to weight ratio of Group A amino acids to Group B amino acids is 3.44:1 and the weight to weight ratio of Group A* amino acids to Group B amino acids is 2.11:1. EXAMPLE 8 A pudding-like nutritional composition is made containing the following ingredients: ______________________________________ wt.%______________________________________gelatin 4.000wheat flour 2.000maltodextrin 10 DE 18.000dextrose 16.000sugar 11.000xanthan gum 0.750flavor 0.250lecithin 0.500canola oil 2.000sunflower oil 5.000water 40.500 100.000______________________________________ Per 150 gram serving, this composition has a protein content of 5.58 grams, a carbohydrate content of 65.98 grams, a fat content of 11.27 grams, and a caloric content of 388. Accordingly, the carbohydrate to protein weight to weight ratio is 11.83:1. The weight to weight ratio of Group A amino acids to Group B amino acids is 5.52:1 and the weight to weight ratio of Group A* amino acids to Group B amino acids is 3.67:1. EXAMPLE 9 A viscous liquid nutritional composition is made containing the following ingredients: ______________________________________ wt.%______________________________________skim milk powder 4.000gelatin 3.500egg white powder 0.500maltodextrin 10 DE 8.000dextrose 5.000sugar 4.000salt 0.100xanthan gum 0.500vitamin/mineral mix 0.900color 0.050flavor 0.200lecithin 0.500canola oil 4.000sunflower oil 6.000water 62.750 100.000______________________________________ Per 150 gram serving, this composition has a protein content of 7.31 grams, a carbohydrate content of 27.47 grams, a fat content of 15.72 grams, and a caloric content of 281. Accordingly, the carbohydrate to protein weight to weight ratio is 3.76:1. The weight to weight ratio of Group A amino acids to Group B amino acids is 3.04:1 and the weight to weight ratio of Group A* amino acids to Group B amino acids is 1.88:1. EXAMPLE 10 A nutritional composition is made having a "chocolate bar"-like consistency by combining the following ingredients in the following weight percentages: ______________________________________ wt.%______________________________________dextrose 23.00sugar 17.70modified corn starch 10.00hydrogenated soybean and cottonseed oil 10.00crisp rice 8.00hydrolyzed gelatin 6.50water 5.00walnut oil 5.00cocoa powder 4.50safflower oil 4.00Duromel coating fat 1.50xanthan gum 1.10peanut butter 1.00skim milk powder 1.00deoiled granular lecithin 1.00mono- and diglycerides (emulsifier - soy based) 0.30natural flavor 0.25salt 0.15 100.00______________________________________ The solid product may contain added vitamins and minerals in desired amounts. Per 100 gram serving, the composition has an energy content of 450 calories (1880 kJ) and contains 7.7 grams of protein, 59 grams of carbohydrate/glucides and 23 grams of fat comprised of 12 grams polyunsaturates, 5.2 grams monounsaturates and 3.8 grams saturates. Thus, the carbohydrate to protein weight to weight ratio is 7.65:1 and the protein to fat weight to weight ratio is 0.34:1. The weight to weight ratios of Group A amino acids to Group B amino acids and of Group A* amino acids to Group B amino acids are 3.32:1 and 2.05:1, respectively. EXAMPLE 11 A composition is made having a pudding-like consistency by combining the following ingredients in the following weight percentages: ______________________________________ wt.%______________________________________water 35.00dextrose 15.00invert sugar (67% solids) 15.00maltodextrin 13.00hydrolyzed gelatin 5.50safflower oil 5.50canola oil 5.00skim milk powder 3.00modified corn starch 2.50mono- and diglycerides (emulsifier - soy based) 0.30flavor 0.15salt 0.04color 0.01 100.00______________________________________ The composition may contain added vitamins and minerals. The composition of pudding-like consistency has per 142 gram serving in an aseptically filled cup an energy content of 400 calories (1670 kJ). The product contains per serving 8.2 grams of protein, 56 grams of carbohydrate/glucides and 15 grams of fat, the latter comprised of 8.2 grams of polyunsaturates, 5.2 grams of monounsaturates, 1.3 grams of saturates and 1 milligram of cholesterol. Accordingly, the composition has a carbohydrate to protein weight to weight ratio of 6.83:1 and a protein to fat weight to weight ratio of 0.55:1. The weight to weight ratios of Group A amino acids to Group B amino acids and of Group A* amino acids to Group B amino acids are 4.21:1 and 2.72:1, respectively. EXAMPLE 12 Eighteen patients suffering from Parkinson's Disease were administered the compositions of Examples 2, 4 and 5, according to their desire for a particular flavoring (chocolate, vanilla or strawberry). The patients were supplied with an 8 ounce (225 ml.) serving per day. Instructions given to the patients were to eat the usual breakfast and supper and substitute the composition for their regular lunch. Additional servings of the composition were made available on a supervised basis so that, if a patient were to go out in the evening from time to time, a serving of the composition could be substituted for that patient's supper as well. The results were as follows: Patient 1: 68 year old male, has had Parkinson's disease for 12 years, drug regimen: SINEMET® 100/25 (levodopa-carbidopa containing per tablet 100 mg. of levodopa and 25 mg. of carbidopa) four times daily, SINEMET® CR (controlled release levodopa-carbidopa containing per tablet 200 mg. of levodopa and 50 mg. of carbidopa) twice nightly, and ELDEPRYL® (selegiline hydrochloride containing per tablet 5 mg. of selegiline hydrochloride) twice daily. Results: For two years prior, Patient 1 was able to work only mornings and had to go to bed after lunch. He began taking a commercial nutritional composition containing low protein (SUPLENA®). He showed some improvement on this regimen but found the product excessively sweet and difficult to drink. Upon commencing to use the composition of the present invention, he reported a great increase in energy levels and has been able to work in the afternoons ever since. He has continued to use the inventive composition and his improvement has continued. Patient 1 noticed some increase in his dyskinesias. He was able to cut his daily dose of levodopa-carbidopa by one-third and of selegiline hydrochloride by one-half, whereupon his dyskinesias have disappeared. Patient 2: 72 year old male, has had Parkinson's disease for 15 years, drug regimen: SINEMET® 100/25 four times daily plus ELDEPRYL® twice daily. Results: Patient 2 is a retired banker. For two years, he was active only in the mornings. As with Patient 1, Patient 2 began taking SUPLENA® instead of his regular lunch. He noticed a slight improvement but, on commencing use of the compositions of Examples 2, 4 and 5 in place of the SUPLENA®, he reported an immediate dramatic improvement. He has since has been active with an increased energy level for a full day. His Parkinson's symptoms have disappeared and he noticed a slight increase in dyskinesias. He reduced his SINEMET® by one pill per day and his dyskinesias have all disappeared. Patient 3: 63 year old male, has had Parkinson's disease for 4 years, drug regimen: PROLOPA® 100/25 (levodopa-benserazide containing per capsule 100 mg. of levodopa and 25 mg. of benserazide). Results: Upon commencing the use of the compositions of the present invention, Patient 3 noticed an immediate improvement in all of his Parkinson's symptoms and particularly noticed an increase of energy. Patient 4: 61 year old female, has had Parkinson's disease for fifteen years, drug regimen: PROLOPA® 100/25 four times daily, SINEMET® CR three times nightly, ELDEPRYL®after breakfast. Results: Patient 4 reported an improvement in energy on the same day as she commenced using the compositions of Examples 2, 4 and 5. She has observed no difference in her dyskinesias. Patient 5: 75 year old female, has had Parkinson's disease for 3 years, drug regimen: SINEMET® 100/25 three times daily, SINEMET® CR once at bedtime, bromocriptine mesylate (an anti-Parkinsonian) twice daily and ELDEPRYL® twice daily. Results: Patient 5 is a literary searcher. Prior to commencing use of the compositions of Examples 2, 4 and 5, she was able to work only two hours per day. Upon commencing use of the compositions, she noticed an immediate increase in energy and was able to return to work at home on a full-time basis. Patient 6: 42 year old male, has had Parkinson's disease for one year, drug regimen: SINEMET® 100/25 twice daily plus bromocryptine mesylate twice daily. Results: Despite the only relatively recent onset of Parkinson's disease, Patient 6 has been hit very quickly and very hard with all the symptoms typical of Parkinson's disease. Upon commencing use of the compositions of Examples 2, 4 and 5, the patient's family reported noticing an immediate increase in Patient 6's energy level. He sleeps less in the afternoon and is more active. He walks to the store, something he could rarely do before. Patient 7: 86 year old female, has had Parkinson's disease for 20 years, drug regimen: SINEMET® 100/25 three times daily, ARTANE® (trihexyphenidyl hydrochloride, an anticholinergic/anti-Parkinsonian) three times daily, SINEMET® CR once at bedtime and ELDEPRYL® once in the morning after breakfast. Results: Patient 7 is in the final stages of Parkinson's disease and is generally confined to bed. Upon commencing the use of the compositions of Examples 2, 4 and 5 and, since, her symptoms have not improved. However, Patient 7 reports that she is feeling better. She stays out of bed for two hours in the morning and in the afternoon, sitting in a chair. She was unable to do this prior to commencing the use of the Examples 2, 4 and 5 compositions. Patient 8: 65 year old female, has had Parkinson's disease for 12 years, drug regimen: PROLOPA® 100/25 three times daily and ELDEPRYL® twice daily. Results: Patient 8 has been unable to work for three years. Upon commencing the use of the compositions of Examples 2, 4 and 5, she noticed a marked increase in her energy levels and dyskinesias. Upon reducing her dose of PROLOPA® to twice daily, the dyskinesias disappeared and her energy level remained improved. Patient 9: 60 year old female, has had Parkinson's disease for 6 years, drug regimen: SINEMET® 100/25 three times daily and bromocryptine mesylate once daily. Results: Patient 9's symptoms are well controlled on the drug regimen noted above. No change was observed upon the patient commencing the use of the composition of the present invention. Patient 10: 57 year old female, has had Parkinson's disease for 6 years, drug regimen: PROLOPA® 50/12.5 (levodopa-benserazide containing per capsule 50 mg. of levodopa and 12.5 mg. of benserazide) three times daily and ELDEPRYL® once daily after breakfast. Results: Prior to commencing the use of the inventive compositions, Patient 10, an office worker, was severely restricted by Parkinson's symptoms after lunch, unless she only had a salad. If she ate anything else for lunch, she would have an onset of sudden weakness thirty minutes after completing her meal and, within minutes, would have to lie down for at least an hour. Alternatively, if Patient 10 had a salad for lunch, by 4:00 pm she was so hungry that she could not stay at work. Her employer and coworkers are very considerate, but Patient 10 felt she was putting too much of a burden on her colleagues and was considering quitting work. Upon commencing the use of the composition of the present invention, Patient 10 has had a striking resurgence in her energy level. She is now able to work a full day. She has noticed a slight increase in dyskinesias but has not changed her medication. Patient 10 has now discarded her plan to retire. Patient 11: 81 year old female, has had Parkinson's disease for 8 years, drug regimen: ARTANE® three times daily, SINEMET® 100/25 three times daily, SINEMET® CR once at bedtime, once at midnight and once at 4:00 a.m., ELDEPRYL® twice daily, bromocriptine mesylate twice daily, DIABETA® (glyburide, an antidiabetic) three times daily and FLORINEF® (fludrocortisone acetate, a salt-regulating adrenocortical steroid) once every morning after breakfast. Results: Patient 11 is managing remarkably well and still does volunteer work at a hospital but shuffles and shakes despite taking numerous medications. Patient 11 has been taking the compositions of Examples 2, 4 and 5 for one and one-half months and feels there has been a reduction in her symptoms. Patient 12: 72 year old male, has had Parkinson's disease for over 20 years, drug regimen: SINEMET® 100/25 four times daily, SINEMET® CR three times daily, at bedtime, midnight and 4:00 a.m., ELDEPRYL® twice daily, after breakfast and lunch and INDERAL® (propanolol hydrochloride, a cardiac depressant) 80 mg. twice daily. Results: Upon commencing the use of the compositions of Examples 2, 4 and 5, Patient 12 showed an immediate improvement. All of his Parkinson's symptoms have improved and he especially notices increased energy levels. He is also more relaxed. Patient 13: 67 year old female, has had Parkinson's disease for 8 years, drug regimen: SINEMET® 100/25 four times daily, SINEMET® CR once at bedtime and ELDEPRYL® twice daily after breakfast and lunch. Results: Commencing in the eighth year of her Parkinson's disease, Patient 13 developed fatigue, in addition to her tremor and rigidity. Her usual lunch was a hamburger until commencing with the use of the compositions of Examples 2, 4 and 5. While on the daily hamburger regimen, Patient 13 would invariably develop weak spells and would have to lie down. Since Patient 13 has been on the regimen of the compositions of Examples 2, 4 and 5, her weak spells have disappeared as has her need to lie down following lunch. She has noticed no change in her major symptoms, but in the first few days of the new regimen, she noticed a slight increase in dyskinesias. She did not alter her medication and her dyskinesias have gradually disappeared. Patient 14: 54 year old female, has had Parkinson's disease for 3 years, drug regimen: no medication. Results: Patient 14 is a librarian whose symptoms of Parkinson's disease at this stage consist of a slight tremor and inability to get out of bed every night. Her work pattern has not yet been interrupted. She has been taking the compositions of Examples 2, 4 and 5 in accordance with the prescribed regimen for three weeks but has noticed no difference in her condition. Patient 15: 53 year old male, has had Parkinson's disease for 6 years, drug regimen: SINEMET® 100/25 three times daily. Results: Patient 15 is a senior Government bureaucrat whose Parkinson's disease, until recently, was well controlled using SINEMET®. In the last four months of his condition, the tremor broke through and he had intended to resign his position due to his extreme fatigue. He commenced using the compositions of Examples 2, 4 and 5 and taking ELDEPRYL® twice daily and has improved remarkably. Patient 15 has abandoned his plan to retire. Patient 16: 55 year old female, has had Parkinson's disease for 4 years, drug regimen: PROLOPA® 50/12.5 three times daily and ELDEPRYL twice daily after breakfast and lunch. Results: In the fourth year of her disease, Patient 16 suffered the rapid onset of Parkinson's symptoms, her major problem being the repeated off/on of the disease. She found that the off/on variations were occurring as many as twelve times daily. Since commencing the use of the compositions of Examples 2, 4 and 5, Patient 16 has seen a remarkable improvement in the off/on nuisance which has been reduced to once or twice every afternoon. Patient 17: 60 year old male, has had Parkinson's disease for 6 years, drug regimen: SINEMET® 100/25 six times daily, SINEMET® CR three times through the night, bromocriptine mesylate once daily, PERMAX® (pergolide mesylate, a dopamine agonist) once at bedtime, ELDEPRYL® twice daily and ARTANE®. Results: Patient 17 is totally confined to his home in a wheelchair. He has been on numerous medications but nothing helps. Upon commencing the use of the compositions of Examples 2, 4 and 5, his symptoms did not improve appreciably nor have his dyskinesias changed. However, he notices that he has much more energy throughout the day and he no longer sleeps in the afternoon. Patient 18: 55 year old female, has had Parkinson's disease for 1 year, drug regimen: SINEMET® 100/25 twice daily and ELDEPRYL® once every morning. Results: Upon commencing the use of the compositions of Examples 2, 4 and 5, Patient 18 reported that her afternoon fatigue had disappeared. At first, she noticed some increase in her dyskinesias but upon discontinuing one SINEMET® and the ELDEPRYL®, the dyskinesias have now disappeared. The foregoing Examples are intended to illustrate the present invention only, and are not to be taken as limiting the scope of the invention as fully disclosed and set out in the appended claims.
Nutritional compositions are provided for the management of protein intake which have a carbohydrate to protein ratio of at least about 3.5:1 and a ratio of one group of amino acids to another group of amino acids of from about 3:1 to about 6.5:1 where the one group consists of glycine, serine, lysine, alanine, aspartic acid, glutamic acid, proline, arginine and hydroxyproline and the other group of amino acids consists of phenylalanine, tryptophan, threonine, valine, isoleucine, histidine, leucine, tyrosine and methionine. The compositions provide minimized interference with large neutral amino acid (LNAA) type therapeutic agents.
0
BACKGROUND OF THE INVENTION The present invention pertains to a strip member that is a component of a muntin bar assembly and to a two-piece muntin bar assembly made therefrom. Muntin bars are often used for decorative purposes to divide light in windows and make a large integral window appear as if it were formed of a number of smaller window panes separated from each other. Decorative muntin bars simulate the colonial style of numerous panes of glass in individual wooden frames. Prior art muntin bars are integrally formed. Such prior art muntin bars may be coated in a variety of matching colors to coordinate with the color of the sash of the window; however, these muntin bars are not suited to easily have two distinct colors or textures respectively located on the interior and exterior surfaces of the muntin bar. Muntin bars in many colors, textures, and surface configurations are required to be stocked by builder's supply houses to satisfy modem interior decorating tastes. In addition to the many colors, textures, and surface configurations desired, many manufacturers and customers are now demanding muntin bars with different colors, textures, and surface configurations on the interior and exterior surfaces of an individual muntin bar. For example, a front door may have a natural wood finish on the outside surface with a white finish on the inside surface. The homeowner may require a muntin bar assembly which duplicates the door and has a wood grain exterior surface and a white interior surface. Such arrangements were not available in integrally formed prior art designs. Painting and roll forming a muntin bar in two different colors, textures, or surface configurations would create major difficulties in manufacturing. A large inventory of different types of muntin bars would have to be maintained in order to satisfy customer requirements for muntin bars having the numerous different color, texture, and surface configuration combinations. For example, if the interior and exterior surface of a muntin bar are each formed with one of four different surface configurations, ten different styles of muntin bars would have to be maintained in inventory to cover all of the possible combinations that may be requested of the four surface configurations. As the number of selections of colors, textures, and configurations increases, the required stock of muntin bars in each combination quickly becomes unmanageable. For the foregoing reasons, there is a need for a versatile muntin bar assembly that can be easily assembled from separate interior and exterior strips. SUMMARY OF THE INVENTION The present invention is directed to a decorative muntin bar assembly formed from an interior first strip member and an exterior second strip member, wherein each strip member may be formed in various colors, textures, and surface configurations. The muntin bar assembly is adapted for use with different types of windows. Each strip member may be adapted to interconnect to a similarly constructed cooperating strip member. Each strip member includes an elongate wall member having first and second longitudinally extending edges. A male coupling member, such as a flange, is attached to the first longitudinal edge of the wall member. A female coupling member, such as a channel, is attached to the second longitudinal edge of the wall member. If desired, the two strip members may be mirror images of each other. The muntin bar assembly is formed by interconnecting the first strip member with the second similarly constructed strip member. The flange of the second strip member is inserted and retained in the channel of the first strip member, and conversely the flange of the first strip member is inserted and retained in the channel of the second strip member. This construction allows each strip member of the muntin bar to be prepainted and roll formed with the desired color, texture, and surface configuration. Each strip member of the muntin bar assembly can be made in a variety of colon, textures, and surface configurations. The different types of prepainted and prefinished strip members can be mixed and matched in assembling a muntin bar to provide a large number of combinations of colors, textures, and surface configurations for the interior and exterior sides of the muntin bar assembly from a relatively few different types of strip members. The muntin bar assembly may be located on only one side of a pane of glass in a window or between panes of glass in an insulated window. The muntin bar assembly is preferably attached to the window frame with end connectors. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front elevational view of the muntin bar of the present invention shown attached to the frame of a window. FIG. 2 is an enlarged partial side elevational view of the muntin bar shown between two panes of glass taken along lines 2--2 of FIG. 1. FIG. 3 is a perspective view of an end connector which may be used to attach the muntin bar assembly to a window frame. FIG. 4 is a front elevational view of an alternate end connector. FIG. 5 is a perspective view of a strip member of the muntin bar assembly of the present invention. FIG. 6 is a cross sectional view of the muntin bar assembly taken along lines 6--6 of FIG. 1. FIG. 7 is a cross sectional view of an alternate embodiment of a muntin bar assembly. FIG. 8 is a cross sectional view of another alternate embodiment of a muntin bar assembly. FIG. 9 is a cross sectional view of another alternate embodiment of a muntin bar assembly. FIG. 10 is a cross sectional view of another alternate embodiment of a muntin bar assembly. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The muntin bar assembly 20 of the present invention is shown in FIG. 1 attached to a window unit 22. The window unit 22 includes a window frame 24 having spaced apart and opposing frame members 26 and 27 and two spaced apart panes of glass 28 and 30. As best shown in FIG. 2, the muntin bar assembly 20 is located between the panes of glass 28 and 30, but may be located to the exterior of either pane 28 or 30 or on opposite sides of a single pane of glass. The muntin bar assembly 20 includes a first end 29 removably attached to the window frame member 26 with an end connector 33A and a second end 31 removably attached to the window frame member 27 with an end connector 33B. Each end connector 33 is preferably molded from nylon or another suitable plastic and can be used to mount a complete grill bar assembly formed from a plurality of muntin bars to a window unit 22. In the embodiment illustrated in FIG. 3, the end connector 33 consists of a spine 32 having a stabilizing end 34 and angled fins 36 projecting outwardly from the spine 32. The stabilizing end 34 is adapted to be inserted into the open ends 29 and 31 of the muntin bar assembly 20. The angled fins 36 press easily into the open ends 29 and 31 of the muntin bar assembly 20 and tend to expand and press against the sides of the muntin bar assembly 20 making the end connector 33 somewhat difficult to remove. The opposite end of the end connector 33 includes an end stop platform 38 for engaging the end 29 or 31 of the muntin bar assembly 20. The end stop platform 38 includes barbed pins 40 that fit into mating holes in the window frame members 26 and 27 to secure the muntin bar 20 in place. FIG. 4 shows an alternate embodiment of an end connector 41 having a narrow spine 43 and a single barbed pin 45. The muntin bar assembly 20 includes two cooperating strip members 42A and 42B, as shown in FIG. 6, which are constructed substantially identical to each other. One of the strip members 42A or B faces the interior of the window while the other strip member faces the exterior of the window. As shown in FIGS. 5 and 6, the strip member 42A has an elongate generally planar wall member 44A having an outer display surface, a first longitudinally extending edge 46A and a spaced apart and generally parallel second longitudinally extending edge 48A. A first side wall 50A is attached to the first edge 46A and a second side wall 52A is attached to the second edge 48A. The side walls 50A and 52A are generally perpendicular to the wall member 44A and extend from the wall member 44A in the same direction. A male coupling member 56A is connected to the side wall 52A. The male coupling member 56A comprises a flange 57A which extends inwardly from the side wall 52A generally parallel to the wall member 44A. A bent-over lip 58A is connected to the flange 57A and extends generally parallel and adjacent thereto. A female coupling member 54A is connected to the side wall 50A. The female coupling member 54A comprises a generally C-shaped channel 60A having a longitudinal groove 62A. The channel 60A extends inwardly from the side wall 50A such that the groove 62A is open in a direction facing away from the flange 57A and to the exterior of the strip member 42A. The female coupling member 54A is adapted to receive and retain a male coupling member on a cooperating strip member. The strip member 42B, as shown in FIG. 6, is constructed similarly to the strip member 42A. The strip member 42B has an elongate generally planar wall member 44B having an inner display surface, a first longitudinally extending edge 46B and a spaced apart and generally parallel second longitudinally extending edge 48B. A first side wall 50B is attached to the first edge 46B and a second side wall 52B is attached to the second edge 48B. The side walls 50B and 52B are generally perpendicular to the wall member 44B. A male coupling member 56B is attached to the side wall 52B. The male coupling member 56B comprises a flange 57B which includes a bent-over lip 58B. The male coupling member 56B is adapted to be inserted into the groove 62A of the female coupling member 54A and to be retained by the female coupling member 54A of the strip member 42A. A female coupling member 54B is attached to the side wall 50B. The female coupling member 54B comprises a generally C-shaped channel 60B having a longitudinal groove 62B. The female coupling member 54B is adapted to receive and retain the male coupling member 56A of the strip member 42A. As shown in FIG. 6, the muntin bar assembly 20 is formed when cooperating strip members 42A and 42B are interconnected. The male coupling member 56A of the strip member 42A is inserted into the groove 62B of the female coupling member 54B of the cooperating strip member 42B and is removably or permanently retained by the female coupling member 54B. The male coupling member 56B of the cooperating strip member 42B is inserted into the longitudinal groove 62A of the female coupling member 54A and is removably or permanently retained by the female coupling member 56B. The strip member 42A may be formed in a first color, or with a first surface texture, while the strip member 42B may be formed in a second color, or with a second surface texture. The muntin bar 20 thereby can provide two different appearances, one appearance being viewed from the exterior of the window and the other being viewed from the interior of the window. FIG. 7 shows an alternate embodiment 70 of a muntin bar assembly. The muntin bar assembly 70 is constructed substantially the same as the muntin bar assembly 20 shown in FIG. 6 except that the strip members 71A and 71B of the muntin bar assembly 70 each include a wall member 72 including two spaced apart coplanar portions 74 and 76 and a center portion 78 located between the coplanar portions 74 and 76. The center portion 78 is parallel to the coplanar portions 74 and 76, but is inwardly displaced forming a depression in the outer surface of the strip member 71. FIG. 8 shows another alternate embodiment 80 of a muntin bar assembly. The muntin bar assembly 80 is constructed substantially the same as the muntin bar assembly 20 shown in FIG. 6 except that the strip members 81A and 81B of the muntin bar assembly 80 each include a wall member 82 including two spaced apart coplanar portions 84 and 86 and a center portion 88 located between the coplanar portions 84 and 86. The center portion 88 is outwardly raised to form a ridge with a surface substantially parallel to the coplanar portions 84 and 86. FIG. 9 shows another alternate embodiment 90 of a muntin bar assembly. The muntin bar assembly 90 is constructed substantially the same as the muntin bar assembly 20 shown in FIG. 6 except that the strip members 91A and 91B of the muntin bar assembly 90 include side walls 92 and 94 and a male coupling member 96 having a flange 97 with a bent lip 98. The bent lip 98 does not overlap the flange 97 of the male coupling member 96, but extends outwardly from the flange 97 to grip the female coupling member 99 at its tip. FIG. 10 shows an alternate embodiment 100 of a muntin bar assembly. The muntin bar assembly 100 is constructed substantially the same as muntin bar assembly 90 shown in FIG. 9 except that each wall member 102A and 102B includes two coplanar potions 104 and 106 and a center portion 108 located between the coplanar potions 104 and 106. The center portion 108 comprises an inwardly formed ridge that is generally V-shaped. The muntin bar assembly has been shown and described herein as including two strip members which are substantially identical to one another. However, it is contemplated that different types of strip members, formed with different colors, textures, or surface configurations, will be used with one another to form a muntin bar assembly that presents different interior and exterior appearances. For example, the strip member 42A, shown in FIG. 6, can be coupled to the strip member 71, shown in FIG. 7, to form a muntin bar assembly. Various features of the invention have been particularly shown and described in connection with the illustrated embodiments of the invention, however, it must be understood that these particular arrangements merely illustrate, and that the invention is to be given its fullest interpretation within the terms of the appended claims.
A muntin bar strip member adapted to interconnect to a cooperating strip member. The strip member has a wall member; a coupling means, such as a flange, extending from a longitudinal edge of the wall member; and a female coupling member, such as a channel, extending along an opposite longitudinal edge of the wall member. A muntin bar can be formed from a strip member interconnected to a second similarly structured strip member, where the flange of the second strip member is engaged in the channel of the first strip member, and conversely the flange of the first strip member engaged in the channel of the second strip member.
4
This is a continuation of Ser. No. 09/035,993 filed Mar. 6, 1998 now U.S. Pat. No. 5,967,714. BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to antimicrobial polymers prepared by copolymerization of tert-butylaminoethyl methacrylate with one or more aliphatically unsaturated monomers, a process for their preparation and their use. More particularly, the invention relates to antimicrobial polymers prepared by graft copolymerization of tert-butylaminoethyl methacrylate with one or more aliphatically unsaturated monomers on a substrate, a process for their preparation and their use. Colonization and spread of bacteria on surfaces of pipelines, containers or packaging are highly undesirable. Layers of slime often form, which allow the microbe populations to rise to extreme levels, lastingly impairing the quality of water, drinks and foodstuffs, and can even lead to decay of the goods and damage to the health of consumers. Bacteria are to be kept away from all areas of life where hygiene is of importance. Since textiles directly contact the body, and in particular the genital area, and are used for the care of the sick and elderly, textiles should be freed of bacteria. Bacteria should also be kept away from the surfaces of furniture and equipment in nursing wards, in particular in the intensive care and infant care sector, in hospitals, especially in rooms for medical operations, and in isolation wards for critical cases of infection, as well as in toilets. Equipment and surfaces of furniture and textiles are currently treated to ward against bacteria as required or also preventively with chemicals or solutions and mixtures thereof which act as disinfectants, such having a more or less broad and massive antimicrobial action. Such chemical compositions have a non-specific action, are often themselves toxic or irritating, or form degradation products which are unacceptable to health. Intolerances are often also found in appropriately sensitized persons. Another procedure which is used to inhibit the spread of bacteria on surfaces is to incorporate antimicrobially active substances into a matrix. Tert-butylaminoethyl methacrylate is a commercially available monomer of methacrylate chemistry and is employed in particular as a hydrophilic monomer in copolymerizations. Thus, EP 0 290 676 describes the use of various polyacrylates and polymethacrylates as a matrix for immobilization of bactericidal quaternary ammonium compounds. U.S. Pat. No. 3,592,805 discloses the preparation of systemic fungicides in which perhalogenated acetone derivatives are reacted with methacrylate esters, such as, for example, tert-butylaminoethyl methacrylate. U.S. Pat. No. 4,515,910 describes the use of polymers of hydrogen fluoride salts of aminomethacrylates in dental medicine. The hydrogen fluoride bonded in the polymers emerges slowly from the polymer matrix and is said to have actions against caries. In another technical field, U.S. Pat. No. 4,532,269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This polymer is used as an antimicrobial paint for ships, the hydrophilic tert-butylaminoethyl methacrylate promoting slow erosion of the polymer and in this way liberating the highly toxic tributyltin methacrylate as an antimicrobially active compound. In these applications, the copolymer prepared with aminomethacrylates is only a matrix or carrier substance for the added microbicidal active compounds, which (an diffuse or migrate out of the carrier. Polymers of this type lose their action at a greater or lesser speed when the necessary “minimum inhibitory concentration” (MIC) is no Longer achieved on the surface. EP 0 204 312 describes a process for the preparation of antimicrobially treated acrylonitrile fibers. The antimicrobial action is based on a protonated amine as a comonomer unit, dimethylaminoethyl methacrylate and tertbutylaminoethyl methacrylate, inter alia, being used as protonated species. However, the antimicrobial action of pronated surfaces is severely reduced after loss of the H ⊕ ions. A need, therefore, continues to exist for an improved method of providing surfaces with anti-bacterial properties. SUMMARY OF THE INVENTION Accordingly, one object of the present invention is to provide materials which have antimicrobial properties, which contain no active compounds which can be washed out, and in which the antimicrobial action is pH-independent. Briefly, this object and other objects of the present invention as hereinafter will become more readily apparent can be attained by a method of imparting antimicrobial activity to the surface(s) of an apparatus or article, by copolymerizing tertbutylaminoethyl methacrylate with at least one other aliphatically unsaturated monomer in the presence of said apparatus or article by which adhesion of the copolymer to said surface(s) is achieved. An aspect of the invention is a process for the preparation of antimicrobial polymers, which comprises subjecting tert-butylaminoethyl methacrylate to grafting copolymerization with one or more aliphatically unsaturated monomers on a substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS It has now been found, surprisingly, that polymers which have a surface which is permanently microbicidal, is not attacked by solvents and physical stresses and shows no migration are obtained by copolymerization of tertbutylaminoethyl methacrylate with one or more other aliphatically unsaturated monomers or by grafting copolymerization of tert-butylaminoethyl methacrylate with one or more aliphatically unsaturated monomers on a substrate. It is not necessary to provide the polymer with biocidally active compounds. The copolymerization of tert-butylaminoethyl methacrylate and one or more other aliphatically unsaturated monomers can be carried out by graft copolymerization on a substrate and is possible with the microbicidal action being largely retained. All aliphatically unsaturated monomers are suitable for this, such as, for example, acrylates and methacrylates of the formula: wherein R 1 is hydrogen or methyl, R 2 is hydrogen, a metal atom or a branched or unbranched aliphatic, cycloaliphatic, heterocyclic or aromatic hydrocarbon group having up to 20 carbon atoms or a branched or unbranched aliphatic, cycloaliphatic, heterocyclic or aromatic hydrocarbon chain having up to 20 carbon atoms, which is derivatized by carboxyl groups, carboxylate groups, sulfonate groups, alkylamino groups, alkoxy groups, halogens, hydroxyl groups, amino groups, dialkyl amino groups, phosphate groups, phosphonate groups, sulfate groups, carboxamido groups, sulfonamido groups, phosphonamido groups or combinations of these groupings. R 3 can be hydrogen or identical to R 2 . It is furthermore possible to employ vinyl compounds of the formula: and maleic and fumaric acid derivatives of the formula R 4 O 2 C—HC═CH—CO 2 R 4 in which R 4 can be hydrogen, an aromatic radical or a methyl group or can be identical to R 2 . R 5 can be hydrogen, a methyl group or a hydroxyl group, and can be identical to R 2 , or can be an ether Of the composition OR 2 . Suitable substrate materials include all polymeric plastics, such as, for example, polyurethanes, polyamides, polyesters, polyethers, polyether-block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), corresponding copolymers and blends, as well as natural and synthetic rubbers, with or without radiation-sensitive groups. The process of the invention can also be applied to surfaces of metal, glass or wooden bodies which are painted or are otherwise coated with plastic. The substrates' surfaces can be activated by a number of methods before the grafting copolymerization. They are expediently freed from oils, greases or other impurities beforehand in a known manner by means of a solvent. The standard polymers can be activated by UV radiation. A suitable source of radiation is, for example, a UV-Excimer apparatus HERAEUS Noblelight, Hanau, Germany. However, mercury vapor lamps are also suitable for activation of the substrate if they emit considerable proportions of the radiation in the ranges mentioned. The exposure time generally ranges from 0.1 second to 20 minutes, preferably 1 second to 10 minutes. The activation of the standard polymers with UV radiation can furthermore be carried out with an additional photosensitizer. Suitable such photosensitizers include, for example, benzophenone, as such are applied to the surface of the substrate and irradiated. In this context, irradiation can be conducted with a mercury vapor lamp using exposure times of 0.1 second to 20 minutes, preferably 1 second to 10 minutes. According to the invention, the activation can also be achieved by a high frequency or microwave plasma (Hexagon, Technics Plasma, 85551 Kirchheim, Germany) in air or a nitrogen or argon atmosphere. The exposure times generally range from 30 seconds to 30 minutes, preferably 2 to 10 minutes. The energy output of laboratory apparatus is between 100 and 500 W, preferably between 200 and 300 W. Corona apparatus (SOFTAL, Hamburg, Germany) can furthermore be used for the activation. In this case, the exposure times are, as a rule, 1-10 minutes, preferably 1-60 seconds. Activation by electron beams or y rays, for example, from a cobalt-60 source, and ozonization allows short exposure times which generally range from 0.1-60 seconds. The flaming of surfaces likewise leads to activation of the surfaces. Suitable apparatus, in particular those having a barrier flame front, can be constructed in a simple manner or obtained, for example, from ARCOTEC, 7129 Mönsheim, Germany. The apparatus can employ hydrocarbons or hydrogen as the combustible gas. In all cases, harmful overheating of the substrate must be avoided, which is easily achieved by intimate contact with a cooled metal surface on the substrate surface facing away from the flaming side. Activation by flaming is accordingly limited to relatively thin, flat substrates. The exposure times generally range from 0.1 second to 1 minute, preferably 0.5-2 seconds, The flames without exception are non-luminant and the distances between the substrate surfaces and the outer flame front range from 0.2-5 cm, preferably 0.5-2 cm. The substrate surfaces activated in this way are coated with tert-butylamino-ethyl methacrylate and one or more other aliphatically unsaturated monomers, if appropriate in solution, by known methods such as by dipping, spraying or brushing. Suitable solvents have proved to be water and water/ethanol mixtures, although other solvents can also be used if they have a sufficient dissolving power for the monomers and wet the substrate surfaces thoroughly. Solutions having monomer contents of 1-10% by weight, for example about 5% by weight, have proved suitable in practice and in general give continuous coatings which cover the substrate surface and have coating thicknesses which can be more than 0.1 μm in one pass. The grafting copolymerization of the monomers applied to the activated surfaces is expediently effected by short wavelength radiation in the visible range or in the long wavelength segment of the UV range of electromagnetic radiation. The radiation of a UV-Excimer of wavelengths 250-500 mm, preferably 290-320 mm, for example, is particularly suitable. Mercury vapor lamps are also suitable here if they emit considerable amounts of radiation in the ranges mentioned. The exposure times generally range from 10 seconds to 30 minutes, preferably 2-15 minutes. Copolymers with tert-butylaminoethyl methacrylate as the comonomer unit also show intrinsic microbicidal properties without grafting to a substrate surface. One embodiment of the present invention comprises a procedure in which the copolymerization of tert-butylaminoethyl methacrylate and one or more other aliphatically unsaturated monomers can be carried out on a substrate. The present polymers of tert-butylaminoethyl methacrylate and at least one other aliphatically unsaturated monomers can be applied to the substrate in solution. Suitable solvents include, for example, water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, methylene chloride, tetrahydrofuran and acetonitrile. The solution of the polymers according to the invention is applied to the standard polymers, for example, by dipping, spraying or painting. If the present polymer is produced directly on the substrate surface without grafting, suitable initiators are added in order to promote polymerization. Initiators which can be used include, inter alia, azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all the customary photoinitiators, such as, for example, acetophenones and benzophenone. The initiation of the polymerization can be carried out by means of heat or by electromagnetic radiation, such as, for example, UV light or γ-radiation. The products coated with the present polymers can be medical articles or hygiene articles. Products of the invention which are obtained by grafting copolymerization can likewise be medical articles or hygiene articles. The products coated with the present polymers can be used for the production of medical articles, such as, for example, catheters, blood bags, drainages, guide wires and surgical instruments, as well as for the production of hygiene articles, such as, for example, toothbrushes, toilet seats, combs and packaging materials. Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified. EXAMPLE 1 A 19.2 g amount of tert-butylaminoethyl methacrylate, 2.6 g of methyl methacrylate and 150 ml of tetrahydrofuran is heated to 60° C. under an inert gas. When the temperature is reached, 0.33 g of azobisisobutyronitrile, dissolved in 10 ml of tetrahydrofuran, is added. At the end of 24 hours, the reaction is ended by stirring the mixture into 1 liter of a water/ice mixture. The reaction product is filtered and washed with 300 ml of n-hexane. The product is then distributed over several Soxhlets and extracted with water for 24 hours, and is then dried at 50° C. in vacuo for 12 hours. EXAMPLE 2 A 4 g amount of copolymer from Example 1 is dissolved in 40 ml of tetrahydrofuran. A polyamide 12 film is immersed in this solution for 5 seconds, removed from the solution for 10 seconds and them immersed again for 5 seconds, so that a uniform film of the copolymer on the polyamide film has formed after subsequent drying at room temperature under normal pressure. The film is then dried at 50° C. in vacuo for 24 hours. The film is subsequently extracted in water at 30° C. five times for 6 hours and then dried at 50° C. for 12 hours. EXAMPLE 3 A 4 g amount of copolymer from Example 1 is dissolved in 40 ml of tetrahydrofuran. A polyvinyl chloride film is immersed in this solution for 2 seconds, removed from the solution for 10 seconds and then immersed again for 2 seconds, so that a uniform film of the copolymer has formed on the polyvinyl chloride film after subsequent drying at room temperature under normal pressure. The film is then dried at 50° C. in vacuo for 24 hours. The film is subsequently extracted in water at 30° C. five times for 6 hours and then dried at 50° C. for 12 hours. EXAMPLE 4 A polyamide 12 film is exposed to the 172 nm radiation of an Excimer radiation source manufactured by Heraeus for 2 minutes under a pressure of 1 mbar. The film activated in this way is laid and fixed in an irradiation reactor under an inert gas. The film is then covered with a layer of 20 ml of a mixture of 3 g of tert-butylaminoethyl methacrylate, 2 g of methyl methacrylate and 95 g of methanol in a countercurrent flow of inert gas. The irradiation chamber is closed and placed a distance of 10 cm underneath an Excimer radiation unit manufactured by Heraeus, which has an emission of wavelength 308 nm. The irradiation is started, and the exposure time is 15 minutes. The film is removed and rinsed with 30 ml of methanol. The film is then dried at 50° C. in vacuo for 12 hours. The film is subsequently extracted in water at 30° C. five times for 6 hours, and then dried at 50° C. for 12 hours. Measurement of bactericidal action: The bactericidal action of coated plastics was measured as follows: A 100 μl amount of a cell suspension of Klebsiella pneumoniae were placed on a piece of film 2×2 cm in size. The bacteria were suspended in PBS buffer (phosphate-buffered saline); the cell concentration was 10 5 cells per ml of buffer solution. This drop was incubated for up to 3 hours. In order to prevent any drying of the applied drop, the piece of film was laid in a polystyrene Petri dish wetted with 1 ml of water. After the end of the contact time, the 100 pl were taken up with an Eppendorf tip and diluted in 1.9 ml of sterile PBS. A 0.2 ml amount of this solution was plated out on nutrient agar. The rate of inactivation was calculated from the number of colonies which had grown. Checking the resistance of the coatings: Before the measurement of the bactericidal action, the coated films were subjected to the following pretreatments: A: Washing in boiling water for 10 minutes B: Washing in 96% strength ethanolic solution for 10 minutes C: Washing in warm water at 25° C. under ultrasonic treatment for 10 minutes D: No pretreatment The results of the measurements, taking into account the particular pretreatment, are listed in Table 1. TABLE 1 Rate of inactivation Example: A B C D 2   2%  <10%   51% 99.9% 3   2%  <10%   50% 99.9% 4 99.9% 99.9% 99.9% 99.9% After thermal, chemical or mechanical pretreatment, the antimicrobial layers produced by grafting of a substrate surface continue to show virtually complete inactivation of the bacteria applied. The physically adhered layers are less stable than the pretreatments of methods A, B and C. In addition to the microbicidal activity against cells of Klebsiella pneumoniae which has been described above, all the coated films also showed a microbicidal action against cells of Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli, Rhizopus oryzae, Candida tropicalis and Tetrahymena pyriformis. The rate of inactivation after treatment method D was also more than 99% in these cases. The disclosure of priority German Application No. 197 09 075.3 filed Mar. 6, 1997 is hereby incorporated into the disclosure of the application. 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.
Antimicrobial activity is imparted to the surface(s) of an apparatus or article by a method, comprising: copolymerizing tertbutylaminoethyl methacrylate with at least one other aliphatically unsaturated monomer in the presence of said apparatus or article by which adhesion of the copolymer to said surface(s) is achieved. In an embodiment of the invention, adhesion of the polymer coating on the apparatus or article occurs by graft copolymerization.
8
[0001] This application claims the benefit of U.S. Provisional Application No. 61/625,448 filed Apr. 17, 2012. U.S. Provisional Application No. 61/625,448 filed Apr. 17, 2012 is hereby incorporated by reference in its entirety. BACKGROUND [0002] The following relates to the nuclear power reactor arts and related arts. [0003] With reference to FIGS. 1 and 2 , the lower portion of a nuclear power plant of the pressurized water configuration, commonly called a pressurized water reactor (PWR) design, is shown. A nuclear reactor core 10 comprises an assembly of vertically oriented fuel rods containing fissile material, typically 235 U. The reactor core 10 is disposed at or near the bottom of a pressure vessel 12 that contains primary coolant water serving as a moderator to moderate the chain reaction and as coolant to cool the reactor core 10 . The primary coolant further acts as a heat transfer medium conveying heat generated in the reactor core 10 to a steam generator. At the steam generator, heat from the primary coolant transfers to a secondary coolant loop to convert the secondary coolant into steam that is used for a useful purpose, such as driving a turbine of an electrical power generation facility. A conventional PWR design includes one or (typically) more steam generators that are external to the pressure vessel containing the nuclear reactor core. Large-diameter piping carries primary coolant from the pressure vessel to the external steam generator and back from the steam generator to the pressure vessel to complete a primary coolant flow loop. In some designs the external steam generator is replaced by an internal steam generator located inside the pressure vessel, which has the advantage of eliminating the large diameter piping (replaced by secondary coolant feedwater and steam outlet lines that are typically of lower diameter and that do not carry the primary coolant that flows through the reactor core). Note that FIG. 1 is a diagrammatic view of the lower reactor core region and does not include features relating to the steam generator or ancillary components. [0004] The vertical fuel rods of the reactor core 10 are organized into fuel assemblies 14 . Illustrative FIG. 1 shows a side view of a 9×9 array of fuel assemblies 14 , although arrays of other sizes and/or dimensions can be employed. In turn, each fuel assembly 14 comprises an array of vertically oriented fuel rods, such as a 18×18 array of fuel rods, or a 14×14 array, or so forth. The fuel assemblies further include a lower end fitting, upper end fitting, vertical guide tubes connecting the end fittings, and a number of spacer grids connected to the guide tubes, instrument tubes and fuel rods. The spacer grids fit around the guide tubes to precisely define the spacing between fuel rods and to add stiffness to the fuel assembly 14 . The spacer grids may or may not be welded to the guide tubes. (Note, FIGS. 1 and 2 represent the fuel rods of each fuel assembly 14 are shown diagrammatically with vertical lines which are not to scale respective to size or quantity, and the spacer grids, guide tubes, and other features are not shown). It is noted that the dimensions of the array of fuel assemblies 14 may in general be different from the dimensions of the array of fuel rods within the fuel assembly 14 . The fuel assemblies may employ rectangular fuel rod packing and have a square cross section, or may employ hexagonal fuel rod packing and have a hexagonal cross section, or so forth). The reactor core 10 comprising fuel assemblies 14 is disposed in a core basket 16 that is mounted inside the pressure vessel 12 . The lower end fitting of each fuel assembly 14 includes features 18 that engage with a core plate. (The core plate, basket mounting, and other details are not shown in diagrammatic FIG. 1 ). [0005] The reactor control system typically includes a control rod assembly (CRA) operated by a control rod drive mechanism (CRDM) (not shown in FIGS. 1 and 2 ). The CRA includes vertically oriented control rods 20 containing neutron poison. A given control rod is controllably inserted into one fuel assembly 14 through a designated vertical guide tube of the fuel assembly 14 . Typically, all the control rods for a given fuel assembly 14 are connected at their top ends to a common termination structure 22 , sometimes called a spider, and a connecting rod 24 connects at its lower end with the spider 22 and at its upper portion with the CRDM (upper end not shown). The CRA for a single fuel assembly 14 thus comprises the control rods 20 , the spider 22 , and the connecting rod 24 , and this CRA moves as a single translating unit. In the PWR design, the CRA is located above the reactor core 10 and moves upward in order to withdraw the control rods 20 from the fuel assembly 14 (and thereby increase reactivity) or downward in order to insert the control rods 20 into the fuel assembly 14 (and thereby decrease reactivity). The CRDM is typically designed to release the control rods so as to fall into the reactor core 10 and quickly quench the chain reaction in the event of a power failure or other abnormal event. [0006] Because the reactor control system is a safety-related feature, applicable nuclear safety regulations (for example, promulgated by the Nuclear Regulatory Commission, NRC, in the United States) pertain to its reliability, and typically dictate that the translation of the CRA be reliable and not prone to jamming. The translation of the CRA should be guided to ensure the control rods move vertically without undue bowing or lateral motion. Toward this end, each CRA is supported by a control rod guide structure 30 which comprises horizontal guide plates 32 mounted in a spaced-apart fashion on vertical frame elements 34 . Each guide plate 32 includes openings or passages or other camming surfaces (not visible in the side view of diagrammatic FIGS. 1 and 2 ) that constrain the CRA so that the rods 20 , 24 are limited to vertical movement without bowing or lateral movement. [0007] With continuing reference to FIGS. 1 and 2 , the CRA guide assemblies 30 have substantial weight indicated by downward arrow F G,weight in FIG. 2 , and are supported by a weight-bearing upper core plate 40 . The fuel assemblies 14 are also relatively heavy. However, in a conventional PWR the primary coolant circulation rises through the fuel assemblies 14 , producing a net lifting force on the fuel assemblies 14 indicated by upward arrow F FA,lift . Accordingly, the fuel assemblies 14 while typically resting on the bottom of the core basket 16 , are susceptible to being lifted upward by the lift force F FA,lift and press against the upper core plate 40 . The lift force F FA,lift is thus also borne by the upper core plate 40 . The upper core plate 40 thus is a spacer element disposed between and spacing apart the lower end of the CRA guide assembly 30 and the upper end of the corresponding fuel assembly 14 . To avoid damaging the fuel rods, each fuel assembly 14 typically includes a hold-down spring sub-assembly 42 that preloads the fuel assembly 14 against the upper core plate 40 and prevents lift-off of the fuel assembly 14 during normal operation. The hold-down spring 42 is thus also disposed between the lower end of the CRA guide assembly 30 and the upper end of the corresponding fuel assembly 14 . Additionally, alignment features 44 , 46 are provided on the upper end of the fuel assembly 14 and the lower end of the CRA guide structure 30 , respectively, to assist alignment. [0008] A PWR such as that of FIGS. 1 and 2 is typically designed to provide electrical power of around 500-1600 megawatts. The fuel assemblies 14 for these reactors are typically between 12 and 14 feet long (i.e., vertical height) and vary in array size from 14×14 fuel rods per fuel assembly to 18×18 fuel rods per fuel assembly. The fuel assemblies for such PWR systems are typically designed to operate between 12- and 24-month cycles before being shuffled in the reactor core. The fuel assemblies are typically operated for three cycles before being moved to a spent fuel pool. The fuel rods typically comprise uranium dioxide (UO 2 ) pellets or mixed UO 2 /gadolinium oxide (UO 2 —Gd 2 O 3 ) pellets, of enrichment chosen based on the desired core power. BRIEF SUMMARY [0009] In one aspect of the disclosure, a pressurized water reactor (PWR) comprises: a pressure vessel containing primary coolant water; a nuclear reactor core disposed in the pressure vessel and including a plurality of fuel assemblies wherein each fuel assembly includes a plurality of fuel rods containing a fissile material; a control system including a plurality of control rod assemblies wherein each control rod assembly is guided by a corresponding control rod assembly guide structure; and a support element disposed above the control rod assembly guide structures wherein the support element supports the control rod assembly guide structures. In some embodiments the pressure vessel is a cylindrical pressure vessel and the support element comprises a support plate having a circular periphery supported by the cylindrical pressure vessel. In some embodiments the control rod assembly guide structures hang downward from the support plate. In some embodiments the lower end of each control rod assembly guide structure includes alignment features that engage corresponding alignment features of the upper end of the corresponding fuel assembly. [0010] In another aspect of the disclosure, a method comprises: operating a pressurized water reactor (PWR) wherein the operating includes circulating primary coolant in a pressure vessel upward through a nuclear reactor core that includes a plurality of fuel assemblies wherein each fuel assembly includes a plurality of fuel rods containing a fissile material; and during the operating, suspending control rod drive assembly guide structures disposed in the pressure vessel from suspension anchors disposed above the control rod drive assembly guide structures. In some such method embodiments, a downward force (other than gravity) is not applied against the fuel assemblies during the operating. In some such method embodiments, upward strain of the fuel assemblies and downward strain of the suspended control rod drive assembly guide structures is accommodated during the operating by a gap between the tops of the fuel assemblies and the bottoms of the suspended control rod drive assembly guide structures. [0011] In another aspect of the disclosure, a pressurized water reactor (PWR) comprises: a pressure vessel containing primary coolant water; a nuclear reactor core disposed in the pressure vessel and including a plurality of fuel assemblies wherein each fuel assembly includes a plurality of fuel rods containing a fissile material; a control system including a plurality of control rod assemblies wherein each control rod assembly includes control rods selectively inserted into the nuclear reactor core and wherein each control rod assembly is guided by a corresponding control rod assembly guide structure; wherein there is a gap between the bottoms of the control rod assembly guide structures and the top of the nuclear reactor core and wherein no spacer element or spring is disposed in the gap. In some embodiments the control rod assembly guide structures are not supported from below the control rod assembly guide structures. In some embodiments there is a one-to-one correspondence between the control rod assembly guide structures and the fuel assemblies of the nuclear reactor core, and the lower end of each control rod assembly guide structure includes alignment features that engage corresponding alignment features of the upper end of the corresponding fuel assembly. In some embodiments the PWR further includes a support element disposed above the control rod assembly guide structures and anchoring the tops of the control rod assembly guide structures such that the control rod assembly guide structures are suspended from the support element. In some embodiments flow of primary coolant water in the pressure vessel in the operational state of the PWR is not sufficient to lift the fuel assemblies upward. [0012] In another aspect of the disclosure, a nuclear reactor fuel assembly is configured for installation and use in a pressurized water nuclear reactor (PWR). The nuclear reactor fuel assembly includes a bundle of fuel rods containing a fissile material, and alignment features disposed at an upper end of the nuclear reactor fuel assembly. The upper end of the nuclear reactor fuel assembly is not configured as a load bearing structure. In some embodiments the upper end of the nuclear reactor fuel assembly does not include any hold-down springs. In some embodiments the alignment features disposed at the upper end of the nuclear reactor fuel assembly are configured to mate with corresponding alignment features of a control rod assembly guide structure. BRIEF DESCRIPTION OF THE DRAWINGS [0013] The invention may take form in various components and arrangements of components, and in various process operations and arrangements of process operations. The drawings are only for purposes of illustrating preferred embodiments and are not to be construed as limiting the invention. [0014] FIG. 1 diagrammatically shows a side sectional view of the lower portion of a pressurized water reactor (PWR) according the the prior art. [0015] FIG. 2 diagrammatically shows an exploded view of a single fuel assembly and the corresponding control rod assembly (CRA) guide structure of the prior art PWR of FIG. 1 . [0016] FIG. 3 diagrammatically shows a side sectional view of the lower portion of a low flow rate PWR as disclosed herein. [0017] FIG. 4 diagrammatically shows an exploded view of a single fuel assembly and the corresponding CRA guide structure of the disclosed PWR of FIG. 3 . [0018] FIG. 5 diagrammatically shows an enlarged view of the lower end of the CRA guide structure and upper end of the fuel assembly of the embodiment of FIGS. 3 and 4 showing the mating features and the gap. [0019] FIG. 6 diagrammatically shows a single fuel assembly and the corresponding CRA guide structure of another disclosed PWR embodiment. [0020] FIG. 7 diagrammatically shows a suitable shipping configuration for shipping the fuel assembly and continuous CRA guide structure via rail or another suitable carrier to a PWR site for installation during a fueling or refueling operation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0021] With reference to FIGS. 3 and 4 , a pressurized water reactor (PWR) is shown which is designed to operate as a small modular reactor (SMR). The SMR preferably outputs 300 megawatts (electrical) or less, although it is contemplated for the SMR to output at higher power. The PWR of FIGS. 3 and 4 is designed to operate at a relatively low primary coolant flow rate, which is feasible because of the relatively low SMR output power. The PWR of FIGS. 3 and 4 includes a number of components that have counterparts in the PWR of FIGS. 1 and 2 , including: a reactor pressure vessel 12 ; a reactor core 10 comprising fuel assemblies 14 in a core basket 16 ; a control rod assembly (CRA) for each fuel assembly that includes control rods 20 mounted on a spider 22 connected to the lower end of a connecting rod 24 ; and a CRA guide structure 30 for each CRA comprising horizontal guide plates 32 mounted in a spaced-apart fashion on vertical frame elements 34 . Although these components have counterparts in the conventional PWR of FIGS. 1 and 2 , it is to be understood that the sizing or other aspects of the components in the PWR of FIGS. 3 and 4 may be optimized for the SMR operational regime. For example, a PWR designed to operate at 150 megawatts electrical may have fuel assemblies 14 that are 8 feet long and use a 17×17 bundle of fuel rods per fuel assembly 14 with 24 guide tubes spaced on a 0.496-inch pitch. [0022] The PWR of FIGS. 3 and 4 omits the upper core plate 40 of the embodiment of FIGS. 1 and 2 . Omitting this weight-bearing plate 40 has substantial advantages. It reduces the total amount of material thus lowering manufacturing cost. Additionally, the upper core plate 40 presents substantial frontal area generating flow resistance. Although this can be mitigated to some extent by including flow passages in the plate 40 , the frontal area occupied by the control rods 20 , the lower end plates of the CRA guide assemblies 30 , and the upper end fittings of the fuel assemblies 14 , limits the amount of remaining frontal area that can be removed. The load-bearing nature of the upper core plate 40 also limits the amount of material that can be safely removed to introduce flow passages through the plate 40 , since removing material to provide flow passages reduces the load-bearing capacity of the plate 40 . [0023] However, omitting the load-bearing upper core plate 40 introduces substantial new issues. In the embodiment of FIGS. 1 and 2 , the plate 40 performs the functions of supporting the weight of the CRA guide assemblies 30 and providing the upper stop against which the lift force F FA,lift on the fuel assemblies 14 operates to stabilize the positions of the fuel assemblies 14 . Moreover, the upper core plate 40 provides a common anchor point for aligning the fuel assemblies 14 with their respective CRA guide assemblies 30 . These issues are addressed in the embodiment of FIGS. 3 and 4 as follows. [0024] In the embodiment of FIGS. 3 and 4 , the CRA guide assemblies 30 are suspended from above by a support element 50 disposed above the CRA guide assemblies 30 . In embodiments in which the pressure vessel 12 is a cylindrical pressure vessel (where it is to be understood that “cylindrical” in this context allows for some deviation from a mathematically perfect cylinder, for example to allow for tapering of the upper end of the pressure vessel 12 , adding various vessel penetrations or recesses, or so forth), the support element 50 is suitably a support plate 50 having a circular periphery supported by the cylindrical pressure vessel (for example supported by an annular ledge, or by welding the periphery of the plate 50 to an inner cylindrical wall of the cylindrical pressure vessel, or so forth). In some embodiments the CRA guide assemblies 30 are not supported from below. This arrangement is feasible because in the SMR design the reduced height of the fuel assemblies 14 reduces the requisite travel for the CRA and hence reduces the requisite height for the CRA guide assemblies 30 in the SMR of FIGS. 3 and 4 as compared with the higher power PWR of FIGS. 1 and 2 . [0025] The support element 50 is located in a less congested area of the pressure vessel 12 as compared with the upper core plate 40 of the PWR of FIGS. 1 and 2 . The area above the CRA support structures 30 includes the upper ends of the CRA assemblies 30 and the connecting rods 24 , but not the fuel assemblies. Accordingly, there is more “unused” frontal area of the support plate 50 , which allows for forming relatively more and/or larger flow passages into the support element 50 . The support element 50 is also further away from the reactor core 10 than the upper core plate 40 of the PWR of FIGS. 1 and 2 , which makes any spatial variation in the flow resistance that may be introduced by the frontage of the support element 50 less problematic as compared with the upper core plate 40 . [0026] The load-bearing provided by the upper core plate 40 respective to the upward lift force F FA,lift is not needed in the SMR of FIGS. 3 and 4 , because the flow rate sufficient to provide SMR output of 300 megawatts (electrical) is generally not sufficient to generate a lift force capable of overcoming the weight of the fuel assemblies 14 . Thus, in the SMR embodiment of FIGS. 3 and 4 the fuel assemblies 14 have a net force F FA,weight which is the weight of the fuel assembly 14 minus the lifting force generated by the relatively low primary coolant flow rate. As a consequence, the fuel assemblies 14 remain supported from below by the core basket 16 (or by a core plate component inside of or forming the bottom of the core basket 16 ). Thus, in the embodiment of FIGS. 3 and 4 the upper end of the fuel assembly 14 is not configured as a load-bearing structure, and both the upper core plate 40 and the hold-down springs 42 are omitted in the SMR embodiment of FIGS. 3 and 4 . [0027] With continuing reference to FIGS. 3 and 4 and with further reference to FIG. 5 , relative alignment between corresponding CRA guide structure 30 and fuel assembly 14 is achieved by engagement of mating features 60 on the top end of the fuel assembly 14 and corresponding mating features 62 on the bottom end of the CRA guide structure 30 . The features 60 , 62 ensure lateral alignment. In the illustrative embodiment the mating features 60 on the top of the fuel assembly 14 are protrusions, e.g. pins, and the mating features 62 on the bottom of the CRA guide structure 30 are mating recesses; however, other mating feature configurations are contemplated. In some embodiments the mating pins 60 on the top of the fuel assembly 14 also serve as anchor points for lifting the fuel assembly 14 out of the PWR during refueling or other maintenance operations, as described in Walton et al., “Nuclear Reactor Refueling Methods and Apparatuses”, U.S. Ser. No. 13/213,389 filed Aug. 19, 2011, which is incorporated herein by reference in its entirety. [0028] With particular reference to FIGS. 4 and 5 , vertical alignment is an additional issue. The fuel assembly 14 and the CRA guide structure 30 are subject to respective strains S G,thermal and S FA,thermal as the components 14 , 30 increase from ambient temperature to operational temperature. In the embodiment of FIGS. 3-5 , the upper end of the CRA guide structure 30 and the lower end of the fuel assembly 14 are both anchored. Thus, the thermal expansion causes the upper end of the fuel assembly 14 and the lower end of the CRA guide structure 30 to come closer together. This is accommodated by a gap G between the lower end of the CRA guide structure 30 and the upper end of the corresponding fuel assembly 14 . The gap G is chosen to accommodate thermal expansion at least up to temperatures credibly expected to be attained during operation or credible malfunction scenarios. The mating features 60 , 62 are designed to span the gap G in order to provide the lateral alignment between the CRA guide structure 30 and corresponding fuel assembly 14 . It will be noted that there is no spacer element or spring in the gap G. (The control rods 20 do pass through the gap G when inserted into the fuel assembly 14 ; however, the control rods 20 are not spacer elements that space apart the CRA guide structure 30 and fuel assembly 14 , and are also not springs. Similarly, primary coolant water fills the gap G but is also neither a spacer element nor a spring). [0029] The embodiment of FIGS. 3-5 employs the CRA guide structure 30 which comprises the spaced apart horizontal guide plates 32 mounted on the vertical frame elements 34 . This is a conventional CRA guide structure design, and is commonly used in conjunction with external control rod drive mechanism (CRDM) units (not shown in FIGS. 3-5 ) disposed outside of and above the pressure vessel 12 of the PWR. In some embodiments, it is contemplated to employ internal CRDM disposed inside the pressure vessel 12 . [0030] With reference to FIG. 6 , it is also contemplated to employ a continuous CRA guide structure 30 C which provides continuous support/guidance of the CRA over the entire length of the continuous CRA guide structure 30 C. The embodiment of FIG. 6 also employs a heavy terminating element 22 H in place of the conventional spider to provide the common termination structure at which the top ends of the control rods 20 are connected. The heavy terminating element 22 H advantageously adds substantial weight to the translating CRA 20 , 22 H, 24 as compared with the conventional CRA 20 , 22 , 24 of the PWR of FIGS. 3-5 . This additional weight reduces SCRAM time and effectively compensates for the otherwise reduced weight of the SMR CRA which is shortened as compared with the CRA of a higher-power PWR. The “Inset” of FIG. 6 shows a perspective view of the heavy terminal element 22 H, while “Section A-A” of FIG. 6 shows a cross-section of the continuous CRA guide structure 30 C. As seen in Section A-A, the CRA guide structure 30 C includes camming surfaces 70 that guide the control rods 20 , and a larger contoured central opening 72 that guides the heavy terminal element 22 H. Additionally, the CRA guide structure 30 C includes flow passages 74 to allow primary coolant water to egress from the internal volume 70 , 72 quickly as the CRA falls during a SCRAM. Additional aspects of the continuous CRA guide structure 30 C and the heavy terminal element 22 H are set forth in Shargots et al., “Support Structure For A Control Rod Assembly Of A Nuclear Reactor”, U.S. Ser. No. 12/909,252 filed Oct. 21, 2010, which is incorporated herein by reference in its entirety. [0031] With reference to FIG. 7 , the fuel assembly 14 , CRA guide structure 30 C, and connecting rod 24 are suitably shipped as components. Because the upper end of the nuclear reactor fuel assembly is not configured as a load-bearing structure and does not include the hold-down spring sub-assembly 42 (cf. FIG. 2 ), shipping weight is reduced, and the possibility of collision or entanglement of the hold-down springs with surrounding objects during shipping is eliminated. As seen in FIG. 7 , the shipping configuration for the fuel assembly 14 includes the control rods 20 fully inserted into the fuel assembly 14 . Optionally, the heavy terminal element 22 H (or, alternatively, the spider 22 in embodiments employing it) is connected to the top ends of the control rods 20 that are inserted into the fuel assembly 14 during shipping. The continuous CRA guide structure 30 C can be shipped as a single pre-assembled unit, as shown in FIG. 7 , or alternatively may be constructed as stacked segments that are shipped in pieces and welded together at the PWR site. The connecting rod 24 is suitably shipped as a separate element that is detached from the spider or heavy terminal element 22 , 22 H. The lower end of the connecting rod 24 optionally includes a J-lock fitting or other coupling 80 via which the lower end may be connected to the spider or heavy terminal element 22 , 22 H during installation into the PWR. Alternatively, the lower end may be directly welded to the spider or heavy terminal element 22 , 22 H. [0032] The preferred embodiments have been illustrated and described. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
A pressurized water reactor (PWR) comprises a pressure vessel containing primary coolant water. A nuclear reactor core is disposed in the pressure vessel and includes a plurality of fuel assemblies. Each fuel assembly includes a plurality of fuel rods containing a fissile material. A control system includes a plurality of control rod assemblies (CRA's). Each CRA is guided by a corresponding CRA guide structure. A support element is disposed above the CRA guide structures and supports the CRA guide structures. The pressure vessel may be cylindrical, and the support element may comprise a support plate having a circular periphery supported by the cylindrical pressure vessel. The CRA guide structures suitably hang downward from the support plate. The lower end of each CRA guide structure may include alignment features that engage corresponding alignment features of the upper end of the corresponding fuel assembly.
8
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a national phase entry under 35 U.S.C. §371 of International Patent Application PCT/BR2009/000414, filed Dec. 18, 2009, designating the United States of America and published in English as International Patent Publication WO 2010/069023 A2 on Jun. 24, 2010, which claims the benefit under Article 8 of the Patent Cooperation Treaty and under 35 U.S.C. §119(e) to Brazilian Patent Application Serial No. P10805365-0, filed Dec. 19, 2008, the disclosure of each of which is hereby incorporated herein in its entirety by this reference. FIELD OF THE INVENTION The present invention relates to the electrodes used to apply transdermal electrical stimuli to patients and/or to detect electrical signals from patients, such as sets of electrodes used in electrical impedance tomography, however, without being limited to the latter. DESCRIPTION OF THE PRIOR ART The medical application of electrodes connected to specific equipment intended for electrical stimulation or detection of electrical signals comprehends both the application of currents or voltages through the skin, examples thereof comprising transcutaneous nerve or muscle stimulation and functional electrical stimulation, such as the detection of electrical signals exemplified by the electrocardiogram, the electroencephalogram, and the electromyiogram, as well as techniques whereby is applied an electrical signal through the skin, simultaneously measuring the resulting signals, as occurs with electrical impedance tomography. The electrical impedance tomography—generally known by the acronym EIT: Electrical Impedance Tomography—is an already known technique which consists of placing a plurality of electrodes in contact with the skin of the patient on a given region, and performing a series of steps comprising the injection of a current between the electrodes of a pair of electrodes, measuring the electrical potentials of the remaining electrodes, and repeating this step for all the electrodes of the entire set of electrodes. The measured values are sent to data processing equipment and are subjected to a treatment, which results in an image showing the electrical impedance within the region of interest. Contrary to other techniques used to follow up the conditions of the patient, the EIT is suitable for continuously monitoring the condition of the patient, due to being non-invasive and due to not involving risks that might limit the number and frequency of monitoring actions, such as occurs, for example, with X-rays. Since the distance between the points on the skin whereto the electrodes are attached may vary, either due to the effects of the patient's breathing (in the case of thoracic or abdominal monitoring) or even due to movements from the part of the patient, it is necessary that the electrode supporting element, normally configured as a strap, be capable of following these movements, in order to warrant permanent contact between the electrodes and the skin. Patent Application No. BR PI0704408, of the same filing applicant of the instant application, illustrated in FIGS. 1 and 2 of the instant application, shows an electrode strap formed of a strip of fabric, both flexible and non-conductive, folded over itself in the longitudinal direction, resulting in a first section turned towards the patient and a second section oriented in the opposite direction, that is, externally to the patient. At spaced locations along the first section there is deposited a flexible conductive material, selectively in order to form a plurality of first circular or oblong regions or zones 34 , intended to contact the skin of the patient. Each of these zones 34 has an extension 24 which extends towards the fold, surrounding the same and extending over the second section whereon it broadens forming a second zone 27 , approximately coincident with the first zone. This second zone 27 serves to provide the electrical and mechanical connection to the points of contact 12 of a flexible, insulating and longitudinally non-deformable supporting strip 10 , each point of contact 12 being connected, by means of a flexible conductive track 39 embedded in the supporting strip 10 , to a connector 42 that is provided with means of contact with the cabling that connects the strap to the monitoring apparatus. As may be observed in FIGS. 1 and 2 , the structure in question is complex, which manufacture involves the performance of cutting/opening of windows 33 and intermediary spaces 37 between the first zones 34 , as well as between the second zones 27 in the fabric material, in addition to the selective placement of the conductive material, the installation of the supporting strip 10 , etc. Moreover, the absence of shielding means of the flexible tracks 39 might entail the detection of interfering signals, thereby compromising the accuracy of the results. One other disadvantage of the object of the cited application resides in the act of there being required the manual application of a conductive gel material on the zones 34 in order to improve the electrical contact with the skin of the patient. There are presently known in the art several alternatives for the preparation of electrodes that dispense the manual application of such gels. In this regard, in U.S. Pat. No. 5,785,040, entitled Medical Electrode System, there is disclosed a system comprising a flexible, non-conductive backing material, having juxtaposed to the face turned towards the patient a plurality of patches made of a conductive material which face a flexible non-conductive blade. The latter is provided with openings or windows in the positions corresponding to the pads, with dimensions slightly lesser than the same. Through such windows, each of these conductive patches contacts the upper side of a conductive gel plate, which lower face adheres to the skin of the patient. The conduction of electrical signals is provided by flexible cables whose ends are permanently secured to the faces of the conductive pads turned towards the flexible backing material. Due to this last characteristic, the assembly cannot be washed, which fact compromises the reuse thereof. It is an expensive solution in light of its complex structure, and its application is limited. In U.S. Pat. No. 6,788,979, entitled Electrical Stimulation Compress Kit there is disclosed a system whereby a flexible insulating strap, equipped with a VELCRO®-type closure means, is applied by tightening around a part of the body of a patient, exerting a compressive force thereon. At certain points, this strap is crossed through by metallic terminals of a fastener type which outer pin provides a point for attachment for the terminal of the cable that conducts the electrical signals. The inner face of each terminal establishes an electrical contact with a conductive hook-loop fastener, which is removably attached to the strap by the adhesion of a first conductive gel layer. A second layer of conductive gel is in contact with the skin of the patient, the second layer being separated by a conductive web that may be made of metal or any other low resistivity material. This conductive web becomes necessary due to the small size of the area of the terminal turned towards the patient, which might result in a concentration of the transcutaneous current. The conductive web provides a uniform distribution of the current throughout the entire surface of the pad, reducing the contact resistance with the skin and avoiding the occurrence of current concentration points. In addition to the disadvantage represented by the need to use the pads, the described system has the disadvantage that the strap, in contact with the skin, is liable to become contaminated by sweat and other secretions; the washing or sterilization of the strap poses problems due to the presence of the metallic terminals and the VELCRO®-type adhesive means. The alternative, consisting in the mere disposal of the strap, constitutes a liability for the users of this system. OBJECTS OF THE INVENTION In view of what has been set forth above, one object of the present invention consists in the provision of a system of electrodes combining low cost and easy applicability to the patient. One other object consists in the provision of a system of electrodes comprising low-cost elements, which disposal might not constitute an excessive burden to hinder the use thereof. One further objective consists in the provision of a system that might dispense the use of conductive pads for uniform distribution of the current at the area of contact with the skin of the patient. BRIEF SUMMARY The objects set forth above, as well as others, are achieved by the invention by means of the provision of a system of electrodes formed of an assembly of electrode parts mechanically and electrically associated to the distal ends of the cables that conduct electrical signals to an equipment provided for the application of electrical stimuli or for the detection of electrical signals, such component parts being provided with an electrically conductive portion, and a low-cost portion comprising a support in the form of a flexible and porous blade, having applied to both faces thereof conductive portions formed by layers of electrically conductive materials, such layers being provided in electrical contact with one another, a first conductive portion, applied to the first side of the flexible and porous blade placed in contact with the electrode parts and a second conductive portion, applied to the second side of the blade placed in contact with the skin of the patient, the removable attachment of the electrode parts to the low-cost portion being provided by a first layer of adhesive material juxtaposed to the first side of the blade, and the removable attachment of the low-cost portion to the skin of the patient being provided by a second layer of adhesive material juxtaposed to the second face of the blade. According to another characteristic of the invention, at least one of the layers of adhesive material forms portions that surround the conductive portions. According to another characteristic of the invention, the electrically conductive material of at least one of the layers is simultaneously an adhesive material and a conductive material. According to another characteristic of the invention, the blade is provided with means for positioning the electrode parts. According to another characteristic of the invention, the positioning means are provided with visual indicators. According to another characteristic of the invention, the positioning means are provided by mechanical means. According to another characteristic of the invention, the positioning means are applied to the first side of the blade. According to another characteristic of the invention, the low-cost portion comprises a support that consists of a strap or strip of flexible fabric (textile) material, having affixed onto at least one of the faces thereof a flexible strip, which the latter comprises a flexible and porous supporting blade coated on both faces thereof with layers of conductive and adhesive materials. According to another characteristic of the invention, the flexible strip, comprising the layers of conductive and adhesive materials, is juxtaposed by means of adhesion of the first layer of adhesive material to the inner face of a strap of electrically insulating fabric/textile material. According to another characteristic of the invention, the means for positioning the electrode parts are comprised by cutouts or openings in the strap of fabric/textile material through which the electrode parts are removably attached to the first layer of adhesive material of the strip. According to another characteristic of the invention, the dimensions of the cutouts are slightly larger than those of the conductive parts of the electrode parts. According to another characteristic of the invention, the means used for positioning the electrode parts comprise protuberant elements provided in correspondence with the outer side of the strap. According to another characteristic of the invention, the means used for positioning the electrode parts comprise a template. According to another characteristic of the invention, the simultaneously adhesive and conductive portions are constituted by at least one layer of solid gel. According to another characteristic of the invention, the flexible strip consists in a continuous strip. According to another characteristic of the invention, the flexible strip is interrupted between the cutouts, the dimensions of the pieces of the conductive strip being sufficient to occlude the cutouts in the strap. According to another characteristic of the invention, the electrical contact between the upper layers of conductive materials is provided by means of pores provided in the supporting blade of the strip. According to another characteristic of the invention, the layers of electrically conductive materials and adhesive materials are applied directly over the fabric/textile material strap. According to another characteristic of the invention, the electrical contact between the layers of conductive materials is provided by means of pores provided in the fabric/textile material strap. According to another characteristic of the invention, the materials of the layers comprise a solid gel that is simultaneously conductive and adhesive. According to another characteristic of the invention, at least one of the solid gel layers is applied in a selective manner. According to another characteristic of the invention, the areas of mechanical fastening and electrical contact of the electrode parts are provided by the first solid conductive and adhesive gel layer applied selectively on the outer side of the strap. According to another characteristic of the invention, the means for electrical contact and removable mechanical attachment to the skin of the patient are provided by the second layer of solid conductive and adhesive gel applied selectively on the inner side of the strap. According to another characteristic of the invention, both layers of solid gel are selectively applied in the form of portions with defined dimensions and spacing distances, each of the portions on the outer side, forming the area of mechanical fastening and electrical contact of the electrode parts, in substantial alignment with the portion applied on the inner side of the strap. According to another characteristic of the invention, the electrode parts are secured, in a semi-permanent manner, to the first layer by means of juxtaposition and slight pressure. According to another characteristic of the invention, the electrode parts comprise, individually, a conductive portion in the form of a conductive blade and a physical and electrical connection thereof with an electrical signal conduction cable, the conductive portion having a shape and size compatible with the openings through which there is provided the contact of the conductive portion with the first conductive layer. According to another characteristic of the invention, the strap is provided with means for positioning the electrode parts. According to another characteristic of the invention, the positioning means comprise the openings provided in the strap. According to another characteristic of the invention, the positioning means are provided by a slab of low density flexible insulating material, such as rubber foam or synthetic resin, applied on the outer side of the strap, provided with openings that are coincident with the areas intended for mechanical fastening and electrical contact of the electrode parts. According to another characteristic of the invention, the slab is substantially continuous. According to another characteristic of the invention, the slab is segmented, being comprised of segments distanced from one another in the longitudinal and transversal directions of the strap According to another characteristic of the invention, the strap is provided, along the longitudinal borders thereof, of flaps that are superimposed by folding on the region of the strap wherein are provided the electrodes, providing a measure of protection thereto as well as to the cables associated therewith. BRIEF DESCRIPTION OF THE DRAWINGS Further characteristics and advantages of the present invention will be better understood by means of the description of exemplary and non-limitative embodiments thereof, and of the figures to which such embodiments refer, wherein: FIGS. 1 and 2 depict an electrode strap (belt) structured in accordance with the prior art, as described in Patent Application No. BR PI 0704408, filed by the same applicant of the instant application. FIG. 3 shows a first embodiment of the inventive concept, using a flexible supporting strip, having applied on both sides thereof portions of conductive and adhesive materials. FIG. 4 shows a second embodiment of the inventive concept, wherein the adhesive material is applied in the form of a continuous layer. FIG. 5 shows, by means of a perspective view of an inner side, which remains in contact with a patient, a strap structured in accordance with the principles of the present invention. FIG. 6 shows, by means of a perspective view, a strip coated on both sides with materials that are simultaneously conductive and adhesive, which may be used together with the strap of the exemplary embodiment of FIG. 5 . FIG. 7 shows a perspective view of the outer face of the strap shown in FIG. 5 , structured in accordance with the principles of the present invention. FIG. 8 shows, by means of a perspective view, an electrode part used in connection with the present invention. FIG. 9 - a through 9 - d show, by means of cross-sectional schematic views, the various stages of the sequence of application of the strap to the patient. FIG. 10 depicts the folding of the outer flaps of protection of the electrode parts and respective cables. FIG. 11 - a and 11 - b depict an additional embodiment of the invention. FIG. 12 - a and 12 - b show a variation of the additional embodiment depicted in the preceding figures. FIG. 13 shows an implementation of the mechanical positioning means of the electrode parts on the strap according to the present invention. FIG. 14 illustrates an additional form of implementation of the means for positioning the electrode parts on the strap according to the present invention. FIG. 15 illustrates another form of an embodiment of the invention. DETAILED DESCRIPTION OF THE INVENTION FIG. 3 shows a first embodiment 30 of the invention, comprising a flexible strip 15 , preferably made of fabric/textile material, coated with conductive parts with defined size and spacing on portions 19 and 19 ′, respectively applied on the first side 15 a and on the second side 15 b thereof, the electrical contact between the conductive portions being provided by means of the material of the flexible strip 15 , either by means of the porous texture thereof, or by means of pores opened by known means, such as by mechanical perforation (not illustrated in the figure). According to the principles of the invention the conductive materials of portions 19 and 19 ′ comprise solid gels. As shown in the figure, the portions 19 and 19 ′ are substantially aligned with one another, that is, they occupy substantially coincident positions on the opposite sides of the flexible strip 15 . Surrounding the portions 19 and 19 ′, there are provided regions 18 and 18 ′ of adhesive material, respectively applied on the first and second sides 15 a , 15 b of the flexible strip 15 . This material, which may consist in a solid gel, provides the retention of the electrode parts 17 on the surface of the flexible strip 15 and the contact of those parts with the conductive material of portion 19 , enabling the transmission to the latter of the electrical signals that travel along the connecting cables 17 ′. Due to the fact that the portions 19 and 19 ′ are in mutual electrical contact, and the latter is in contact with the skin of the patient, the arrangement shown in FIG. 3 effectively provides the transmission of electrical signals between the skin of the patient (not illustrated) and the connecting cable 17 ′. According to what is shown in FIG. 3 , the dimensions of contact area 16 , formed by the conductive portions 19 , 19 ′and adhesive regions 18 , 18 ′, correspond substantially to the dimensions of the lower part (not visible in the figure) of the electrode part 17 , the lower part comprising an electrically conductive area. FIG. 4 illustrates a variation 40 of the arrangement shown in FIG. 3 , differing therefrom in that an adhesive gel layer 20 is applied in a continuous manner, this gel providing the means for removable retention of the electrode parts (not shown) and physical contact thereof with conductive gel portions 21 . The accurate positioning of the electrode parts may be aided by the provisions of positioning means, which in FIG. 4 are indicative signs 22 that are preferably printed on the surface of the flexible strip 15 . Notwithstanding that FIGS. 3 and 4 exemplify strips, wherein are employed conductive materials distinct from the adhesive materials, there may be used, in the invention, materials that simultaneously exhibit adhesive properties and conductive properties, such materials being known and available in the form of solid gel. Furthermore, the composition of the gel that is applied to the first side of the flexible strip 15 may be the same or different from that which is applied to the second side, since the latter is supposed to establish the contact with the skin of the patient, while the other is intended to contact the electrode parts. FIG. 5 illustrates a non-restrictive exemplary embodiment 50 of the invention, whereto were added elements that complement the functionalities provided by the exemplary embodiments of FIGS. 3 and 4 . The embodiment 50 comprises a strap of flexible non-conductive material 51 , which inner surface 51 a is intended to be placed in contact with the skin when applied to the patient, with the opposite side 51 b being provided facing outwards to allow the installation of the electrode parts. As illustrated in FIG. 5 , the flexible strap 51 is provided with a plurality of cutouts with the shape of oblong openings spaced along a region that extends substantially along the center thereof. According to the principles of the invention and as illustrated in FIG. 5 , a flexible strip 54 structured in accordance with the principles exemplified in the embodiments of FIGS. 3 and 4 is glued on the region occupied by the openings, a width 55 thereof being sufficient to obstruct entirely the openings. In practice, the width 55 is slightly larger than dimension 56 of the openings in the transversal direction of the flexible strap 51 , in order to ensure the full occlusion thereof. The flexible strip 54 is permanently bound to the inner side 51 a of the flexible strap 51 , and it should be noted that the raising of one of the ends 54 ′ thereof as illustrated in FIG. 5 constitutes a mere graphical resource intended to enhance openings 52 and render the same more visible to the viewer hereof. FIG. 6 illustrates the flexible strip 54 , by means of a view in perspective wherein the vertical dimension—the thickness—is considerably enlarged in order to evidence the elements that compose the same. As may be observed, the strip comprises a central element or supporting blade 54 c intercalated between a first layer of adhesive and conductive gel 54 a and a second layer of adhesive and conductive gel 54 b . The central element 54 c may be constituted by a screen which mesh size is substantially open, in order to allow, through the openings therethrough, the contact and mutual adhesion between the first and second adhesive and conductive gel layers 54 a , 54 b , that are electrically conductive, wherein there may be used a non-woven screen in a preferred embodiment of the invention. The characteristics of the adhesive and conductive gel layers 54 a , 54 b may be the same or may be mutually distinct, in light of their different functions. The adhesive and conductive gel layer 54 a , which stays adhered to the flexible strap 51 , ( FIG. 5 ), should further allow the adhesion and removal of the electrode parts, as will be seen in the following. On the other hand, the adhesive and conductive gel layer 54 b ( FIG. 5 ) should allow the attachment and removal of the flexible strap 51 to/from the skin of the patient, and should thereby exhibit characteristics compatible therewith, without causing irritation or allergic reactions. FIG. 7 shows the same flexible strap 51 , observed on its outer side, which side will stay exposed upon the application thereof to the patient. As may be seen in the FIG. 7 , in this position the openings 52 allow selective access to the contact areas 57 of the conductive and adhesive and conductive gel layer 54 a of the flexible strip 54 ( FIGS. 5 and 6 ), such cutouts 52 serving as means for positioning and spacing the electrode parts 58 . For the assembly of the latter it will suffice to remove the protective film 49 and juxtapose, applying thereby a slight pressure, the electrode parts 58 against the contact areas 57 . Still in accordance with FIG. 7 , in a preferred embodiment of the invention, there are provided, parallel to a longitudinal axis 41 of the flexible strap 51 , flaps 69 , 71 , 73 and 75 intended to protect, by folding, the electrode parts 58 and respective cable assemblies 68 upon the assembly thereof on the flexible strap 51 . The flaps 69 , 71 , 73 , 75 may be provided with retention means upon the folding, such as adhesive bands along the outer borders thereof or VELCRO®-type or equivalent closure means. However, these flaps 69 , 71 , 73 , 75 may not be present in other embodiments. According to the detail shown in FIG. 8 , each electrode part comprises on the lower side thereof a conductive portion 59 , which may comprise a metal plate—for example, made of copper, stainless steel, or an equivalent metal—or made of a conductive plastic material. Internally to the body of the part, preferably made of an insulating plastic, there is provided the union, preferably by welding 63 , of an end of a cable 62 for carrying electrical signals between the patient and the monitoring equipment, for example, an EIT apparatus. As illustrated in the figure, the dimensions of the opening 52 are provided to accommodate, with a minimal spacing gap, the conductive portions 59 of the electrode parts 58 . FIG. 9 - a through 9 - d illustrate a preferred method of application of the flexible strap 51 to the patient, by means of a sequence of simplified sectional views corresponding to a cross-sectional plane 41 indicated in FIG. 7 . The initial condition of the embodiment 50 is shown in FIG. 9 - a , wherein there may be observed that the conductive and adhesive gel sides 54 a , 54 b of the flexible strip 54 are protected by disposable films: the protective film 64 protects the conductive and adhesive gel side 54 b oriented towards the patient and the protective film 49 protects the conductive and adhesive gel side 54 a oriented towards the flexible strap 51 and accessible from the outside through the openings 52 (not referenced in this figure). The first step of the application method, illustrated in FIG. 9 - b , consists in the removal of the protective film 49 , represented by the arrow 67 , thereby exposing the conductive and adhesive gel side 54 a that forms the areas of contact with the electrode parts 58 (these areas of contact are referred with the numeral 57 in FIG. 7 ), in addition to becoming adhered to the inner side 51 a of the flexible strap 51 . To each of these exposed contact areas there is juxtaposed an electrode part 58 , which adhesion is provided by the simple compression of the conductive side 59 against the surface of the conductive and adhesive gel 54 a , 54 b. Subsequently, the electrode parts 58 and their respective cables are protected by folding over the same side flaps of the strap, if such flaps are present, as illustrated in FIG. 10 . FIG. 10 illustrates the strap upon the first flap 69 ( FIG. 5 ) having been folded to the position 69 ′, becoming superimposed over the electrode parts 58 , there being noted that cable assemblies 68 , each of the same corresponding to a set of four electrode parts 58 , extend to the outside through the cutouts 72 ′. After this first folding, the flap 71 is folded in the direction indicated by the arrow 71 a , becoming superimposed over the already folded flap 69 ′. Subsequently, the cable assemblies 68 are deviated as indicated by arrows 68 a , in order to be juxtaposed to the border 69 b of the folded flap 69 ′, and are brought together forming a set of cable assemblies 68 , which protuberates through the cutout present between the flaps 73 and 74 . Finally, these last flaps 73 , 74 are folded, as indicated by the arrows 69 a and 74 a. Subsequently, an assembly formed by a strap carrying electrodes is applied to a patient. To that end, the protective film 64 of the conductive and adhesive and conductive gel layer 54 b is removed, as indicated by the arrow 66 in FIG. 9 - c . The assembly is then pressed against the skin of a patient 65 , as illustrated in FIG. 9 - d , whereby the retention thereof is provided by the adhesive and conductive gel layer 54 b , which also intermediates the carrying of the electrical signals. In FIG. 9 - d the protective flap 69 ′ is superimposed over the electrode part 58 . For better clarity of the figure, the remaining protective flaps have been omitted in the drawing. As illustrated in FIG. 5 , the flexible strip 54 is provided in the form of a single piece, without interruptions between the adjacent openings 52 . Notwithstanding the fact that the continuity of the flexible strip 54 provides a resistive path between the adjacent electrode parts in contact with the skin of the patient, the effect of such continuity is negligible, and does not substantially influence the electrical behavior of the assembly. Thus, for example, considering the typical values of 4 cm 2 of a contact area 57 ( FIG. 7 ) for each electrode, a distance of 1.5 cm between the borders of adjacent electrodes, a thickness of 0.3 mm for the conductive gel layer and a gel resistivity p=1000 ohm-cm, there are obtained as a result the approximate values of from 10 to 20 kΩ between adjacent electrodes, while the resistance between the electrode part and the skin of the patient is of the order of only 5 to 10 Ω. However, the inventive concept disclosed herein also includes an assembly in which the flexible strip 54 is segmented, that is, having interruptions between adjacent electrodes, with the segments having dimensions that are slightly larger, both in length and in width, than the openings 52 , in order to fully occlude the latter. In an additional embodiment 50 ′ of the disclosed concept, the flexible strip 54 is not used, and the adhesive and conductive gel layers 54 a and 54 b are deposited directly on the opposite sides of the flexible strap 51 . A first variant of that embodiment is shown in FIGS. 11 - a and 11 - b , of which the first shows a part of a strap 51 ′ seen in its inner side 51 ′ a , that is, which will be in contact with the patient, and the second is a cross-sectional view with the vertical dimension having been enlarged. As illustrated, in this embodiment there have been omitted the cutouts or openings 52 of the preceding embodiment 50 . In the areas 74 corresponding to the positions of the electrodes there are practiced a plurality of small through-openings or pores that provide communication between the outer side 51 ′ b and the inner side 51 ′ a of the strap 51 ′. Such openings 52 may be obtained by mechanical means or by any other known means of perforation, and this communication may further be provided by the web, itself, of the strap 51 ′, provided that the same is sufficiently porous. Upon the provision of the porous areas 74 , there are applied on opposite sides the conductive gel layers, to wit, the internal layer, which is continuous, of the gel 54 ′ b on the inner side 51 ′ a of the strap 51 ′ and the outer layer of the gel 54 ′ a , which is segmented, on the outer side 51 ′ b of the strap 51 ′, such gels being equivalent to the adhesive and conductive gel layers 54 b and 54 a , respectively, of the embodiment illustrated in FIGS. 5 and 6 . This application may be provided using any known process, such as by spraying, silk-screen printing, offset printing, etc., provided that there is maintained the alignment between the areas coated with adhesive and conductive gel and the porous areas 74 , whose pores enable the physical and electrical contact between the inner and outer layers. In FIGS. 12 - a and 12 - b there is illustrated a constructive variation of the preceding embodiment 50 ″, which differs from this latter only in regard of the inner layer of adhesive and conductive gel, which is deposited in segments 54 ″ b , using the already cited application processes. It should be noted that, in this case, there should exist an alignment between the internal gel portions 54 ′ b , the external gel portions 54 ′ a and the areas 74 , that is, these elements should be provided substantially coincident with one another. In a preferred embodiment of the invention, the dimensions of the segments 54 ″ b and portions 54 ′ a are substantially coincident with those of the conductive portions 59 of the electrode parts 58 . As mentioned in connection with FIGS. 5 and 7 , the means for positioning the electrode parts 58 may be provided by the openings 52 , as indicated in those figures. However, there may be used other positioning means, such as printed insignia, elements in relief glued on the outer surface of the strap 51 ′, or equivalent elements. In FIG. 13 there is illustrated the use of a slab of soft elastic material 75 , such as rubber foam, a plastic material or an equivalent material, extending along the region occupied by the electrode parts 58 . This slab 75 is provided with openings or windows forming holes or frames 76 having dimensions compatible with those of the contact areas 57 that remain exposed at the bottom of the holes 76 , over which are applied the electrode parts 58 . In order to provide an enhanced flexibility to the assembly, the positioning slab 75 described in connection with FIG. 13 may be segmented, as indicated in FIG. 14 . In this figure, positioning elements 77 are mutually distanced both in the lengthwise direction and across the width of strap 80 . This transversal distancing allows the use of a protective film 78 , which covers the exposed contact areas 57 during the storage of the strap 80 , and is removed at the time of use thereof. Although the invention has been described with reference to specific exemplary embodiments, it should be understood that there may be introduced modifications therein by technicians skilled in the art, without deviation from the scope of the basic inventive concept thereof. In an additional form of an embodiment of the invention, the electrode parts are positioned separately with relation to the strap 51 , by means of use of an auxiliary template, not illustrated in the figures, whereon these electrode parts are mounted. After this mounting, the template carrying the electrode parts is applied to the flexible strap 51 , the parts then remaining attached by adhesion to the strap 51 , which is subsequently applied to the patient. Optionally, the strap 51 will not be used, and the template with the electrode parts 58 may be applied directly on the flexible strip 54 having been previously applied on the skin of the patient, in which case the protection of the electrode parts 58 and their respective cables may be provided by the template itself, or eventually by a protective band (not illustrated) placed externally. In another alternative form of an embodiment of the invention, the template is constituted by the flexible strap 51 per se without the flexible strip 54 . This embodiment is shown in FIG. 15 , wherein the border of each opening 52 is coated, on the outer side 51 b of the flexible strap 51 , by adhesive strips 79 . The assembly of the electrode parts 58 ′ shall be provided by superimposing the borders thereof onto the adhesive strips 79 , as indicated in FIG. 15 , and it should be noted that in this case at least one of dimensions 81 of the electrode part 58 ′ shall correspond to the sum of the dimension of the opening 52 and the width of the adhesive strips 79 . Upon mounting the electrode parts 58 ′, according to the illustration of FIG. 15 , the flaps are folded as described in connection with FIG. 10 . At the time of use, the flexible strip 54 is applied to the skin of the patient, thereupon superimposing over this flexible strip 54 , the assembly formed by the strap 51 carrying the electrode parts 58 ′. Therefore, the present invention is defined and delimited by the set of claims that follow.
There is disclosed a system of electrodes used for transdermal conduction of electrical signals and a method of use thereof, the system comprising a plurality of electrode parts connected by means of electrical conductors to electric impedance tomography apparatuses, as well as other devices, the parts being secured to an outer side of a flexible and porous blade coated on both sides thereof by layers of electrically conductive and adhesive materials, such electrically conductive and adhesive materials being in mutual contact through the pores of the blade, the inner face of the latter being removably secured, by means of adhesion, to the patient. The invention comprises means for positioning the electrode parts, as well as means for external protection thereof and of their respective conductors.
0
FIELD OF THE INVENTION [0001] The present invention relates to a wireless communication system and, more particularly, to a method for generating and transmitting feedback information for performing CoMP operations. BACKGROUND ART [0002] In order to meet with the requirements of LTE-Advanced systems and to enhance the performance of the conventional systems, a series of new techniques, such as relay, carrier aggregation, and CoMP (Coordinated Multi-Point) transmission and reception have been proposed. Among the newly proposed techniques, the CoMP (generally referred to as Co-MIMO, collaborative MIMO, network MIMO, etc.) is being highly appraised as a technique that can enhance communication performance of a cell boundary user equipment and increase a throughput of a sector. Generally, in an multiple cell environment, wherein a frequency re-usage rate is equal to 1, inter-cell interference may degrade the performance of the user equipments and may also decrease the throughput of the corresponding sector. A simple manual method for reducing the inter-cell interference (i.e., an FFR (Fractional Frequency Reuse) method of a user equipment (UE)-specific power control) is applied in the LTE systems in order to enhance the throughput of a cell boundary user equipment within an interference-limited environment. Instead of reducing the usage of frequency resource in each cell, it is more preferable to reduce inter-cell interference by re-using inter-cell interference by means of a desirable signal. In order to achieve this object, a plurality of CoMP (Coordinated Multi-Point) methods has been proposed. Hereinafter, a CoMP system will hereinafter be described briefly. [0003] A CoMP system refers to a system for enhancing the throughput of a user located within a cell boundary by applying an enhanced MIMO (Multiple-Input Multiple-Output) transmission in a multiple cell environment. By adopting the CoMP system, the Inter-Cell Interference within a multiple cell environment may be reduced. By using such CoMP system, a user equipment may be commonly supported with data from a Multi-cell base station. [0004] Also, by simultaneously supporting one or more user equipments (UE 1 , UE 2 , . . . UE K) using the same radio frequency resource, each base station may enhance the system performance. Also, based upon channel state information (CSI) between the base station and the user equipments, the base station may perform an SDMA (Space Division Multiple Access) method. [0005] The above-described CoMP method may be divided into a JP (Joint Processing) method of a coordinated MIMO (Co-MIMO) format via data sharing and a CS/CB (Coordinated Scheduling scheme/Beamforming scheme). [0006] FIG. 1 illustrates a conceptual view of CoMP operations of an intra base station (intra eNB) and an inter base station (inter eNB). [0007] Referring to FIG. 1 , intra base stations ( 110 , 120 ) and an inter base station ( 130 ) exist in a Multi Cell environment. In an LTE (Long Term Evolution), an intra base station is configured of several cells (or sectors). Cells belonging to a base station, to which a specific user equipment belongs, are related with the specific user equipment and the intra base stations ( 110 , 120 ). More specifically, cells sharing the same base station as the user equipments belonging to the cells are referred to as the cells corresponding to the intra base stations ( 110 , 120 ), and the cells belonging to other base stations may be referred to as cells corresponding to the inter base station ( 130 ). As described above, although cells that are based upon the same base station as the specific user equipment transmit and receive information (e.g., data, CSI (Channel State Information)) to and from one another through an x2 interface, cells that are based upon another base station may transmit and receive inter-cell information to and from one another via Backhaul ( 140 ). [0008] As shown in FIG. 1 , a single-cell MIMO user ( 150 ) located within a single cell may communicate with a single serving base station within a single cell (sector), and a multi-cell MIMO user ( 160 ) located at a cell boundary may communicate with multiple serving base stations within multiple cells (sectors). [0009] In order to perform such CoMP operations, the user equipment is required to feed-back the CSI to the serving base station. Among the CSI, PMI, RI may be used in all CoMP operation methods, and PMI, RI formats may be used in all CoMP operation methods. However, among the CSI within an LTE system, it may be difficult to apply the format of the CQI in all CoMP operation methods without any modification. Therefore, as a new measurement is required to be performed in order to allow the user equipment to feed-back CQI values of neighboring cells, which perform CoMP operations, a problem of having a large overhead with respect to the measurement may occur. DETAILED DESCRIPTION OF THE INVENTION Technical Objects [0010] The technical object which the present invention seeks to achieve is to provide a method of a user equipment performing CoMP operations for transmitting feedback information in a wireless communication system. [0011] Another technical object of the present invention is to provide a user equipment device for transmitting feedback information in order to perform CoMP operations in a wireless communication system. [0012] Another technical object of the present invention is to provide a method of a base station performing CoMP operations for generating channel state information values in a wireless communication system. [0013] A further technical object of the present invention is to provide a base station for generating channel state information in order to perform CoMP operations in a wireless communication system. [0014] The technical objects of the present invention will not be limited only to the objects described above. Accordingly, additional technical objects of the present application will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the present application. Technical Solutions [0015] In order to achieve the technical object of the present invention, a method for transmitting CoMP feedback information includes the steps of measuring an intensity or interference level of a signal of each cell performing the CoMP operations, by using a reference signal received from the each cell, and a sum of signal intensity or a sum of interference levels of remaining neighboring cells excluding a serving cell, among the cell performing the CoMP operations, and cell that does not perform the CoMP operations; generating channel quality information respective to each cell performing the CoMP operations, by using, the measured intensity or interference levels values of the signals corresponding to each cell performing the CoMP operations, an average value of the measured sum of the signal intensity or interference level values of each cell that odes not perform the CoMP operations, the average value of the measured sum being accumulated for a predetermined time period; and transmitting the generated channel quality information to a serving base station. [0016] In order to achieve another technical object of the present invention, a user equipment (UE) apparatus for transmitting CoMP feedback information includes a measurement module configured to measure an intensity or interference level of a signal of each cell performing the CoMP operations, by using a reference signal received from the each cell, and a sum of signal intensity or a sum of interference levels of remaining neighboring cells excluding a serving cell, among the cell performing the CoMP operations, and cell that does not perform the CoMP operations; a generation module configured to generate channel quality information respective to each cell performing the CoMP operations, by using, the measured intensity or interference levels values of the signals corresponding to each cell performing the CoMP operations, and an average value of the measured sum of the signal intensity or interference level values of each cell that does not perform the CoMP operations, the average value of the measured sum being accumulated for a predetermined time period. [0017] In order to achieve yet another technical object of the present invention, a method for generating Channel Quality Information values at a base station (BS) performing CoMP (Coordinated Multi-Point) operations in a wireless communication system includes the steps of receiving a channel quality information value respective to each cell performing the CoMP operations from a user equipment; and generating at least one or more channel quality information values, among a channel quality information value corresponding to a first CoMP operation scheme and a channel quality information value corresponding to a second CoMP operation method, by using the received channel quality information value respective to each cell. Herein, the received channel quality information may be generated by using, the measured intensity or interference levels values of the signals corresponding to each cell performing the CoMP operations, and an average value of sum of the signal intensity or interference level values of each cell that does not perform the CoMP operations, the average value of sum being accumulated for a predetermined time period. [0018] In order to achieve a further technical object of the present invention, a base station (BS) apparatus for generating Channel Quality Information values includes a reception module configured to receive a channel quality information value respective to each cell performing the CoMP operations from a user equipment; and a generation module configured to generate at least one channel quality information value, among a channel quality information value corresponding to a first CoMP operation scheme and a channel quality information value corresponding to a second CoMP operation scheme, by using the received channel quality information value respective to each cell. Herein, the received channel quality information may be generated by using, the measured intensity or interference levels values of the signals corresponding to each cell performing the CoMP operations, an average value of sum of the signal intensity or interference level values of each cell that does not perform the CoMP operations, the average value of sum being accumulated for a predetermined time period. Effects of the Invention [0019] According to the present invention, by generating and transmitting CQI values respective to neighboring cells, which perform CoMP operations, using a CQI value of a serving cell, based upon conventional single-cell operations, a more efficient feedback information transmission may be available. [0020] The effects that may be gained from the embodiment of the present invention will not be limited only to the effects described above. Accordingly, additional effects of the present application will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the present application. More specifically, unintended effects obtained upon the practice of the present invention may also be derived by anyone having ordinary skill in the art. BRIEF DESCRIPTION OF THE DRAWINGS [0021] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and along with the description serve to explain the spirit and scope (or principle) of the invention. [0022] FIG. 1 illustrates a conceptual view of CoMP operations of an intra base station (intra eNB) and an inter base station (inter eNB), [0023] FIG. 2 illustrates physical channels that are used in a 3GPP (3rd Generation Partnership Project) LTE (Long Term Evolution) system, which corresponds to an example of a mobile communication system, and a general method for transmitting signals using such physical channels, [0024] FIG. 3 illustrates a conceptual view of a method for performing CoMP operations according to the present invention, [0025] FIG. 4 illustrates a structure of a user equipment device according to a preferred embodiment of the present invention, and [0026] FIG. 5 illustrates a structure of a base station device according to a preferred embodiment of the present invention. BEST MODE FOR CARRYING OUT THE PRESENT INVENTION [0027] Hereinafter, the preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings. The detailed description of the present invention that is to be disclosed along with the appended drawings is merely given to provide to describe the exemplary embodiment of the present invention. In other words, the embodiments presented in this specification do not correspond to the only embodiments that can be realized according to the present invention. In the following description of the present invention, the description of detailed features of the present invention will be given in order to provide a full and complete understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention can be realized even without the detailed features described herein. For example, the present invention will be described in detail as follows based upon an assumption that the mobile communication system used in the present invention corresponds to a 3GPP LTE system. However, with the exception for the unique features of the 3GPP LTE system, other mobile communication systems may also be randomly applied in the present invention. [0028] In some cases, in order to avoid any ambiguity in the concept (or idea) of the present invention, some of the structures and devices disclosed (or mentioned) in the present invention may be omitted from the accompanying drawings of the present invention, or the present invention may be illustrated in the form of a block view focusing only on the essential features or functions of each structure and device. Furthermore, throughout the entire description of the present invention, the same reference numerals will be used for the same elements of the present invention. [0029] Furthermore, in the following description of the present invention, it is assumed that the user terminal (or user equipment) universally refers to a mobile or fixed user-end device, such as a UE (User Equipment), an MS (Mobile Station), and so on. Additionally, it is also assumed that the base station universally refers to as an arbitrary node of a network end, which communicates with the user equipment, such as a Node B, an eNode B, a Base Station, and so on. [0030] In a mobile communication system, a user equipment may receive information from a base station via downlink, and the user equipment may also transmit information via uplink. The information received or transmitted by the user equipment includes data and diverse control information. And, various physical channels may exist depending upon the type and purpose of the information received or transmitted by the user equipment. [0031] FIG. 2 illustrates physical channels that are used in a 3GPP (3rd Generation Partnership Project) LTE (Long Term Evolution) system, which corresponds to an example of a mobile communication system, and a general method for transmitting signals using such physical channels. [0032] In step S 201 , the user equipment performs initial cell search such as synchronization with the base station, when the power is turned on from a power off state, or when it newly enters a cell. In order to do so, the user equipment synchronizes with the base station by receiving a P-SCH (Primary Synchronization Channel) and a S-SCH (Secondary Synchronization Channel) from the base station, and then acquires information such as a cell ID (Identifier), and so on. Thereafter, the user equipment may acquire broadcast information within the cell by receiving a Physical Broadcast Channel from the base station. Meanwhile, in the step of initial cell search, the user equipment may receive a DL RS (Downlink Reference Signal) so as to verify the downlink channel status. [0033] In step S 202 , once the user equipment has completed the initial cell search, the corresponding user equipment may acquire more detailed system information by receiving a PDCCH (Physical Downlink Control Channel) and a PDSCH (Physical Downlink Control Channel) respective to the respective Physical Downlink Control Channel information. [0034] Meanwhile, if the user equipment initially accesses the base station, or if there are no radio resources for signal transmission, the user equipment may perform a Random Access Procedure, such as in step S 203 to step S 204 , with respect to the base station. In order to do so, the user equipment may transmit a specific sequence to a preamble through a PRACH (Physical Random Access Channel) (S 203 ), and may receive a response message respective to the random access through the PDCCH and its corresponding PDSCH (S 204 ). In case of a contention based random access excluding the case of a Handover, a Contention Resolution Procedure, such as a PRACH transmission (S 205 ) and a PDCCH/PDSCH reception (S 206 ) may be additionally performed. [0035] After performing the above-described process steps, the user equipment may perform PDCCH/PDSCH reception (S 207 ) and PUSCH (Physical Uplink Shared Channel)/PUCCH (Physical Uplink Control Channel) transmission (S 208 ), as general uplink/downlink signal transmission procedures. At this point, the control information, which is transmitted by the user equipment to the base station or received by the user equipment from the base station via uplink, may include downlink/uplink ACK/NACK signals, a CQI (Channel Quality Indicator, hereinafter referred to as ‘CQI’)/PMI (Precoding Matrix Index, hereinafter referred to as ‘PMI’)/RI (Rank Indicator, hereinafter referred to as ‘RI’), and so on. In case of the 3GPP LTE (3rd Generation Partnership Project Long Term Evolution) system, the user equipment may transmit control information, such as the above-described CQI, PMI, RI, and so on, through the PUSCH and/or the PUCCH. [0036] When the term base station, which is used in the description of the present invention, is used as a regional concept, the term base station may also be referred to as a cell or a sector. A serving base station (or cell) may be viewed as a base station (or cell) providing main services to the user equipment, and the serving base station (or cell) may also perform transmission and/or reception of control information over a coordinated multiple transmission point. Accordingly, the serving base station (or cell) may also be referred to as an anchor base station (or cell). The serving base station may transmit diverse information, which the service base station has received from the user equipment to a neighboring base station (cell). Similarly, when used as a regional concept, the term neighboring base station may also be referred to as a neighboring cell. [0037] When the CoMP method is used under a multiple cell environment, the communication performance of a cell boundary user equipment may be enhanced. Such CoMP method may include a JP (Joint Processing) method of a coordinated MIMO format via data sharing and a CS/CB (Coordinated Scheduling/Beamforming) method for reducing inter-cell interference, such as a worst companion and a best companion. Herein, the worst companion method corresponds to a method wherein, by having the user equipment report a PMI, which causes the greatest interference among the cells performing CoMP, to the serving base station, the corresponding cells may remove (or eliminate) inter-cell interference by using a second-best PMI excluding the corresponding (or reported) PMI. And, the best companion method corresponds to a method wherein, by having the user equipment report a PMI, which causes the least interference among the cells performing CoMP, to the serving base station, the corresponding cells may remove (or eliminate) inter-cell interference by using the corresponding (or reported) PMI. [0038] A cell boundary user equipment, which performs CoMP operations, is required to transmit feedback information having a common format (e.g., a common CQI format for all CoMP methods), which allows the user equipment to easily perform all CoMP operations (e.g., JP method, CS/CB method), to the serving base station. By transmitting the feedback information having the common format, diverse CoMP methods may be efficiently performed without having to perform complex signaling. Most particularly, in order to support such CoMP methods, measurement of CQI values among multiple cells and feedback of such measured values act as important factors. [0039] The user equipment, which performs CoMP operations, is required to measure adequate CQI values respective not only to the serving base station, which performs the CoMP operations, but also to neighboring cells providing interference or desirable signals, and also required to feed-back such measured values to the serving base station. The base stations sharing the same feedback information should be capable of performing all CoMP operations. In order to do so, the user equipment may additionally transmit a CQI value of a serving cell, which performs feedback in a single cell operation, and transmit CQI values of the neighboring cells. [0040] The CQI value of the serving cell, which performs feedback in a single cell operation, may be expressed by using Equation 1 shown below. [0000] CQI A = Q A = S A N _ + S B _ + S C _ = S A V Equation   1 [0041] Herein, [0000] CQI A corresponds to a CQI value of Cell A, being the serving cell, and S A indicates a power level (or interference level) of a signal received from a neighboring Cell A, which performs CoMP operations, N indicates a time average value of noise and interference power level measured from a cell that does not perform CoMP operations, S B indicates a power level (or interference level) received from a neighboring Cell B, which performs CoMP operations, S C indicates a power level (or interference level) received from a neighboring Cell C, which performs CoMP operations. V indicates a time average value of noise and interference power level measured from all of the remaining cells excluding the serving cell by using a [0000] N _ + S B _ + S C _ [0000] value. [0042] In order to allow the cells performing the CoMP operations to easily perform both the CS/CB method and the JP method, the user equipment is required to transmit CQI information on the neighboring cells that perform the CoMP operations (which may be referred to as ‘CoMP neighboring cells’ for short) to the serving base station. The user equipment may generate a CQI value respective to a CoMP neighboring cell by using a denominator value of the CQI value respective to the serving cell (i.e., time average value of the sum of noise and interference power levels measured from all of the remaining cells excluding the serving cell and by also using received power level (or interference level) values of each CoMP neighboring cell, which is measured by using a reference signal received from each neighboring cell. Such CQI value of each CoMP neighboring cell, which is generated as described above, may be expressed by using Equation 2 and Equation 3 shown below. [0000] CQI B = Q B = S B N _ + S B _ + S C _ = S B V Equation   2 CQI C = Q C = S C N _ + S B _ + S C _ = S C V Equation   3 [0043] Herein, S B indicates a power level (or interference level) of a signal received from a neighboring Cell B, which performs CoMP operations, and S C indicates a power level (or interference level) of a signal received from a neighboring Cell C, which performs CoMP operations. [0044] The intensity or interference level of a signal measured by the user equipment from a neighboring cell may be expressed in diverse formats, such as SINR (Signal to Interference plus Noise Ratio), CINR (Carrier to Interference plus Noise Ratio), RSRP (Reference Signal Received Power), RSRQ (Reference Signal Received Quality), and so on. For example, among the CoMP operation methods, when the user equipment performs Joint Processing, the user equipment may use reference signals received from cells performing Joint Processing so as to measure the intensity of the received signals. [0045] FIG. 3 illustrates a conceptual view of a method for performing CoMP operations according to the present invention. [0046] Referring to FIG. 3 , it will be assumed that Cells A, B, and C are performing CoMP on a user equipment (UE 1 ), which belongs to (or is located at) the boundary (or edge) of Cell A. The user equipment belonging to the Serving Cell A may transmit common feedback information for supporting all available CoMP methods to the serving base station. Most particularly, in case of the CQI value, the value respective to the CoMP neighboring cell may be generated in the above-described format, so as to be fed-back. After receiving such feedback information, in order to perform the Coordinated Beamforming (CB) method or the Joint Processing (JP) method, the base station may calculate each CQI value based upon the received feedback information. If the cells performing the CoMP operations use the Coordinated Beamforming (CB) method, among the diverse CoMP methods, the CQI value, which may be expressed by using Equation 4 shown below, may be generated. [0000] S A V - S B - S C = S A V - Q B · V - Q C · V = S A V · 1 1 - Q B - Q C = Q A 1 - Q B - Q C Equation   4 [0047] Equation 4 shown above indicates a CQI value corresponding to a case where the Coordinated Beamforming (CB) method is applied with respect to the serving Cell A. As expressed in Equation 4, the CQI value respective to the case where the base station uses the Coordinated Beamforming (CB) method, may be obtained by directly using the CQI value respective to the cell performing the CoMP operations, which is received from the user equipment, without any modifications. More specifically, the CQI value of the Coordinated Beamforming (CB) method may be expressed as [0000] Q A 1 - Q B - Q C [0000] by using CQI A (=Q A ), CQI B (=Q B ), and CQI C (=Q C ), which correspond to CQI values respective to cells performing the CoMP operations. [0048] If the cells performing the CoMP operations use the Joint Processing (JP) method, among the diverse CoMP operations, the CQI value may be generated by using Equation 5 shown below. [0000] ( S A + S B + S C V - S B - S C ) 2 = ( Q A · V + Q B · V + Q C · V V - Q B · V - Q C · V ) 2 = ( Q A + Q B + Q C 1 - Q B - Q C ) 2 Equation   5 [0049] As shown in Equation 5, the CQI value respective to the case when the base station uses the Joint Processing (JP) method, may be obtained by directly using the CQI value respective to the cell performing the CoMP operations, which is received from the user equipment, without any modifications. More specifically, the CQI value of the Coordinated Beamforming (CB) method may be expressed as [0000] ( Q A + Q B + Q C 1 - Q B - Q C ) 2 [0000] by using CQI A (=Q A ), CQI B (=Q B ), and CQI C (=Q C ), which correspond to CQI values respective to cells performing the CoMP operations. [0050] As described above, when the Coordinated Beamforming (CB) method is operated, among the CoMP operations, the CQI value may be generated by using Equation 4. And, when the Joint Processing method is operated, among the CoMP operations, the CQI value may be generated by using Equation 5. Furthermore, in case the CoMP method that is to be operated between the user equipment and the cells is yet to be decided, it is advantageous in that the base station may generate the CQI values respective to both the Coordinated Beamforming (CB) method and the Joint Processing method, which are expressed in Equation 4 and Equation 5. As described above, when generating the CQI values for both CoMP methods, it is advantageous in that the base station can easily perform dynamic switching with respect to the CoMP method. [0051] As described above, the CQI value for the Coordinated Beamforming (CB) method or the Joint Processing method may be easily deduced from the CQI A (=Q A ), CQI B (=Q B ), and CQI C (=Q C ) values, which are transmitted from the user equipment. Accordingly, common feedback of the user equipment may be available. Furthermore, in transmitting the CQI value of a neighboring cell to the CQI value of the serving cell based upon the conventional single cell operations, since an average interference level value is being used, measurement values that are defined in the conventional LTE system may be used. Therefore, it is advantageous in that a new measurement value is not required to be defined herein. [0052] FIG. 4 illustrates a structure of a user equipment device according to a preferred embodiment of the present invention. [0053] Referring to FIG. 4 , the user equipment device according to the present invention is provided with a reception module ( 410 ), a processor ( 420 ), a memory unit ( 430 ), and a transmission module ( 440 ). [0054] The reception module ( 410 ) may receive reference signals from at least one or more cells existing within the radio network. The processor ( 420 ) is provided with a measurement module ( 421 ) and a CQI value generation module ( 422 ). [0055] The measurement module ( 421 ) may measure the intensity or interference level of the signal corresponding to each cell by using the reference signal received by the reception module ( 410 ) from each of the at least one or more cells performing the CoMP operations. Also, the measurement module ( 421 ) may measure the intensity or interference level of the signal corresponding to each cell by using the reference signal received from each cell performing the CoMP operations. Furthermore, the measurement module ( 421 ) may measure a sum of signal intensity or a sum of interference levels of the remaining neighboring cells excluding the serving cell, among the cell that are performing CoMP operation, and the cells that do not perform the CoMP operations. Among the measured intensity or interference level values of the signal corresponding to each cell performing the CoMP operations, the CQI value generation module ( 422 ) may use an average value calculated from intensity or interference level values of the signal corresponding to each cell performing the CoMP operations and from a sum of signal intensity or a sum of interference level values of the signal corresponding to each cell that does not perform the CoMP operations, the values being accumulated for a predetermined time period, so as to generate channel quality information for each cell performing the CoMP operations. [0056] The memory unit ( 430 ) may store the values measured by the measurement module ( 422 ) and the CQI values generated from the CQI value generation module for a predetermined period of time. The memory unit ( 430 ) may also be replaced with another element, such as a buffer (not shown). The transmission module ( 440 ) may transmit the generated CQI value to the serving base station. [0057] FIG. 5 illustrates a structure of a base station device according to a preferred embodiment of the present invention. [0058] Referring to FIG. 5 , the user equipment device according to the present invention is provided with a reception module ( 510 ), a processor ( 520 ), a memory unit ( 530 ), and a transmission module ( 540 ). [0059] The reception module ( 510 ) may receive channel quality information values respective to each cell performing the CoMP operations from the user equipment. At this point, the reception module ( 510 ) may receive channel quality information values respective to each cell performing the CoMP operations from another base station or user equipment. [0060] The processor ( 520 ) is provided with a CQI value generation module ( 521 ). The CQI value generation module ( 521 ) may generate CQI values corresponding to a specific CoMP operation scheme by using the channel quality information values respective to each cell performing CoMP operations, the channel quality information values being received by the reception module ( 510 ). The CQI value generation module ( 521 ) may generate at least one channel quality information value, among the channel quality information value corresponding to a first CoMP operation scheme and the channel quality information value corresponding to a second CoMP operation method. At this point, the channel quality information value received by the base station device from the user equipment may be generated by using an average value calculated from intensity or interference level values of the signal corresponding to each cell performing the CoMP operations and from a sum of signal intensity or a sum of interference level values of the signal corresponding to each cell that does not perform the measured CoMP operations, the values being accumulated for a predetermined period of time. Furthermore, the first CoMP operation scheme may correspond to the Coordinated Beamforming method, and the second CoMP operation scheme may correspond to the Joint Processing method. [0061] The memory unit ( 530 ) may store the CQI values received by the reception module ( 510 ) and the CQI values generated from the CQI value generation module ( 521 ) for a predetermined period of time. The memory unit ( 530 ) may also be replaced with another element, such as a buffer (not shown). [0062] The transmission module ( 540 ) may transmit the CQI values generated by the CQI value generation module ( 521 ) to another base station or user equipment. [0063] As described above, a detailed description of the preferred embodiments of the present invention disclosed herein is provided so that anyone skilled in the art can be capable of realizing and performing the present invention. It will be apparent to those skilled in the art that the present invention can be embodied in other specific forms without departing from the spirit and essential characteristics of the invention. Thus, the above embodiments are to be considered in all respects as illustrative and not restrictive. The scope of the invention should be determined by reasonable interpretation of the appended claims and all change which comes within the equivalent scope of the invention are included in the scope of the invention. For example, anyone skilled in the art may apply the exemplary embodiments presented herein by combining each structure disclosed in the description of the present invention. [0064] Therefore, the present invention will not be limited only to the exemplary embodiments disclosed herein. Instead, the present invention seeks to provide a broader scope of the present invention best fitting the disclosed principles and new characteristics of the invention described herein. INDUSTRIAL APPLICABILITY [0065] The method for transmitting CoMP feedback information, and a user equipment device and a base station device both using the same may be industrially applied to communication systems, such as 3GPP LTE, LTE-A, and IEEE 802 systems.
Disclosed are a method for transmitting CoMP feedback information in a wireless communication system and a terminal apparatus using the same. Measured values of adjacent cells for performing a CoMP operation can be generated by using measured values defined in an existing LTE system. Consequently, the present invention doesn't need to define new measured values in a LTE-Advanced system.
7
BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to a process for the recovery from a reaction mixture of cellulose carbamate produced by conversion of cellulose with excess urea in an inert organic liquid reaction carrier. 2. Description of the Related Art U.S. Pat. No. 5,378,827 discloses a multi-step process for the production of cellulose carbamate in which the cellulose is mixed with aqueous urea solution, the water portion of the mixture is exchanged for an organic reaction carrier, the conversion to the carbamate is carried out under formation or addition of an inert vaporous or gaseous medium which is led off from the reaction zone, a part of the organic reaction carrier is separated mechanically from the conversion mixture, the remaining mixture is added with aqueous urea solution, the remaining organic reaction carrier removed by distillation, the aqueous cellulose carbamate-containing mixture cooled by lowering its pressure, and the cellulose carbamate separated on a band filter from the aqueous urea solution and washed with water. The financial expense for the separation of the cellulose carbamate and the recovery of urea and reaction carrier is considerable. According to DE-A 44 17 140, the organic reaction carrier can also be washed out with methanol or ethanol and recovered from the washing filtrate by extraction with water. The remaining extraction mixture can be separated by rectification in alcohol and aqueous urea solution. A disadvantage is that in addition to the reaction carrier, another auxiliary material must be used, namely, alcohol. In the process of the EP Patent 97 685, the whole organic reaction carrier is separated from the reaction mixture through vacuum distillation and the remaining mixture washed with water. Because of the voluminous nature of the cellulose carbamate, there remains a considerable amount of organic reaction carrier in the cellulose carbamate after the distillation. Also, biuret, the by-product formed, is washed out only with difficulty. SUMMARY OF THE INVENTION The present invention comprises a process for the recovery from a reaction mixture of cellulose carbamate produced by conversion of cellulose with excess urea in an inert organic liquid reaction carrier. The process is more economical than those of the prior art. An advantage of the invention is that one can obtain water-wet cellulose carbamate that is practically free from excess urea, biuret, and organic reaction carrier. The process comprises treating the cellulose carbamate reaction mixture with water under heat, separating the liquid phase from this mixture as much as possible on a filter, washing the cellulose carbamate remaining on the filter with water, which is then optionally pre-dried and/or dried and recovered, and recovering the organic reaction carrier by phase separation from the combined liquids for further use. The foregoing merely summarizes certain aspects of the invention and is not intended, nor should it be construed, as limiting the invention in any manner. The invention is described in full detail below. BRIEF DESCRIPTION OF THE DRAWING The FIGURE is a schematic diagram of an illustrative process according to the invention. DETAILED DESCRIPTION OF THE INVENTION Synthesis of cellulose carbamate can be conducted according to the process of U.S. Pat. No. 5,378,827, DE Patent Applications 196 35 473.0 and 197 15 617.7 or any similar process. In addition to cellulose carbamate, the reaction mixture thereby produced contains an inert organic liquid reaction carrier, unconverted excess urea, and reaction by-products, such as biuret. The inert organic liquid reaction carrier is generally an aliphatic hydrocarbon, such as linear or branched alkanes, or a hydroaromatic or alkyl aromatic hydrocarbon or a mixture of such compounds with boiling points in the range of 100 to 215° C. at atmospheric pressure. Preferred are mono- di- or trialkylbenzenes, such as xylenes (dimethyl benzenes) or toluene (methyl benzene), or a mixture of them, where the sum of the carbon atoms of the alkyl group(s) lies in the range of 1 to 4, inclusive. Longer-chain alkanes, e.g., a mixture of C 11 -alkanes commercially known as isoundecan, or hydroaromatic hydrocarbons, such as tetralin (1,2,3,4-tetrahdyronaphthalene) or decalin (decahydronaphthalene), with a boiling point of over 185° C. are likewise useful. According to the present invention, the hot reaction mixture issuing from the last synthesis reactor is mixed with water in a stirrer vessel and stirred under heat or otherwise mixed until the excess unconverted urea embedded in the cellulose carbamate and the reaction byproducts (primarily biuret) have gone into solution in the aqueous phase. The amount of water to be added is preferably 10 to 100 times the amount by weight of the unconverted urea. The temperature in the stirrer vessel is about 70 to 100° C. The temperature is preferably established by the heat exchange of the cold water with the hot reaction mixture, whereby at the same time the temperature of the cellulose carbamate wash water can be raised to the appropriate point. To bring excess urea and reaction by-products into solution, a total of 5 to 120 min, preferably 30 to 90 min are required. In particular, in continuous operation, instead of one stirrer vessel a stirrer vessel cascade, consisting of up to five (preferably two) stirrer vessels in sequence can be used. The dwell time is distributed proportionately among the individual vessels according to the throughput. The temperature in the individual stirrer vessels can be the same or different; likewise, the entire water amount can be added to the first stirrer vessel or distributed among the individual vessels. To prevent explosive vapor mixtures, the stirrer vessels are charged with an inert gas, e.g., nitrogen. The waste vapors are preferably worked up together with the vapors from the synthesis reactor, for example as described in U.S. Pat. No. 5,378,827. After mixing and treating with water, the reaction mixture is laid evenly on a filter, e.g., a band filter, drum filter, or trough filter, which are commercially available. Upon passage through the first filtration zone, the liquid part (consisting of organic reaction carrier and diluted aqueous urea/biuret solution) is separated as much as possible. The remaining filter cake is then washed (preferably in at least two stages) with 30 to 90° C. (preferably 50 to 90° C.) hot water. The wash water for the last wash stage can be water that had been previously used to wash said used filter or the used portion of said filter freed from the filter cake (e.g., the used portion of a band filter). This way, cellulose carbamate residues adhering to the filter are returned to the process. With several wash stages the temperature of the wash water can be the same or different from one stage to the next. The filtration can take place under vacuum or under pressure. To prevent the dangers of explosive vapor mixtures, the filtration apparatus can be charged with inert gas. The washed cellulose carbamate, which will generally have a water content of over 50% by weight, can, after removal of the filter, be further processed. Preferably, however, the cellulose carbamate is first pre-dried on the filter after leaving the wash zone and only thereafter further processed. For this purpose, hot inert gas is passed through the filter cake so that residual organic reaction carriers along with water vapor are removed. Then a mild drying can follow. Instead of the pre-drying, the filter cake can also be pressed off. The drying of the cellulose carbamate is continued until a residual moisture content of about 3 to 10% by weight (preferably 6 to 8%) is achieved. The inert gas emerging from pre-drying and/or drying is freed from the condensable components by condensation and re-circulated. All filtrates, including the organic reaction carrier mixed with water and the wash water, as well as, possibly, the condensate from the drying stage, are combined and worked up together. The combined fluid phases are first cooled to below 50° C. and then through phase separation divided into an organic reaction carrier, which is returned to the process, as well as into a diluted aqueous urea/biuret solution. The following example is provided for illustrative purposes only and is not intended, nor should it be construed, as limiting the invention in any manner. EXAMPLE An exemplary process according to the invention is explained below based on the process scheme of FIG. 1 . All parts/h are parts by weight per h. 43 parts by weight/h of 145° C. reaction mixture consisting of 2.37 pts./h cellulose carbamate , 40 pts/h o-xylene (1,2-dimethylbenzene), about 0.30 pts./h of unconverted urea, as well as biuret and other reaction products, were cooled in heat exchange with demineralized water to 100° C. and fed (1) into the first of two stirrer vessels( 10 ) of a stirrer vessel cascade ( 10 and 11 ). At the same time, 10 pts/h of about 70° C. demineralized water are introduced (2). The total average dwell time in the stirrer vessel cascade was about 60 min. The waste vapors ( 9 ) from the stirrer vessels ( 10 and 11 ) were worked up in the cellulose carbamate synthesis together with the vapors from the synthesis reactors. Then the mixture was brought evenly through a conduit ( 12 ) to the beginning (3) of the first filter zone of a band filter set ( 13 ). Upon passing through the first of three filter zones ( 15 ) about 47 pts/h of a mixture ( 23 ) of o-xylene and water were separated. The remaining filter cake was washed in the next filter zone ( 15 ) with 5 pts/h of 70° C. hot water (4). A further washing with 5 pts/h of 65° C. hot water (5), with which (as described below) the filter band ( 14 ) had been previously rinsed ( 19 ), followed. Finally the filter cake, consisting of about 2.37 pts/h cellulose carbamate and about 3.6 pts/h water, was passed through a predrying zone ( 16 , 17 ), where hot nitrogen (6) was passed through it. The condensable components were condensed in the waste gas ( 26 ) and separated ( 21 ) and the nitrogen re-circulated. After the pre-drying, the cellulose carbamate, dried to a residual moisture of about 40%, was taken off the filter band ( 14 ) at the guide roller ( 18 ), carried out over the bucket wheel sluice ( 20 ), and led over line ( 8 ) to further processing. Thereafter the filter band ( 14 ) was rinsed ( 19 ) with hot water ( 7 ) and the water recirculated ( 5 ) to the last washing zone of the filter cake. The filtrate ( 23 ), the wash waters ( 24 and 25 ), as well as the condensate ( 22 ) from the vessel ( 21 ), were combined in the vessel ( 27 ) and, after cooling to 40° C., led over line ( 28 ) to the separator ( 29 ). About 40 pts/h of o-xylene were recovered and led back over the line ( 31 ) into the cellulose carbamate synthesis. At the same time, there resulted a biuret-containing, diluted aqueous urea solution ( 30 ) that was further processed.
The present invention comprises a process for the recovery from a reaction mixture of cellulose carbamate produced by conversion of cellulose with excess urea in an inert organic liquid reaction carrier, wherein the reaction mixture is treated with added water under heat, then the liquid phase is separated as much as possible on a filter, the cellulose carbamate remaining on the filter is washed with water, optionally pre-dried and, if desired, dried and recovered, and the organic reaction carrier is recovered by phase separation from the combined liquids.
2
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a method and apparatus to control the fuel/air mixture of a diesel engine and, more particularly, to a method and apparatus to control the fuel and air ratio of a diesel engine during a load increase. [0003] 2. Description of the Related Art [0004] In modern low-emission diesel engines, the fuel/air mixture is typically set lean of the stoichiometric level with exhaust gas recirculation (EGR) used to reduce NOx during steady state operation. During rapid load increases on turbocharged diesel engines, the air flow increase lags behind the fuel flow increase and results in relatively rich operating conditions. This results in increased smoke and particulate emissions. Typically, the EGR flow is reduced or eliminated during rapid load increases to reduce smoke and particulates. However, this causes high NOx emissions from the engine. [0005] In internal combustion engines, EGR is a NOx emission reduction technique used in most gasoline and diesel engines. EGR works by recycling a portion of an engine's exhaust gas back to the engine cylinders. Often, the EGR gas is cooled through a heat exchanger to allow introduction of a greater mass of the recirculated gas into a diesel engine. Since diesel engines are typically unthrottled, EGR does not lower throttling losses in the way that it does for gasoline engines. However, the exhaust gas, which is largely carbon dioxide and water vapor, has a much lower oxygen mass fraction than air, and so it serves to lower peak combustion temperatures. There are tradeoffs, however, adding EGR to a diesel reduces the specific heat ratio of the combustion gases in the power stroke. This reduces the amount of power that can be extracted by the piston. EGR also tends to reduce the amount of fuel burned in the power stroke. This is evident by the increase in particulate emissions that correspond to an increase in EGR. Particulate matter, which may mainly be composed of carbon, but is not burned in the power stroke is wasted energy. [0006] Usually, an engine recirculates exhaust gas by piping it from the exhaust manifold to the inlet manifold. A control valve (EGR valve) within the EGR circuit regulates the time and the amount of return flow. [0007] The air/fuel ratio is the mass ratio of air to fuel present during combustion. When all of the fuel is combined with all of the free oxygen, typically within a vehicle's combustion chamber, the mixture is chemically balanced and this air/fuel ratio is called a stoichiometric mixture. In theory, a stoichiometric mixture has just enough air to completely burn the available fuel. In practice, this is never quite achieved, due primarily to the very short time available for the combustion in an internal combustion engine for each combustion cycle. [0008] What is needed in the art is a method and an apparatus to reduce pollutants during an increased torque requirement transition for diesel engines. SUMMARY OF THE INVENTION [0009] The present invention relates to a method and apparatus for controlling fuel/air mixture ratio during a load increase transition in a diesel engine. [0010] The invention in one form is directed to a method of controlling a diesel engine connected to a load including the step of detecting the need for a higher torque output by the engine and matching a fuel flow with the airflow going to the engine during the load increase. The matching of the fuel flow with the air flow keeps the fuel flow and airflow during the load increase at a substantially stoichiometric level. BRIEF DESCRIPTION OF THE DRAWINGS [0011] The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of an embodiment of the invention taken in conjunction with the accompanying drawings, wherein: [0012] FIG. 1 is a vehicle having a diesel engine utilizing an embodiment of the fuel control system of the present invention; [0013] FIG. 2 is a block diagram illustrating an apparatus that utilizes the method used in FIG. 1 ; [0014] FIG. 3 illustrates the steps of an embodiment of the method utilized in the apparatus of FIG. 2 ; and [0015] FIG. 4 illustrates an embodiment of another method utilized in conjunction with the method of FIG. 3 of the present invention. [0016] Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate embodiment of the invention and such exemplification is not to be construed as limiting the scope of the invention in any manner. DETAILED DESCRIPTION OF THE INVENTION [0017] Referring now to the drawings, and more particularly to FIG. 1 , there is illustrated a vehicle 10 in the form of an agricultural vehicle 10 also known as a tractor 10 having a loader attached thereto. Vehicle 10 includes a power generating system 12 that provides power to various aspects of vehicle 10 including motive power for wheels 14 . Although vehicle 10 is illustrated as a tractor 10 , it is to be understood that the present invention relates to any vehicle 10 and, more generally, to any power generating system 12 whether utilized by vehicle 10 or not. [0018] Now, additionally referring to FIG. 2 , there is illustrated details of power generating system 12 including engine 16 having an air cleaner 18 , a turbocharger compressor 20 , an air cooler 22 , an EGR cooler 24 , an EGR valve 26 , an EGR mixer 28 , a turbocharger turbine 30 , a diesel oxidization catalyst 32 , a diesel particulate filter 34 , a controller 36 , a torque or speed sensor 38 , a gas sensor 40 , and a fuel metering system 42 . Ambient air flows through air cleaner 18 , is compressed in turbocharger compressor 20 , is then cooled by cooler 22 , has exhaust gas mixed with the airflow in EGR mixer 28 , the mixture then flows to combustion chambers in engine 16 . Assuming, for the sake of clarity, that engine 16 is a diesel engine, fuel is then injected into each of the cylinders when the compression and cycle of the engine is appropriate for the injection thereof. Fuel is injected by way of fuel metering system 42 causing combustion to take place in the cylinders and the exhaust flows out from engine 16 passing either to an EGR cooler 24 or past turbocharger turbine 30 . The exhaust gas flow past turbocharger turbine 30 causes it to rotate and drives turbocharger compressor 20 . The exhaust gas flows by gas sensor 40 and then continues through diesel oxidization catalyst 32 and particulate filter 34 and the remaining gas is exhausted to the ambient atmosphere. [0019] The exhaust gas that flows by gas sensor 40 has a particular NOx and/or oxygen content, which is sensed by gas sensor 40 . The exhaust gas that is diverted through the exhaust gas recirculation system first goes through a cooling process by EGR cooler 24 and EGR valve 26 is under the control of controller 36 which can moderate the flow or completely shut-off the flow of the EGR. Exhaust gas that is recirculated may enter directly into EGR mixer 28 rather than into the flow as shown in FIG. 2 . Controller 36 is communicatively connected to speed sensor 38 , gas sensor 40 , fuel metering device 42 , and EGR valve 26 . [0020] Now, additionally referring to FIGS. 3 and 4 , there is illustrated methods 100 and 150 that carry out the control steps of the present invention. The steps may be carried out by way of hardware, an algorithm stored in controller 36 , or a combination of hardware and software. At step 102 , there is a detection of an increase in torque requirement for engine 16 that is sensed by speed sensor 38 and conveyed to controller 36 . Although schematically shown as a speed sensor connected to engine 16 , the sensing of torque requirement can be a combination of an anticipated load sensing system as well as increased load detection. Once the increase in needed torque is detected, the amount of the torque that is anticipated is utilized in step 104 to select the amount of fuel to match with the available airflow to engine 16 . The selection of the amount of fuel can be a selection based upon an entry in a look-up table having an amount that matches the detected torque requirement to a selected fuel amount or the amount of fuel may be determined as a result of an algorithm that may include fixed and changeable coefficients. [0021] At step 106 , the fuel and air is matched and sent to engine 16 based upon the selection that occurred in step 104 . The selection at step 104 and the matching of the fuel to the air at step 106 is part of the adaptive control system of the present invention and is carried out to cause the fuel and air mixture to be substantially stoichiometric during the load increase. [0022] While the fuel is being sent to engine 16 , the EGR may be shut off at step 108 or be moderated at step 108 for a certain period of time and then subsequently turned on at step 110 which may correspond to the meeting of the torque increase and engine 16 is then operating at a new static load level. At step 112 , the engine control is returned to its normal operating mode. The normal operating mode may include active controls that adjust the EGR flow as well as the fuel metering based upon information from gas sensor 40 . However, it should be noted that during the carrying out of the steps of the present invention that the current input from the gas sensor 40 is not utilized to select the fuel and air flow to engine 16 , rather, fuel is selected based upon the detected torque requirement and the amount of fuel is determined from a data look-up table or an algorithm based on the available air as previously discussed. Controller 36 evaluates the performance of engine 16 during the torque increase response with data from, among other things, gas sensor 40 and, in the event the information indicates a need to adjust the look up table and/or algorithm utilized by step 104 , controller 36 updates the values and/or variables so that the next time an increase in torque in the amount encountered occurs a more appropriate fuel selection can be utilized by controller 36 . This adaptive control system is needed since the open loop response inherent in such a system is evaluated and updated for an improved response the next time a torque requirement in a similar amount is encountered. [0023] This updating process is illustrated in method 150 where the detection of NOx or O 2 carried out at step 152 by utilizing gas sensor 40 and the data is updated at step 154 . Method 150 may run in parallel to method 100 as part of the adaptive control system. [0024] In the present invention, it can be considered that engine 16 is calibrated so that rapid load increases occur with a substantially stoichiometric fuel/air ratio, preferably with little or no EGR. Because the load increases will occur at or near stoichiometric conditions, the three-way catalyst which may be diesel oxidization catalyst 32 , which consists of one or more precious metal such as palladium, platinum, rhodium, etc., can be used to remove NOx emissions from the exhaust gas. Catalyst 32 and filter 32 could be modified to enhance the NOx removing function by changing the catalyst wash coat or precious metal. [0025] As methods 100 and 150 are carried out, engine 16 operates at or substantially at stoichiometric conditions, with or without EGR, during rapid load increases. Catalyst 32 serves to react with and remove NOx emissions from the exhaust gas. The operating range of the catalyst is approximately 200° C. to above 1000° C. so it will effectively remove NOx throughout the operating range of engine 16 . [0026] Gas sensor 40 may be a switching oxygen sensor that is used to confirm that the fuel/air mixture was substantially stoichiometric during the rapid load increase as described regarding method 150 , and the calibration elements contained in a data table are adjusted if the mixture has strayed from stoichiometric conditions due to changes in power generating system 12 , such as fuel injector wear, air flow measurement drift, or other changes to the engine. [0027] Advantageously, the present invention controls the engine operating conditions during torque load increases so that a near stoichiometric combustion occurs during these rapid load increases, thereby reducing NOx due to the high efficiency of the catalyst and high torque is output because fueling is appropriate to the air flowing into engine 16 . If the torque demand and trapped air is such that the fueling would not be sufficient to reach stoichiometric, EGR would be added to reduce the trapped air to reach near stoichiometric exhaust conditions. Advantageously, this concept provides a more responsive engine with lower NOx than conventional fueling controls. It does not require additional hardware on an engine that already has a catalyst for hydrocarbon control or a diesel particulate regeneration or a diesel particulate filter for diesel particulate removal. Advantageously, the switching oxygen sensor 40 is used to adjust the calibration to compensate for engine wear and other changes to power generating system 12 . The present invention can be used with or without EGR, although low emission diesel engines typically have EGR. [0028] While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
A method of controlling a diesel engine connected to a load, the method including the steps of detecting an increased torque requirement and matching a fuel flow with an airflow. The detecting an increased torque requirement step detects an increased torque requirement for the engine, the increased torque requirement taking place during a period of time. The matching a fuel flow step matches a fuel flow with an airflow going to the engine during the increased torque requirement, the matching step keeps the airflow and the fuel flow during the period of time at a substantially stoichiometric level enabling the use of a three-way catalyst to reduce NOx emissions during transients.
5
BACKGROUND OF THE INVENTION The present invention relates to a spring retainer for a poppet valve in an engine. Poppet valves in an engine are biased into a closed position by a pre-loaded spring. The force of the preloaded spring is transferred to a valve stem of the poppet valve by a spring retainer which is locked onto the valve stem. Spring retainers are often locked onto the valve stem via separate lock members. However, the separate lock members must be manufactured, handled and installed in addition to the manufacture handling and installation of the spring retainer. Also, spring retainers with integral locking means are known. A spring retainer with an integral locking means should be easily installed, provide sufficient locking force, and have a reasonable life. SUMMARY OF THE INVENTION The present invention provides a spring retainer for a poppet valve having a valve stem and a groove in the valve stem. The poppet valve is biased by a valve spring. The spring retainer comprises a one-piece annular body having an opening through which the valve stem extends. The body is preferably made of plastic composite material. The body has a spring flange encircling the body. The spring flange has a surface against which the valve spring acts. The surface lies in a plane. The body also has means which deflects outwardly as the valve stem is inserted into the opening and which snaps into the groove to lock the spring retainer to the valve stem. The means includes a plurality of fingers extending inwardly toward the opening and extending upwardly from the plane of the spring flange surface against which the valve spring acts. Each of the fingers has an upper surface which tapers upwardly as it extends from the spring flange and an inner surface for engaging the valve stem. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other features of the present invention will become apparent to one skilled in the art upon a consideration of the following description of the invention with reference to the accompanying drawings, wherein: FIG. 1 is a partial sectional view of an engine with a poppet valve and a spring retainer embodying the present invention; FIG. 2 is a top view of the spring retainer shown in FIG. 1; FIG. 3 is a cross-sectional view of the spring retainer taken along line 3--3 of FIG. 2; FIGS. 4 and 5 are cross-sectional views showing the installation of the spring retainer; FIG. 6 is a top view of a second embodiment of a spring retainer of the present invention; and FIG. 7 is a cross-sectional view of the second embodiment of the spring retainer of FIG. 6 taken along line 7--7 of FIG. 6. DESCRIPTION OF PREFERRED EMBODIMENT The present invention comprises a one-piece spring retainer 10 (FIG. 1). The spring retainer 10 retains a preloaded valve spring 14 concentrically around a valve stem 18 of a poppet valve 20 in an engine 24. The valve spring 14 biases the poppet valve 20 closed. The spring retainer 10 includes an annular spring flange 28. The spring flange 28 includes an annular planar surface 30 which engages the valve spring 14. The spring retainer 10 includes a downwardly projecting annular ring 32. The annular ring 32 is positioned radially inward of the planar surface 30. The annular ring 32 engages an upper portion 33 of the valve spring 14. The upper portion 33 applies a radially inward force to the annular ring 32. The valve spring 14 resists outward movement of the annular ring 32 to provide additional strength. The spring retainer 10 includes a plurality of resiliently flexible fingers 34. The spring retainer 10 could include any number of fingers 34, the present embodiment includes four fingers 34. The plurality of fingers 34 are lockingly engaged with the valve stem 18 to transfer the spring force from the valve spring 14 to the valve stem 18. The spring force biases the poppet valve 20 upwardly to engage valve seat 38 in the engine 24. The spring retainer 10 is annular in shape (FIG. 2). The spring retainer 10 has a center opening 40 which includes an upper portion 56 and a lower portion 58 (FIG. 3). The center opening 40 is generally circular to receive the valve stem 18 (FIG. 1). The plurality of fingers 34 (FIGS. 2 and 3) define the center opening 40. The plurality of fingers 34 are separated by a plurality of slots 48. The slots 48 are defined by curved surfaces 52. The plurality of fingers 34 have upper surfaces 66. The upper surfaces 66 taper upward from the spring flange 28. The upper surfaces 66 taper inward toward the central axis 68 of the center opening 40. The plurality of fingers 34 have inner surfaces 70 partially defining the upper portion 56 of the center opening 40. The inner surfaces 70 extend up from the lower portion 58 of the central opening 40. The inner surfaces 70 taper inwardly toward the central axis 68. Thus, the upper portion 56 of the center opening 40 has the shape of a truncated cone. The upper portion 56 of the center opening 40 is sized such that the valve stem 18 will engage the inner surfaces 70 when the valve stem 18 is forced through the upper portion 56 of the center opening 40. The upper surfaces 66 and the inner surfaces 70 taper to tips 74 of the plurality of fingers 34. Each of the plurality of fingers 34 ar wedge-shaped along a vertical cross-section between the upper surfaces 66 and the inner surfaces 70. The resilience of the plurality of fingers 34, the resilience of the spring flange 28 and the inwardly directed force of the upper portion 33 of the valve spring 14 bias the plurality of fingers 34 toward the central opening 40. Thus, the inner surfaces 70 are biased into engagement with the valve stem 18. The body of the spring retainer 10 is formed as a single piece. The spring retainer 10 is made of a resilient material. The resilience of the material allows flexibility of the plurality of fingers 34, without fracture or shear. The resilient material has a preferred ultimate tensile strength to flexural modulus ratio of 0.03±0.01. The resilient material may be metal or plastic or a composite. In the preferred embodiment, the resilient material is a plastic composite material primarily comprised of high temperature nylon and fibrous material, such as glass fiber. Such materials are STANYL®, marketed by DSM N.V. (formerly Naamloze Vennootschap DSM), and AMODEL®, marketed by AMOCO Oil Co. During installation, the valve spring 14 is press-fit onto the annular ring 32 of the spring retainer 10. The poppet valve 20 is positioned in the engine 24 (FIG. 1). The spring retainer 10 and the valve spring 14 are positioned adjoining the valve stem 18 such that the tip 84 (FIG. 4) of the valve stem 18 is positioned in the center opening 40. With the tip 84 thus positioned, the valve stem 18 extends through the lower portion 58 of the opening 40. A downwardly directed force A is applied to the spring retainer 10 by a mounting tool (not shown). A restraining force B is applied to the poppet valve 20 to prevent it from moving. The spring retainer 10 is moved downward relative to the valve stem 18. As the spring retainer 10 is moved relatively downward, the valve spring 14 is compressed and thereby preloaded. The tip 84 of the valve stem 18 engages the inner surfaces 70 of the plurality of fingers 34. The tip 84 applies an upward force which pushes upward on the plurality of fingers 34 as the valve stem 18 is moved up through the open center 40 of the spring retainer 10. The plurality of fingers 34 resiliently flex and rotate upwardly and outwardly at an angle Δ as the valve stem 18 moves relatively upward. As the plurality of fingers 34 move relatively down the valve stem 18, the tip 84 of the valve stem 18 moves further upward through the upper portion 56 of the center opening 40. The tip 84 of the valve stem 18 emerge above the tips 74 of the plurality of fingers 34 as the stem 18 continues to move upward relative to the spring retainer 10. As the tip 84 of the valve stem 18 moves past the tips 74 of the plurality of fingers 34, the plurality of fingers 34 are fully flexed or deflected upwardly and outwardly. The maximum normal deflection angle Δ of each of the plurality of fingers 34 is about 10° from an unflexed position. Once the tip 84 of the valve stem 18 clears the tips 74 of the plurality of fingers 34, the tips 74 of the plurality of fingers 34 each snap back toward an unflexed position, moving inwardly and downwardly into a groove 88 on the valve stem 18 (FIG. 5). The plurality of fingers 34 are urged inwardly by the natural resilience of the plurality of fingers 34, augmented by the radially inward force from the upper portion 33 of the valve spring 14. The mounting tool is then retracted, leaving the spring retainer 10 on the valve stem 18. As the tool is retracted, the valve spring 14 forces the spring retainer 10 axially upward until the tips 74 of the plurality of fingers 34 engage the lower surface 90 of the valve tip 84. The abutment between the plurality of fingers 34 and the tip 84 of the valve stem 18 force the plurality of fingers 34 to rotate into tight contact with the valve stem 18 at the groove 88, thus locking the spring retainer 10 into position on the valve stem 18. During operation of the poppet valve 20, the upward spring force of the valve spring 14 and the restraining force of the valve tip 84 tend to rotate the tips 74 of the plurality of fingers 34 inward and downward relative to the spring flange 28. However, the radially inward force of the upper portion 33 of the valve spring 14 resists excessive inward and downward rotation of the plurality of fingers and thus prevents excessive outward strain of the spring flange 28. Another embodiment of the invention is shown in FIGS. 6 and 7. The second embodiment of the invention comprises a spring retainer 110 (FIGS. 6 and 7). The spring retainer 110 retains a preloaded valve spring 14 (not shown in FIGS. 6 or 7) concentrically around a valve stem 18 (not shown) of a poppet valve 20 in an engine 24, as in the previous embodiment (FIG. 1). The spring retainer 110 (FIG. 6) includes an annular spring flange 128. The spring flange 128 includes an annular planar surface 130 (FIG. 7) which engages the valve spring 14. The spring retainer 110 includes a downwardly projecting annular portion 132. The annular portion 132 is positioned radially inward from the planar surface 130. The annular portion 132 engages the upper portion 33 (not shown) of the valve spring 14. The upper portion 33 applies a radially inward force to the annular portion 132. The valve spring 14 resists outward movement of the annular portion 132 to provide additional strength. The spring retainer 110 includes a plurality of resiliently flexible fingers 134. The plurality of fingers 134 are lockingly engaged with the valve stem 18 (not shown) to transfer the spring force from the spring 14 to the valve stem 18. The spring force biases the poppet valve 20 upwardly to engage the valve seat 38 of the engine 24 (as in FIG. 1). The spring retainer 110 (FIG. 6) is annular in shape. The spring retainer 110 has a center opening 140 which includes an upper portion 156 and a lower portion 158 (FIG. 7). The center opening 140 is generally circular to receive the valve stem 18. The plurality of fingers 134 define the center opening 140. The plurality of fingers 134 are separated by a plurality of vertical slots 148. Each of the slots 148 has a first narrow segment 152 and a second oval segment 154. The narrow segments 152 extend radially from the open center 140 and through the annular portion 132. The oval segments 154 perpendicularly intersect the narrow segments 152. The oval segments 152 extend in an arc along the junction of the plurality of fingers 134 and the spring flange 128. The oval segments 154 are partially defined by curved surfaces. The plurality of fingers 134 have upper surfaces 166. The upper surfaces 166 taper upwardly from the spring flange 128. The upper surfaces 166 extend inward toward the central axis 168 of the center opening 140. The plurality of fingers 134 have inner surfaces 170. The inner surfaces 170 extend upward from the lower portion 158 of the center opening 140. The inner surfaces 170 taper inwardly toward the central axis 168. The inner surfaces 170 partially define the upper portion 156 of the center opening 140. Thus, the upper portion 156 has the shape of a truncated cone. The upper portion 156 of the center opening 140 is sized such that the valve stem 18 (not shown) will engage the inner surfaces 170 as the valve stem 18 is forced through the upper portion 156 of the center opening 140. The upper surfaces 166 and the inner surfaces 170 taper to tips 174 of the plurality of fingers 134. Thus, the plurality of fingers 134 ar wedge-shaped in cross-section between the upper surfaces 166 and the inner surfaces 170. The resilience of the plurality of fingers 134 bias the plurality of fingers 134 toward the central opening 40. Thus, the inner surfaces 170 are biased into engagement with the valve stem 18. The body of the spring retainer 110 is made as a single piece. The spring retainer 110 is made of a resilient material, preferably the same materials referred to with respect to the first embodiment. The spring retainer 110 is installed in the engine 24 in the same fashion described with respect to the first embodiment (as shown in FIGS. 4 and 5). During installation of the spring retainer 110 (FIGS. 6 and 7), the oval segments 154 provides increased flexibility for the plurality of fingers 134. From the above description of the invention, those skilled in the art will perceive improvements, changes and modifications. Such improvements, changes and modifications within the skill of the art are intended to be covered by the appended claims.
A spring retainer for a poppet valve having a valve stem and a groove in the valve stem. The poppet valve is biased by a valve spring. The spring retainer includes a one-piece annular body having an opening through which the valve stem extends. The body has a spring flange encircling the body. The spring flange has a surface agains which the valve spring acts. The surface lies in a plane. The body further has members which deflect outwardly as the valve stem is inserted into the opening. The members snap into the groove to lock the retainer to the valve stem. The members include a plurality of fingers extending inwardly toward the opening and extending upwardly from the plane. Each of the fingers has an upper surface which tapers upwardly and inwardly as it extends from the spring flange and an inner surface for engaging the valve stem.
5
CROSS-REFERENCE TO RELATED APPLICATIONS The present application is related to and claims priority from U.S. provisional patent application Ser. No. 61/654,159 filed Jun. 1, 2012, which is herein incorporated by reference. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH Not Applicable. BACKGROUND OF THE INVENTION The present application is generally related to large bearing cage configurations, and in particular, but not exclusively, to a cage assembly for a large diameter bearing containing multiple heavy rolling elements and including discrete bridge elements coupled between axially-spaced cage wire rings located adjacent opposite axial ends of the rolling elements. The usual approach to designing large-bearing cages (typically 1-4 meters in diameter) has been to extend the design styles for smaller, conventional bearings to the larger bearing sizes. The first and most common attempt at meeting the needs of larger bearings uses pin style cages to facilitate placement and retention of the rolling elements. While pin style cages provide excellent retention, they are heavy, complex, and costly to assemble. Furthermore, some pin style cage designs can partially block flow of lubricants (especially grease) to critical wear surfaces. They also cannot be disassembled without damaging either the cage rings or the cage pins. Another cage design often considered is an “L” type design produced using various combinations of forging, forming, machining and precision cutting. The resulting cost of bearing cages produced using combinations of these various processes are unacceptably high, especially for the larger bearing sizes. Yet another cage design is a polymer segmented style cage. While these cages have a demonstrated ability to perform satisfactorily, there are potential limitations in scaling up this design for larger bearings containing heavy rollers. Current polymer cages for very large bearings are made from polyether ether ketone (PEEK), an organic polymer thermoplastic which is relatively expensive. For extremely large bearings containing large rollers, the size and strength of the cage must be increased. The greater amount of PEEK required to make a sufficiently strong cage can therefore often be cost prohibitive. Accordingly, polymer segmented cages appear to be most suited for bearing cages with small to medium size rollers which only require small to medium size PEEK segments. Based on the foregoing, it would be advantageous to provide a large bearing cage design having full functionality (roller retention, roller spacing, roller alignment, lubricant flow) for various sizes and types of bearings (e.g., tapered roller, cylindrical roller, spherical roller bearings, etc.) and which can be manufactured at a lower cost than is currently possible. BRIEF SUMMARY OF THE INVENTION Briefly stated, the present disclosure provides a bearing assembly having a plurality of rolling elements (rollers) disposed about the circumference of a race member and positioned in a spaced configuration by a segmented bearing retainer assembly. The segmented bearing retainer assembly comprises a plurality of discrete bridge elements coupled between first and second wire support rings located adjacent axially opposite ends of the bearing assembly. Each discrete bridge element has a cross-sectional shape adapted to contact adjacent rolling elements on the rolling element's circumferential surface and radially displaced from the pitch diameter of the bearing. This maintains the spacing between adjacent rolling elements in the bearing assembly, and retains the rolling elements relative to the race member. A desired spacing arrangement about the circumference of the bearing assembly, between the wire support rings, is achieved using a plurality of spacers disposed on the rings. In a preferred embodiment the bridge elements and spacers have a piloted engagement. The rings extend through attachment eyelets formed in each end of each bridge element. In one embodiment, the discrete bridge elements of the segmented bearing retainer assembly are disposed between adjacent rolling elements in the bearing assembly. Each bridge element includes an axially aligned bridge segment traversing between adjacent rolling elements. An end block at each axial end of the bridge element includes the attachment eyelet through which a wire support ring passes. Each discrete bridge element further has a cross-sectional profile designed to distribute a contact load between a rolling element and an adjacent bridge element above (radially outward from) a pitch diameter of the bearing assembly. At least one surface on the end block is profiled to position the cage assembly against an end surface of the rolling elements. In another disclosed embodiment, each discrete bridge element has a cross-sectional shape adapted to contact adjacent rolling elements on the rolling body's circumferential surface at a position which is radially inward from the pitch diameter of the bearing. Additional surface profiling on a bridge element's end faces may be optimized to position the segmented bearing retainer assembly on the large end of the rolling elements so to establish and maintain a beneficial lubricant film between them. In a preferred embodiment, the discrete bridge elements are of a powdered metal or sintered steel. The discrete bridge elements may be impregnated with a lubricant, or dipped in a lubricant for a period of time for the lubricant to be absorbed into the bridge element, or the bridge element may be vacuum impregnated with a lubricant. Optionally, the bridge elements may have surface features or finishes configured to, over time, trap and release lubricants. The rings are initially open ended to allow for assembly of the bridge segments and spacers onto the rings. The free ends of the rings have a feature which facilitates subsequently joining the ends together as part of the final assembly. In one embodiment the rings have a groove near each end which allows the rings to be connected by a joining spacer, using a crimp joint. In another embodiment the free ends of the rings are threaded with opposite handed threads and a joining spacer in the form of a turnbuckle is used to join the ends of the rings together. This embodiment allows the spacers and bridge segments to be drawn together to a desired degree of force. By drawing the spacers and bridge elements tightly together a more rigid cage structure is obtained. In another embodiment one end of the ring has a groove formed in it to receive a crimp connection and the other end of the ring is threaded. In this embodiment, the common right handed threads only may be used and the need to use the less common left handed threads is eliminated. The joining spacer in this case has threads on only one side and is crimped on the other end. For the embodiments using a threaded joining spacer to connect the respective ends of each ring together, a means to prevent the threaded engagement from backing off is desired. This may be accomplished by a thread adhesive, by a set screw engaging the spacer and ring or by welding the adjusting spacer to the ring. The joining spacer may have features to make rotation easier when drawing the cage together. Common features employed are one or more flats, or octagonal or hexagon external geometries that will accept an open end wrench, or radial holes for rotation by a simple pin or by a spanner wrench. A method of the present disclosure for assembling a segmented bearing retainer assembly about an inner race of a tapered bearing is accomplished by initially threading a plurality of discrete bridge elements and spacers onto ends of the first and second wire support rings. Each wire ring is then formed into an open loop and the ends of the rings are threaded with opposite handed threads. Discrete bridge elements and the spacers between them are first inserted onto the wire support rings. Individual rollers (rolling elements) are then inserted into the assembly by moving the bridge elements and spacers circumferentially around the wire support rings so to provide sufficient space for insertion of the rollers. After the final roller is installed on the inner race, the rings are parted in opposite directions to open up a space for insertion of a turnbuckle. The turnbuckle is then used to draw all of the bridge elements and spacers tightly together. The foregoing features and advantages set forth in the present disclosure as well as presently preferred embodiments will become more apparent from the reading of the following description in connection with the accompanying drawings. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS In the accompanying drawings which form part of the specification: FIG. 1 is a view, partly in section, of a portion of a segmented bearing retainer assembly of the present disclosure; FIG. 2 is a perspective view of a discrete bridge element of the segmented bearing retainer assembly of FIG. 1 ; FIG. 3 is a sectional view of the discrete bridge element taken along line 3 - 3 in FIG. 2 ; FIG. 4 is a perspective view of an alternate embodiment of a discrete bridge element in which each eyelet has a counter-bore formed at each of its ends; FIG. 5 is a sectional view, taken along line 5 - 5 in FIG. 4 , of an end block and illustrating the counter-bores formed at the ends of an eyelet; FIG. 6 is a perspective view of another alternate embodiment of a discrete bridge element in which bosses are formed at the ends of the eyelets; FIGS. 7A-7C illustrate different assembly methods by which a piloted spacer is secured to a wire support ring; FIGS. 8 and 9 represent portions of the segmented bearing retainer assembly using differently shaped turnbuckles; and. FIG. 10 is a perspective view of a slotted or open sided spacer used in the assembly. Corresponding reference numerals indicate corresponding parts throughout the several figures of the drawings. It is to be understood that the drawings are for illustrating the concepts set forth in the present disclosure and are not to scale. DETAILED DESCRIPTION The following detailed description illustrates the invention by way of example and not by way of limitation. The description enables one skilled in the art to make and use the present disclosure, and describes several embodiments, adaptations, variations, alternatives, and uses of the present disclosure, including what is presently believed to be the best mode of carrying out the present disclosure. Referring to FIGS. 1 , 8 , and 9 , a preassembled segmented bearing retainer or cage 100 comprises first circular hoop or ring 102 and a second and correspondingly sized and shaped circular hoop or ring 104 . As particularly shown in FIG. 1 , ring 104 is axially displaced from ring 102 . Cage 100 also includes multiple discrete bridge elements 206 each of which spans the axial distance between rings 102 , 104 . The bridge elements are preferably made of a powdered metal material including sintered steel. Cage 100 further includes tubular spacers 110 each of which has a longitudinal bore 111 (see FIGS. 7A-7C ) by which the spacers are inserted onto one of the rings 102 , 104 and positioned between adjacent bridge elements 206 as shown in FIGS. 1 , 8 , and 9 . As shown in FIGS. 1 , 7 A, and 7 B, the spacers (which may comprise a turnbuckle 140 ) have a reduced diameter section at each of their ends. Also, while the outer surface of the spacers is generally round, as shown in FIG. 9 , a spacer (turnbuckle) 150 has a polygonal shaped outer contour; for example, it may have a hexagonal or octagonal outer contour. Such a construction results in at least one flat surface on the outer contour of the spacer. Referring to FIG. 7C , a spacer (turnbuckle) 160 has a threaded longitudinal bore 161 in which threaded ends of rings 102 , 104 are received. In this embodiment, the spacer has a uniform outer diameter throughout its length. As designed and constructed, each roller 112 moves freely within its respective pocket in bearing retainer 100 such that the load on any bridge element 206 is only a function of the mass of the roller 112 either ahead of or behind it, or a combination of the masses of both rollers, depending on the dynamic conditions. Different embodiments of bridge element 206 are shown in FIGS. 2-6 . Regardless of the particular bridge element design, at each end of the bridge element an end block 208 is formed. The end blocks are axially spaced from each other and an eyelet 214 is formed in each end block. Each eyelet comprises a bore extending longitudinally through the end block, and the eyelets are sized to allow one of the rings 102 , 104 to be inserted through a respective one of the end blocks as shown in FIGS. 1 , 8 , and 9 . Referring to FIGS. 2 , 4 , and 6 , the end blocks 208 of each bridge element 206 are separated by a retention web 216 which is attached to the inner surface of a bridge 215 that extends between the end blocks. Retention web 216 helps keep bridge element 206 in alignment with the external curvature of the rollers 112 . This, in turn, helps restrict radial deflection of cage 100 during operation, as well as maintain adequate lubrication. As shown in FIG. 1 , for example, as a roller 112 travels through a load zone of the bearing, it moves through a pocket space S formed between adjacent bridge elements 206 until the roller contacts the bridge element rotationally ahead of it. In a preferred embodiment, retention web 216 of a bridge element 206 has straight and flat surfaces 217 (see FIG. 3 ) which distribute the contact load between a roller 112 and the bridge element. A contact region is disposed radially outward from the pitch diameter of the bearing in substantially the same location as the contact region provided by a conventional above centerline “L” type bearing cage. If retention web 216 does not extend radially inwardly past the bearing pitch diameter, additional space is provided between adjacent rollers 112 as to permit the storage and resupply of grease (or other lubricant) to the various contact regions located about the roller. Those of ordinary skill in the art will recognize that bridge element 206 may be configured with a retention web 216 and bridge 215 in a position which is radially inward from the pitch circle or diameter of the bearing. Thus, the contact load between a roller 112 and a bridge element 206 is within a contact region which is correspondingly disposed radially inward from the pitch diameter of the bearing. Those of ordinary skill in the art will further understand that the particular construction of a bridge 215 and retention web 216 depends upon the particular usage of the segmented bearing retainer 100 . Construction of the bearing retainer or cage 100 , as shown in FIG. 1 , is for use with a tapered bearing. Based on the size of an inner race 118 (see FIGS. 1 and 8 ), the required diameters of rings 102 , 104 are determined. During assembly, each ring 102 , 104 is initially open, thus allowing all of the bridge elements 206 , spacers 110 , and a turnbuckle 140 (see FIG. 1 ) if one is used, to be slipped onto and positioned around the respective rings. In a preferred embodiment, the number of spacers 110 is one less (N−1) than the number N of rollers 112 employed in the bearing. In alternate embodiments, the number of bridge elements 206 equals the number N of rollers 112 . After all the bridge elements and spacers are installed on the rings, the ends of the rings are brought together and joined together. For example, as shown in FIG. 1 , the opposite ends of rings 102 , 104 are threaded, as indicated at T, and the respective ends of each ring are threaded into a turnbuckle 140 to form a continuous ring. Alternate ways of closing rings 102 , 104 are shown in FIGS. 7A-7C . In FIG. 7A , a turnbuckle/spacer 141 has a radial bore 142 extending both through it and the ring 102 , 104 whose ends are captured in the turnbuckle/spacer. An anti-rotation pin 143 is inserted through this bore. In FIG. 7B , bore 142 extends only through one side of the turnbuckle/spacer and a set screw 144 is used to secure the turnbuckle/spacer to the ring. In FIG. 7C , a weld W is formed at the inner end of a radial bore 162 in spacer 160 to attach the turnbuckle/spacer and the ring together. Also, although not shown in the drawings, the ends of the spacer 141 can be crimped about the ends of the support ring inserted in the spacer. It will be appreciated that the ends of the ring can be secured to a turnbuckle/spacer using a combination of the above techniques. For example, one end of the ring may be threadably received in a turnbuckle with the other end of the ring crimped in place in the other end of it. Attachment of the ends of ring 102 , 104 to the spacer can further be done using an adhesive material. Regardless of the method (or methods) of attachment used, in addition to securely attaching the ends of ring 102 , 104 together to form a completed ring, the turnbuckle/spacer to which the ring ends are secured is now prevented from rotational movement which could otherwise, over time, loosen the connection. Those of ordinary skill in the art will recognize that the spacers 110 may float on the rings 102 , 104 between the discrete bridge elements 206 . Referring to FIGS. 2 and 3 , the outer ends of the bores 214 formed in each end block 208 of a bridge element 206 are flush with the sides of the end block. Accordingly, spacers 110 installed between the adjacent bridge elements float between the bridge elements. Referring to the bridge element 206 shown in FIGS. 4 and 5 , spacers installed between adjacent bridge elements as shown in these figures may be in a piloted engagement with the discrete bridge elements so to maintain a desired relative positioning of the components. In this embodiment of bridge element 206 , each end block 208 includes a counter-bore 214 cb formed at the outer end of each bore (eyelet) 214 that extends through the respective end block. As shown in FIG. 1 , the counter-bores are sized to receive the spacers 110 . Alternatively, as shown in FIG. 6 , each end block 208 on a bridge segment 206 is formed to have a raised boss 214 b surrounding the outer ends of each bore 214 . The bosses 214 b are sized to seat inside the inner end of an adjacent spacer 160 as shown in FIG. 7C . In one method of assembly, bearing retainer 100 is formed by supporting inner race 118 on a work table (or other surface) with its back face or large end facing downward. The assembled cage is then brought into position over and around the inner race. One by one, each roller 112 is inserted onto the assembly by moving the bridge elements 206 and spacers 110 (if required) circumferentially around the rings 102 , 104 so to make space available for insertion of the next roller. For installation of the final roller into its space on inner race 118 , the already assembled rollers 112 , bridge segments 206 , and spacers 110 are moved in opposite directions about the circumference of the rings thereby to create sufficient space into which to fit this roller. If required, after the last roller is inserted into place, a final bridge element 206 is installed to fill any remaining gap between the rollers 112 . In an alternate method of assembly, the ends of rings 102 , 104 remain separated during the assembly process. The rings are brought into position over and around inner race 118 and are moved apart to create a circumferential gap of sufficient width to allow bridge elements 206 and spacers 110 (if the design so requires them) to be slipped onto the rings. The bridge elements and spacers are spread equally around inner race 118 with rollers 112 positioned between them. When all of the rollers, bridge elements and spacers are installed, the ends of each ring are drawn together until a proper tension is created and an appropriate clearance is established between the rollers and the cage assembly. This clearance is referred to as “cage shake”. Once the requisite cage shake is established through proper tensioning of the rings, the ends of the rings are joined together as previously described. The method used for joining the separated ends of rings 102 , 104 must close the gap between the installed components so a correct amount of circumferential clearance exists in the “stack up” of spacers 110 and bridge elements 206 . This is conveniently accomplished by modifying the width(s) of one or more spacers, if necessary. The assembly methods described with respect to FIGS. 7A-7C limit circumferential movement of the spacers and bridge segments 206 on the ring should tension on the ring be lost over time due, for example, to creep or wear. By limiting the stack of potential gaps between the spacers and bridge elements, the ability of cage 100 to retain rollers 112 will be preserved for longer periods should the cage begin to lose tension. To further limit the stack up of potential gaps, one or more spacers 110 are fixed to a ring 102 , 104 by welding. This will limit the stack up of accumulated gap between each of the fixed spacers, including the turnbuckle spacer. To facilitate spacing, the spacers 141 , 150 , and 160 have a radial bore 142 , 162 respectively, in which a welding material is deposited. Or, as shown in FIG. 10 , a spacer 170 is a split spacer having a longitudinal slot 171 extending the length of the spacer as shown in FIG. 10 . When spacer 170 is used, the welding material is deposited in slot 171 to attach the spacer to a ring 102 , 104 . Compared with some previous segmented bearing cage designs, bearing retainer 100 of the present disclosure is configured to provide an improved flow of lubricant to critical wear surfaces within the bearing assembly; for example, between bridge elements 206 and rollers 112 . Use of circular cross-section rings 102 , 104 and eyelet couplings 214 for the bridge elements provides openings for the axial movement of lubricant into the spaces between adjacent rollers. Again to further enhance lubrication, exposed surfaces of the bridge elements or segments may receive special finishes or textures to entrap and release lubricants in the contact regions between the bridge elements and rollers. These features can be applied to the appropriate surfaces as previously described. Those of ordinary skill in the art will recognize that the bridge elements 206 may have more complex geometries than those shown in the drawings without departing from the scope of the invention. While, as previously noted, the bridge segments are preferably made of a powdered metal, they may also be formed from a variety of materials including polymers and metals. Examples of suitable constructions include a compacted and sintered powered metal or steel construction which produces very strong bridge elements suitable for use with very large and heavy bearing designs, and which can optionally be impregnated (for example, by vacuum impregnation) with lubricating materials so to provide improved resistance to wear at critical surfaces within the bearing assembly. These type bridge elements may also have surface features or finishes which promote the trapping and releasing of lubricants. As various changes could be made in the above constructions without departing from the scope of the disclosure, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
A bearing cage assembly ( 100 ) comprises a plurality of discrete bridge elements ( 206 ) disposed between adjacent rolling elements ( 112 ) and coupled between first and second axially spaced cage support wire rings ( 102, 104 ) which are appropriately tensioned. Spacers ( 110 ) are disposed between adjacent bridge elements and engage the bridge elements in a piloted engagement. The bridge elements maintain a separation between rolling elements, retain the rolling elements within the bearing assembly, and function as a lubrication reservoir for grease lubricated bearings. Profiled surfaces on the bridge elements position the bearing cage assembly on at least one axial end of the rolling elements.
5
CROSS-REFERENCE TO RELATED APPLICATIONS The present application is a continuation of International Patent Application PCT/EP2005/003338 filed on Mar. 30, 2005 and published in German language, which International Patent Application claims priority under the Paris Convention from German Patent Application DE 10 2004 016 029.5, filed Mar. 30, 2004. BACKGROUND AND SUMMARY Touch-sensitive surfaces can be used for making computer inputs with flexible adaptation to the hands. In this field there are innovative opportunities which have been unutilized until now. In particular, for the application on the steering wheel of a vehicle it is appropriate to use versions of the dynamic inputs which are related continuously to the instantaneous positions of the hands. The switching functions, for example travel direction indicators, dipping of headlights, wiping, which are the most important in particular for the hands are made available at the steering wheel—cf. FIG. 1 and FIG. 2 . The surface of the steering wheel can therefore be used for controlling specific functions which relate to the vehicle, but it can also be used for controlling the telephone or PDA and finally also for controlling a personal computer by simulating a keyboard which is continuously dynamically adapted to the hands—cf. FIG. 3 —only when the vehicle is stationary for the sake of safety. For the latter application cases, positions of the instantaneous touch zones can be displayed visually. And it is possible for the through connection of a finger to be perceived in a sensitive fashion as a nonlinear profile of force and travel. Here, variants of the design of such sensitive surfaces are explained. In particular, touch-sensitive surfaces can be implemented elastically by means of specific fabric-fiber structures which provide a nonlinear through-connection behavior which can be perceived sensitively. Corresponding structural solutions are mentioned. It is also possible to integrate visual display properties, in particular by means of light-emitting fibers or by means of a layer of light-emitting polymers or “electronic ink”. Such structures can finally also be used for separate, mobile computer input devices—cf. FIG. 3 again. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagrammatical view of a first portion of the steering wheel of a vehicle adapted for use as a computer input device having a first array of touch-sensitive surface areas according to the present invention; FIG. 2 is a diagrammatical view of a second portion of the steering wheel shown in FIG. 1 having a second array of touch-sensitive surface areas according to the present invention; FIG. 3 is a diagrammatical view of a portion of the steering wheel of a vehicle having touch-sensitive zones for simulating an alphanumeric computer keyboard; FIG. 4 is a cross-sectional view of a portion of the steering wheel shown in FIGS. 1-3 ; FIG. 5 comprises top, side and front views of elastic elements, such as pre-formed wires, integrated into one of the layers of material in the vehicle steering wheel; FIG. 6 is a cross-sectional view of a vehicle steering wheel illustrating an alternative manner of integrating elastic elements, such as pre-formed wires, into one of the layers of material in the steering wheel; and FIG. 7 is a top view of the integrated elastic elements, such as pre-formed wires, shown in FIG. 6 . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As shown in the accompanying drawings, the positions of the areas of the hand and fingers which are to be applied to the device are interrogated in order to generate a basic topography of the maximum ten fingers by means of which in turn an assignment topography is calculated for the relevant input face zones. As a result, pressure triggering processes give rise to respective control signals or alphanumeric signals. This assignment topography can comprise different signals for bent, relaxed or extended fingers. It is also still possible to determine the identity of areas of the hand and of fingers, for example by means of a pattern detection system, when the hands are moved or the gripping position changed. A plurality of small input face zones is continuously interrogated electronically and analyzed by means of a pattern detection method in order to update the basic topography and assignment topography. The input zone, in particular the steering wheel surface, is therefore composed of a plurality of small input face zones in a specific resolution. The assignment between an instantaneously activated input face zone and the control signal or alphanumeric signal which is triggered with it follows the continuously updated assignment topography. This is calculated from the available basic topography according to a pattern detection system and from the actually touched locations in relation to the previous assignment topography. That is to say the actually touched input face zones within the grid of the assignment topography firstly trigger a signal and secondly correct the position of the respective input face zone in the assignment topography by averaging within an adjustable empirical time period or within an adjustable number of actual activation processes. It is possible for continuously corrected characteristic values to be included in this calculation. That is to say the assignment topography is adapted individually and dynamically to the hands, habits and instantaneous movement and change in gripping position. FIG. 3 shows, for example, the surface of the computer input device, here with touch zones of a simulated alphanumeric computer keyboard 30 , that is to say with the instantaneous input face zones to which a respective alphanumeric character or a control character is assigned. This optional example of the instantaneous arrangement of the touch zones or of the input face zones shows, by means of ellipses, the instantaneous basic topography of the ten fingers 32 and the position of the hand rest surfaces 34 . And the illustrated alphanumeric characters mark the instantaneous assignment topography which, if appropriate, can also be displayed by means of a display unit. This figure shows a view of the input face which is, for example, developed from the steering wheel. In this concept which can be used in particular for the steering wheel, the areas of the hand positioned on the steering wheel, in particular the balls of the hand 34 , also contribute to the process of determining the basic topography. The individual and dynamic adaptation of the assignment topography is in particular possible for an extensive computer keyboard (only when the vehicle is stationary for the sake of safety), for PDA keypads and for mobile phone keypads, for touch zones arranged in longitudinal rows and primarily for simple touch zones around an index finger and a thumb, which can also differentiate touch zones for bent fingers from those for extended fingers. This concept can in particular be applied by means of a touch-sensitive surface which can integrate tactile feedback in the through-connection behavior in a sensitive fashion and can also integrate visual feedback—for use in a stationary vehicle—with display properties (see below). It is additionally possible to agree a double click in order to provide the possibility of differentiating desired triggering from unintentional contact. This concept provides data input possibilities for moving hands. Inputs of the devices of the data communication and control activities which are related to the vehicle take place on a homogeneous or quasi-homogeneous surface which acts as a plurality of input faces. The differentiation between a change in the hands and fingers which is not intended to be a data input—for example when changing the gripping position on the steering wheel—and the intentional triggering of pressure by the hands which has been carried out in order to input data can either be recognized from the type of deviation of the positions and pressure-triggering processes with respect to the instantaneously applicable basic topography or should be characterized, for example, as a double click. This concept provides in particular four applications: 1.) The input face simulates a computer keyboard. For example, a sensitive steering wheel surface can then be used as a computer keyboard, when the passenger car is stationary. For the purpose of initialization it is sufficient to position the ten fingers. The necessary deviations from the basic topography which are necessary to trigger signals can remain relatively small because this system can also operate in this way. This system which is capable of learning can also recognize very small distances, for example between normal and extended finger positions as sufficient. In this way a computer keyboard also fits onto the surface of a steering wheel. 2.) The input face simulates a PDA keypad or mobile phone keypad. A) For the purpose of initialization by means of, for example, two to five—or up to ten—fingers which have been positioned in a spread-out fashion, the extent of the standard mobile phone keypad is predefined. When two pressure locations are perceived it is possible, for example by means of the presetting of the system, to assume that the fingers are an index and a middle finger, from which the position of the other fingers follows. In this sense it is also possible to interpret three, four or five pressure locations per presetting in a self-evident fashion. B) Alternatively, for the purpose of initialization, that is to say for acquiring the basic topography, the steering wheel is held tight with one hand and, for example, two to five fingers of the other hand are spread out. The basic topography follows from this, and ultimately the assignment topography. 3.) The input face provides approximately ten input face zones which are arranged in longitudinal rows, i.e. touch zones which control, in particular, a PDA or a mobile phone. By means of, for example, two to five—or up to ten—fingers which are positioned in a spread-out fashion it is possible to predefine the extent of the touch zones for the purpose of initialization—see also item 2. The basic topography follows from this, and ultimately the assignment topography. A distinct distance in the centre separates the input face zones of the left and right hands. 4.) The input face interprets, in particular, the touch zones around the index finger and thumb as controlling input face zones. In this way it is possible, for example, to control travel direction indicators, means for setting headlights to full beam and for dipping them and windshield wipers, without removing one's hand from the steering wheel. In order to perform initialization it is sufficient to grasp the steering wheel in the usual way. Continuous changes in the gripping position of the hands is corrected and adapted computationally. The detection of the control signal of a finger is relatively simple here because the basic topography can be continuously detected by means of the supported hand, that is to say in particular by means of the supported balls of the hands. The presettings may be, for example, as follows: A) For the control of the direction indicator display the following applies, for example, double click on the loosely extended left-hand index finger as a “left-turn” travel direction indicator and double click on the loosely extended right-hand index finger as a “right-turn” travel direction indicator. The occasionally necessary switching off of the travel direction indicator can then be carried out by a double click on a position approximately centrally between the two basic positions of the hands or can be cancelled by a further double click. B) For example the headlight can be set to full beam by a double click by the slightly bent left-hand index finger. The beam can be dipped by a double click by the left-hand thumb. C) For example the windshield wiper can be switched to a faster speed—from the intermittent setting to normal setting and to a fast setting—by double click by the slightly bent right-hand index finger. The windshield wiper can be switched to a slower speed by a double click by the right-hand thumb. D) Alternatively the most important control functions of the vehicle can be triggered with just one hand on the steering wheel. In order, for example, to have the right hand free for switching or other operations it is possible to activate the most important control functions with the left hand—cf. FIGS. 1 and 2 . As diagrammatically shown in FIG. 1 , the upper portion of the steering wheel 10 facing the driver may be provided at instantaneous touch zones for the left-hand thumb positioned towards the hand 12 , in the relaxed position 14 , and extended from the hand 16 . Similarly, as shown in FIG. 2 , the upper portion of the steering wheel 10 facing away from the driver may be provided with instantaneous touch zones for the middle finger of the left-hand in the non-extended 18 and extended 20 positions, and for the index finger of the left-hand in the non-extended 22 and extended 24 positions. The assignments for these touch zones can be set individually. For example, the double click by the loosely extended left-hand middle finger of the travel direction indicator can mean “turn left” and the double click on the loosely extended left-hand index finger as a travel direction indicator can mean “turn right”. The dipped headlights and wipers can be activated, for example, by the left-hand thumb. E) The essential identification of the thumbs and index fingers follows from the currently available basic topography. Moreover, in this example it is only necessary to differentiate between slightly bent and loosely extended index finger. This differentiation can take the form of the individual and dynamic adaptation of the system, i.e. it can ultimately be “trained” and reduced by the “learning-enabled” system to a small and convenient difference. Hazardous control signals should not be possible here for safety reasons, i.e. for example it should not be possible for this system to switch off the headlights or to completely switch off the windshield wiper. (Both of these would then have to be done by customary switches on the dashboard). It is possible to agree, for example, a quadruple click by an index finger as a means of activating the entire system. In order to differentiate between an unintentional movement as against intentional pressing in order to trigger a control signal it is possible, for example, for the double click to apply as a presetting which relates in particular in applications 2 , 3 and 4 . In the case of uses with frequent movement and relatively large changes in the gripping position of the hands, for example when steering a motor vehicle, the double click can therefore be agreed in order to actually trigger a corresponding control signal, for example setting the headlights to full beam. On top of this, large movements of the areas of the hand, in particular of the balls of the hand, can be checked and recognized by a pattern detection system which determines the identity of the areas of the hands and fingers from the topology of large and small pressure areas and thus supplements the determination of the basic topography. Each change in gripping position requires renewed checking or, as it were, renewed initialization of the basic topography. The sensitive steering wheel surfaces or input devices which can be continuously adapted for individual hands and instantaneous situations can be implemented, in particular, as fabric in a number of variants. It is possible to use and combine fabric types or layers which (a) react in an electrically effective fashion on contact, for example through a measurable change in resistance or capacitance, (b) provide sensitive, tactile feedback during a through connection and (c) fabrics or layers which provide visual feedback, for example fabrics with light-emitting fibers. These fabric types or layers are either placed one on top of the other or the aforesaid qualities are integrated into a complex fabric. The solutions specified here therefore (a) make the input face touch-sensitive or approach-sensitive to a plurality of fingers positioned simultaneously, (b) they provide a perceptible through-connection behavior and (c) they simultaneously make the instantaneously effective characters visually recognizable in their arrangement on the input area. They are thus in a certain competition with customary computer keyboards and with customary touch screens or interactive displays. The provision of both sensory input qualities and visual display qualities in one area is appropriate in order to adapt the interface in a continuously dynamic fashion to hands, handling habits and situations. The important factor is therefore to make the input face zones which respectively apply to the characters at a particular time visible with an appropriate resolution. It is thus already sufficient to provide visual characterization of the assignment locations or of the various input face zones, for example through textile fibers which can be illuminated, in order to mark this instantaneous assignment topography. At best, the characters or control instructions can be displayed with fine resolution, for example by means of “electronic ink” or very fine textile fibers which can be illuminated or by organic LEDs. “Electronic ink” is currently being developed, for example, by Xerox and E-Ink. These computer input devices can therefore be coated with a layer of “electronic ink” or light-emitting polymer, in particular OLED, in order to visually display the instantaneous assignment between the input face zone and the respective character. This applies both to a steering wheel, which can also be used for example, as, a computer keyboard in a stationary vehicle, and to another computer input device. The properties of such a device or of such a method therefore vary in the range between, on the one hand, a keyboard-like surface which does not provide any visual information, or only very simple visual information, and, on the other hand, a high quality visual touch screen. The solutions explained here can ideally also differentiate a plurality of fingers simultaneously. It can also be sufficient for just part of the visually displayed area—in particular the lower part—to represent the aforesaid instantaneous arrangement of the characters while the other—upper—part of the area serves only as a screen. Different variants which respectively make compromises between optical and tactile qualities, are conceivable. In particular the following solutions with particular properties are suitable as a steering wheel cover and as a lightweight and transportable computer input device. These fabrics can be implemented, inter alia, by laying certain types of fabrics one on top of the other: one type made of touch-sensitive fibers or lamellas which is effective electrically or through changes in electrical capacitance, if appropriate a separate fabric type of tactile feedback of the nonlinear through-connection behavior, and a further fabric type with display properties, which fabric type acts, in particular, by means of light-emitting fibers. These fabrics can be linked to one another at specific intervals in such a way that an appropriately precise assignment between touch-sensitive input face zones and visually recognizable display zones is brought about. These fabrics can be implemented in particular by this input face being composed both of touch-sensitive fibers or lamellas which are effective electrically or electrostatically or through changes in electrical capacitance and of fibers with a light-emitting capability which are woven thereto. These light-emitting fibers act as visually recognizable display zones and indicate the instantaneous assignment between the input face zone and respective character visually. Specifically shaped fibers or lamellas which have a specific flexural rigidity or torsional rigidity and which have a nonlinear behavior in the proportion—which can be perceived by the fingers—of the application force to the spring travel can be woven into these touch-sensitive fabrics or into adjacent fabric layers: after a certain small spring travel, the further application force no longer increases but rather stays the same or decreases again. As a result, a through connection which can be clearly felt in a sensitive fashion is provided in the sense of a toggle lever effect. This effect can be achieved in particular by weaving in elastic fibers or lamellas 40 with an appropriate pretension which form small arches which protrude slightly out of the surface of this fabric layer 42 and can be pressed in elastically by the pressure of a finger. This fabric layer can be supported on adjacent fixed fabric layers 44 and 46 . Within the fabric layers, “action reaction” applies to the activation of such a point on this input face. That is to say the force applied by a finger is passed on through a plurality of fabric layers and the fabric with the aforesaid sensitive feedback can be introduced as any of the fabric layers. This position does not have to be identical to the fabric layer which produces the signal. It is thus perfectly possible for the functions of the tactile feedback and of the electrically effective deformation to be installed in separate layers. One simple variant with, in particular, metallic fiber with a circular cross section which, as described below, is specially preformed, has to be supported laterally by the spatial fabric. In contrast, in the “lamella arches” variant a lamella-like semifinished product is woven in. As described below and illustrated in FIG. 4 , specially shaped ribbons or lamellas 40 are woven into one of the fabric layers. The lamella arches formed in this way are stable in the lateral direction owing to their cross-sectional profile, as a result of which their spring travel is directed predominantly perpendicularly to the input face. In each case an elastic lamella arch produces an input face zone which can be perceived in a tactile fashion. It is supported with a hinge-like, relatively tight curvature in each case at the bottom on one or more transversely extending fibers 48 in order to ensure that springing back occurs after activation. These transversely extending fibers 48 conduct the horizontal forces into a lower tensile-force-resistant layer. These arches should be composed of fibers, lamellas or ribbon which are preformed in such a way that in each case a downward and an upward curvature and again a curvature in the initial direction occur along the surface at specific intervals, said curvatures forming slight arches during the fixing of every second, in particular every third or fourth or fifth of these curvature points in the fabric, and when pressure is exerted by a finger said arches experience downward spring compression like an overloaded bridge arch and are also compressed in a longitudinal direction without moving out laterally to an appreciable degree in order therefore to support, through their ratio of the height of these curvature points to the length of the material located between them and through the compressibility in the approximately horizontal direction, the spring compression of an arch with a toggle lever effect. This is therefore a type of extended zigzag form or else with more gentle radii a type of wave form. Cf. FIG. 4 . For example, two arches with, for example, four of these zigzag sections each can be implemented per centimeter so that a fingertip continuously touches at least one of these microswitches. Basically, it is also possible to position two—or more—of these feedback fabric layers approximately offset one on top of the other in order to achieve finer resolution. Between the bindings by means of the transverse fibers there are therefore a plurality—for example two, three or four—of the aforesaid curvature sections unattached and they permit the spring compression of this arch with a certain toggle lever effect: as the pressure on the arch increases it experiences a spring compression, and with further spring compression it loses its load bearing capacity—in the direction perpendicular to the input face—and can finally experience spring compression without a relatively large application force and can move down onto transversely extending fibers located below it. Instead of the aforesaid continuous zigzag shape or wave shape, those curvature sections which are bound into the tensile-force-resistant fabric layer can also continuously already be made slightly higher in the preforming process that those located between them. As a result, such an arch experiences spring compression somewhat further when activation occurs and has a somewhat clearer toggle lever effect. For example, the variant with two or four free curvature sections within an arch is satisfactorily compatible with the variant with three or five or seven fibers which extend transversely below it and lie one next to the other: this is because the spring compression of a lamella arch touches, with the centre between its curvature sections, in a downward direction the electrically conductive central transverse fiber, which is possibly to be measured, of the three or five or seven transverse fibers, which can produce a clear electrical measuring signal. Cf. FIG. 4 . In the lower fabric area, the other fibers as it were support and fix the position of the fiber which is possibly to be measured under the centre of the arch. The advantage of this solution is that at first, without activation, there is a clear distance between the arch and the fiber to be measured, but then when activation occurs a touching or approaching process gives rise to large differences in measured values. Depending on the method, it is possible (a) for the change in resistance between noninsulated conductive fiber elements and arch elements to be measured or (b) for the change in capacitance between insulated fiber elements and arch elements to be measured. The fiber arches or lamella arches can also be supported on one another laterally through a horizontal offset—“phase shifted” in the direction along the arch—in relation to the respective adjacent arch or lamella arch. The spring travel is thus guided predominantly in the perpendicular direction to the input face by this lateral support. And the tensile stresses can be absorbed within a (lower) tensile-force-resistant layer: in the longitudinal direction the fiber arches or lamella arches can be supported on one another by the forces which are tangential to the surface and which occur during pressure activation compensating one another. Optionally, the fibers or lamellas with the aforesaid properties of feedback by a toggle lever effect can be woven in two directions—in particular orthogonal to one another—and thus additionally stabilize one another in their position. Small “vaults”, which are respectively formed from intersecting fibers or lamellas and which can experience spring compression, are formed. Within the entire structure, just one of the fabric layers can produce the sensitive feedback. For this purpose, this layer should be composed of a lower fabric area which gives it mechanical stability, in particular tensile strength, and it should be composed of an upper fabric area which is essentially composed of the electrically effective fibers or ribbon lamellas to be activated. The upper area has sprung sections by virtue of the fact that fibers or ribbon lamella arches are woven in small sections which are self-supporting in themselves. These two aforesaid fabric areas are woven tightly to one another. As an entire unit they form the fabric layer which produces a sensitively perceptible feedback for the fingers. The nonlinear through-connection behavior which can be perceived in a sensitive fashion can, for example, also be implemented by means of the following structure: variant “flexural torsion loops”. Referring to FIG. 5 , a spring wire is preformed in such a way that it repeatedly protrudes laterally through a tight curvature ( 1 ), returns with a tight curvature ( 2 ) after a certain distance, at the same time gaining some height, before, at a certain distance from the initial main line—horizontal axis according to FIG. 5 —at a curvature point ( 3 ) it both gains height more steeply and points to the side in a somewhat more pronounced fashion until it reaches a wire section ( 4 ) with maximum height, which takes up the pressure exerted by fingers or areas of the hand. The wire section between the curvature point ( 3 ) and the highest area ( 4 ) has a gradient of, for example, approximately 30 to 45 degrees in a side view. And in the top view is inclined by, for example, approximately 45 degrees with respect to the main line—horizontal axis. This wire section results, owing to its leverage, in, in particular, a torsion load for the section ( 2 ) to ( 3 ) which, when activation occurs, even at first allows this leverage to increase still more so that the torsion loading increases superlinearly and promotes the further torsion. If the section ( 3 ) to ( 4 ) is approximately horizontal in the side view, the effect of rigidity of this design due to torsion is relatively low. This gives rise to the perceptibly gentle through-connection behavior. The proportion of the rigidity of this design which is brought about by bending also has an area with gentle through connection: in a side view it becomes apparent that the points ( 1 ) and ( 4 ) approach one another by virtue of the fact that the wire sections lying between them are bent elastically. The proportion of the forces in the direction from point ( 1 ) to point ( 4 ) loses supporting capability considerably under spring compression and its vertically supporting component finally collapses and provides a toggle lever effect. The relation between the components of the two effects can be selected structurally within certain limits by selecting the angles and dimensions. Thus, it would be possible, for example, to dispense with the nonlinear torsion effect by connecting the points ( 2 ) to ( 4 ) of the wire without curvature. Alternatively, the curvature could even be emphasized by integrating a joint additionally into the structure described above, in the region of the point ( 4 ). A further variant of elastic elements is composed, in particular, of the preformed wire or lamella element—“cantilever” variant: elements which are frequently integrated into the input face cf. FIGS. 6 and 7 —are constructed in such a way that part of a respectively acutely angled cantilever 60 is subjected to tensile loading and another part 62 of this cantilever is subjected to compressive loading. The latter produces flexural loading through lateral protrusion of this second part 62 so that when the cantilever is activated approximately perpendicularly with respect to the input face this protrusion bulges out further elastically and the lever thus loses its supporting capability as a result of leverage which becomes progressively more unfavorable, and finally yields at a minimum activation force. These elements provide a nonlinear through connection which can be perceived sensitively. It is possible to roll up all these structures by leaving the fiber arches or lamella arches or the bending torsion loops on the outside and stretching them somewhat during the rolling up process. The interweaving or knitting together of the aforesaid electrically effective fibers, lamellas or fabric layers on the one hand and the light-emitting fibers on the other is possible provided that electrically capacitively effective fibers can be insulated, because a sufficiently large change in, particularly, the electrical capacitance between the fibers is already produced as they approach and can be evaluated as a signal triggering means, but on the other hand the aforesaid visually active display fibers, in particular light-emitting polymer fibers, emit light at the actual contact points of intersecting fibers and are not to be insulated. In the computer input devices proposed here it is possible for the visual display to give rise to interfering electrical or electromagnetic fields. However, they can be corrected again and eliminated by calculation during the evaluation of the input data of the touch-sensitive and approach-sensitive layer. These possibly interfering changes in fields are known in principle by virtue of the data to be displayed and can thus be corrected for the respective small input face zones. The signals from this sensitive surface which are to be passed on to a computer unit can be continuously standardized in the unloaded position of rest as a “zero signal”. The input device is therefore also to be used in arched layers. It is thus also possible to compensate possible gradual deformations of the fabric. In the case of the steering wheel, in particular holding it in a static fashion is to be interpreted as being position of rest which does not trigger any control signals. Accordingly, sensitive surfaces which are generally made of textiles can be standardized with various kinds of arching as a neutral output position.
The steering wheel input is a flexible, interactive input, based on a touch-sensitive surface. Groups of functions are available from many positions of hands and fingers, gripping and controlling the steering wheel. For example travel direction indicators, headlight flashing/dipping and windscreen wipers can be controlled without having to raise the hand from the steering wheel. The keypad of a mobile telephone can also be simulated. PDA inputs can be carried out. A computer keyboard can be simulated. Continuous encompassment of the hands is corrected by computer. The touch areas are continuously and dynamically adapted in the relationship thereof with respect to the balls of the hands or the thumb and fingers. This concept produces ergonomically appropriate and dynamically updated touch areas.
3
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates in general to polymer rupture disks and specifically to a thermoformed polymer rupture disk that can be economically manufactured and utilized in systems where no metal is desired. 2. Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98 Reverse buckling rupture disks are, of course, well known in the art. To applicant's knowledge, they are all formed of metal and have score lines therein that enable the disks to buckle or burst in a predetermined fashion. For many, many years Teflon® film has been thermoformed as liners for metal reverse buckling rupture disks in order to separate the metal from any fluids that may be detrimentally affected by metal contact. Further, flat Teflon® rupture disks have been used for many years. Some of the flat Teflon® rupture disks develop a “domed” center section resulting from room temperature pressure applied thereto. All such polymer rupture disks in the prior art have a flow area after burst that is relatively small and unpredictable. Second, the burst pressure is difficult to change when the burst pressure is controlled by the construction of the customer's rupture disk holder or flanges. It would be extremely useful to have a reverse buckling, thermoformed, rupture disk with a relatively large, predictable flow area with buckling pressures controlled by score lines or thin areas or buckling points formed therein. SUMMARY OF THE INVENTION The present invention discloses and teaches a reverse buckling, thermoformed, polymer rupture disk with a raised center and having score lines therein, or thinned areas that are in predetermined locations and that provide a predetermined flow area after burst and enable the burst pressure to be changed even though the disk's constraining geometry is controlled by the customer's holder or flanges. The present reverse buckling polymer rupture disk is thermoformed and has an annular flange and a raised center portion, both having a predetermined thickness. The raised portion may be of various shapes including dome-shaped and has an upstream convex side and a downstream concave side and buckles when pressure is applied to the upstream convex side thereof. It has at least one score line formed in the thermoformed polymer rupture disk to create a line of weakness that forms a predetermined burst pattern when rupturing under a predetermined pressure applied to the upstream convex side. Note that the disk can buckle independently of the score lines. In some cases the score lines are used to influence the location of the buckling point or the magnitude of the buckling pressure. In the preferred embodiment, the buckling pressure and location are primarily defined by the thermoformed shape and thickness. The score line(s) are primarily used as a means to create a weakened and predictable rupture path. The score line may be formed in several ways. One of the ways is to cause a predetermined thinning in a predetermined area of the rupture disk during thermoforming by applying a vacuum to the area where it is desired to be thinned. Another method of forming a score line is to use a razor blade that can cut into the polymer material to a predetermined depth. Still another method of forming the score line is to utilize a press having a relatively sharp blade extending therefrom in the shape of the score line and apply a force to the blades to force them into the surface of the polymer rupture disk to create the very narrow but deep score lines. The score lines may be formed in the polymer rupture disk either before, after, or during thermoforming the polymer rupture disk. The desired score line is formed in the flange of the polymer rupture disk adjacent the dome-shaped center portion and extending at least partially around the dome-shaped center portion. In another embodiment, the score line is formed in the dome-shaped center portion with two score lines perpendicular to each other. It is desired that the score line be preferably formed on the downstream side of the rupture disk. However, under certain circumstances, it could be formed on the upstream side thereof. In addition, because some of the rupture disk holding means have centering recesses formed in the annular base thereof, the rupture disk can have a corresponding raised annual centering ring formed in the annular flange, preferably on the upstream side of the polymer rupture disk, to position the rupture disk in fluid flow line in relation to the holding means having the annular recesses. Further, where first and second holding means have identical fluid flow orifice sizes, a flat rigid annular plate may be placed in the downstream side of the polymer rupture disk with an orifice therein having a diameter that is less than the fluid flow line holding means diameter to form an offset shoulder on the downstream side of the thermoformed polymer rupture disk with respect to the fluid line inside diameter to provide support to the flange area of the rupture disk and prevent bending of said flange area when pressure is applied to the convex side of the rupture disk. In some cases, the outer portion of the annular rupture disk flange can form as a skirt that extends perpendicular to the plane of the annular flange in the direction of the downstream side of the polymer rupture disk to aid in centering the polymer rupture disk in the flow line and contain the flat rigid annular plate. Thus, it is an object of the present invention to form the reverse buckling polymer rupture disk by thermoforming the disk. It is another object of the present invention to use Teflon® as the polymer material forming the rupture disk. It is yet another object of the present invention to provide a reverse buckling, thermoformed, polymer rupture disk with a relatively large, predictable flow area after rupture and that has a buckling pressure that is controlled by score lines or thinned areas or buckling points created in the thermoforming process. It is still another object of the present invention to provide a thermoformed reverse buckling polymer rupture disk having a score line therein that penetrates through at least 60% of the polymer rupture disk thickness. It is yet another object of the present invention to provide a rupture disk wherein the score line is thermoformed into the flange of the polymer rupture disk adjacent its dome-shaped center portion and extending at least partially around the dome-shaped center portion. It is also an object of the present invention to provide a reverse buckling, thermoformed, polymer rupture disk having a score line that is cut into the annular flange of the polymer rupture disk adjacent the dome-shaped center portion and extending at least partially around the dome-shaped center portion. It is still another object of the present invention to provide a reverse buckling, thermoformed, polymer rupture disk having a score line mechanically pressed into the annular flange of the polymer rupture disk adjacent the dome-shaped center portion and extending at least partially around the dome-shaped center portion. It is yet another object of the present invention to provide a reverse buckling, thermoformed, polymer rupture disk wherein the score line is formed in the dome-shaped center portion of the polymer rupture disk. It is also an object of the present invention to provide a reverse buckling polymer rupture disk having a score line preferably formed on the downstream side of the rupture disk. It is yet another object of the present invention to provide a reverse buckling, thermoformed, polymer rupture disk that has a raised annular centering ring formed in the annular flange on the upstream side thereof and a skirt formed on the outer portion of the annular flange that extends perpendicular to the plane of the annular flange in the direction of the downstream side of the polymer rupture disk to center a flat, rigid, annular plate placed on the downstream side of the polymer rupture disk. An orifice in the annular plate has a diameter less than the fluid flow line inside diameter and forms an offset shoulder on the downstream side of the thermoformed polymer rupture disk with respect to the fluid line inside diameter to provide support to the flange area of the rupture disk and prevent bending of said flange area when pressure is applied to the convex side of the rupture disk. Thus, the present invention relates to a reverse buckling polymer rupture disk for mounting in a fluid flow line fixture having a predetermined inside diameter and comprising a thermoformed polymer rupture disk having an annular flange and a dome-shaped center portion, both having a predetermined thickness; the dome-shaped portion having an upstream convex side and a downstream concave side and being reverse buckling when pressure is applied to the upstream convex side thereof. At least one score line is formed in the thermoformed polymer rupture disk, either in the annular flange or in the dome-shaped center portion, to create a line of weakness that forms a predetermined burst pattern when rupturing under a predetermined pressure applied to the upstream convex side. BRIEF DESCRIPTION OF THE DRAWINGS These and other features of the present invention will be more filly disclosed when taken in conjunction with the following Detailed Description of the Invention in which like numerals represent like elements and in which: FIG. 1 is a side view of the novel thermoformed polymer rupture disk showing the state of the disk in its unstressed condition, an intermediate condition and the final “ruptured” condition; FIG. 2 is a bottom plan view of the novel thermoformed polymer rupture disk shown in FIG. 1; FIG. 3 is a bottom plan view of a thermoformed polymer rupture disk in which score lines are formed in the domed center portion thereof; FIG. 4 is a partial view of a flange and portion of the domed center of the thermoformed polymer rupture disk illustrating the score line cut in the downstream side thereof; FIGS. 5A and 5B illustrate first and second adapters that are used to contain the novel thermoformed rupture disk therebetween in a fluid line; FIG. 6 is a partial cross-sectional view of the novel thermoformed rupture disk to be mounted between the first and second flanges shown in FIG. 5 A and FIG. 5 B and having a flat, rigid, annular plate placed on the downstream side thereof for providing an offset shoulder to create proper buckling of the thermoformed polymer rupture disk; FIG. 7 is a cross-sectional view of a gasket holding the novel thermoformed polymer rupture disk and the flat annular plate for forming the offset shoulder such that a single package (gasket plus disk plus flat annular plate) can be inserted between two standard flanges in a fluid flow line; FIG. 8 is a cross-sectional view of one type of the mounting device for holding a thermoformed polymer rupture disk therein in a fluid flow line; FIG. 9 is a cross-sectional view of a second type of holder illustrating that, in this particular holder, the skirt from the outer edge of the novel thermoformed polymer rupture disk extends perpendicular to the plane of the flange and in the direction of the upstream side of the fixture; and FIG. 10 is a diagrammatic representation of a scoring die device that includes a cutting edge for forming score lines therein. DETAILED DESCRIPTION OF THE INVENTION FIG. 1 is a side view of a novel thermoformed polymer rupture disk 10 of the present invention. The polymer material is preferably Teflon® but could be other polymers. It has a flange portion 12 and a raised center portion 14 in the shape of a dome that has a convex side 16 in the direction of the operating pressure or upstream side, all shown in phantom lines to the left of flange 12 . A transition area 13 joins the raised center portion 14 and the flange 12 . For illustration purposes and as will be discussed in more detail later, there is also shown an irregular area 17 representing the start of buckling in dome 14 . To the right of flange portion 12 and also in phantom lines, there is shown an intermediate condition where the original convex side 16 of the dome has inverted and is now concave and the dome portion 14 has partially separated from flange 12 . The solid lines represent the final position and condition of disk 10 after rupture is complete. FIG. 2 is a bottom view of the novel thermoformed polymer rupture disk of FIG. 1 illustrating the concave side 18 of the raised portion, which, in the present embodiment, is shown as the center domed portion 14 and the score line 20 that extends at least partially around the dome-shaped center portion 14 . It should be understood that although a raised dome or hemispherical shape is illustrated in the figures as the raised portion, many other raised shapes including but not limited to cylindrical, conical, non-spherical domes, and even combinations of these and other shapes are also intended to be included in the scope of this invention. The score line 20 in the particular case having a dome as shown in FIG. 2 is on the downstream side of the novel thermoformed polymer rupture disk. However, under certain circumstances, as desired, it could be on the upstream side. When pressure is applied to the convex side 16 of the novel thermoformed polymer rupture disk 10 and a predetermined pressure is reached, the disk first buckles in the dome section 14 or in the transition section 13 . The pressure continues to reverse the dome of the disk until the dome becomes taut. The force of reversal then exceeds the strength of the material in the score lines and the disk ruptures along the score lines creating a flow area that is large and predictable. The score line may be formed in a number of ways as will be shown hereafter. One way is to cut it into the flange material 12 . It can be cut to a depth of at least 60% of the thickness of the polymer disk material and preferably 80%. The groove 20 may also be formed by pressing a sharp edge in the shape of the desired groove into the surface of the novel thermoformed polymer rupture disk to a desired depth. Finally, the score line 20 may be formed by the thermoforming process by applying a vacuum in the thermoforming device to the area in which the score line is to be formed, thus thinning the material. Thus, with the knife or the pressure-formed score line, the score line may be formed either before, after, or during thermoforming. However, the score line formed by thinning the material is formed during the thermoforming process itself. FIG. 3 is a plan view of a thermoformed polymer rupture disk having the score line 20 formed of score lines 24 and 26 formed perpendicular to each other in the dome of the disk 22 . FIG. 4 is a partial cross-sectional view of the novel thermoformed polymer rupture disk 10 showing the outer flange 12 , the domed center portion 14 with its convex side 16 , transition portion 13 , and concave side 18 , and the score line 20 formed in the annular flange 12 on the downstream side thereof extending at least partially around the dome-shaped center portion 14 . Note that score line 20 is narrow and deep. FIGS. 5A and 5B illustrate two mating adapters 28 and 42 that can be used to mount one of the novel thermoformed polymer rupture disks therebetween. Note, in FIG. 5A, that a first adapter or body portion 28 , well known in the art, has a first orifice 30 extending axially therethrough in fluid engagement with the fluid flow line with fluid flow being in the direction shown by the arrow. A first end 32 on the first adapter 28 provides for attachment to the fluid flow line and a second end 34 has an annular flange 36 with a flat face 38 thereon and extending outwardly from first end 32 diameter for mating with one flange side of the thermoformed polymer rupture disk as will be shown hereafter. A first annular recess 40 , preferably semicylindrical in shape, is formed in flat face 38 for engaging at least a portion of the flange of the polymer rupture disk to center it. A second adapter or body portion 42 is shown in FIG. 5 B and is substantially identical to the first adapter 28 so that an essentially universal adapter is obtained and either adapter 28 or 42 may be used in place of the other. It has a first end 44 for mating with the other flange side of the thermoformed polymer rupture disk as will be seen in relation to FIG. 6 and a second end 46 that is vented to atmosphere. A second orifice 48 extends through the second body portion 42 in axial alignment with, and having the same diameter as, the first orifice 30 . A second annular recess 50 , similar to annular recess 40 , is formed in the flat face 52 of the annular flange 54 that extends outwardly from the outer diameter of the second end 46 . Flat face 52 is used for mating with the other flange side of the thermoformed polymer rupture disk. A reverse buckling polymer rupture disk holding device 56 , shown in FIG. 6, is mounted in the fluid line. It includes novel thermoformed polymer rupture disk 58 and annular plate support 60 . Because the first and second orifices 30 and 48 of the first and second adapters 28 and 42 have the same diameter, the annular plate support 60 in the form of a flat, rigid washer, has an orifice 62 therein that has a smaller diameter than the adapter orifices 30 and 48 . Thus, support 60 forms an offset shoulder 61 with respect to the flat faces 38 and 52 of the first and second adapters 28 and 42 . The offset shoulder 61 is on the downstream side of rupture disk 58 and therefore the rupture disk 58 first buckles in the dome section 14 or in the transition section 13 . The pressure continues to reverse the dome of the disk until the dome becomes taut. The force of reversal then exceeds the strength of the material in the score lines and the disk ruptures along the score lines creating a flow area that is large and predictable. It will be noted that in FIG. 6 rupture disk 58 has an annular skirt 68 formed on the outer edge 64 of the flange 70 that extends generally perpendicular to the flange 70 in the direction of fluid flow. This skirt is not always needed but when placed in a fixture such as illustrated in FIG. 6 where the annular support 60 is required, the skirt 68 assists in holding the annular support 60 in proper relationship with the rupture disk 58 . In some installations that will be shown later, the skirt 68 could extend in the opposite direction perpendicular to the flange 70 . It will also be noted that rupture disk 58 has an annular centering ring 72 extending outwardly from flange 70 on the upstream side of the rupture disk 58 . This annular centering ring 72 is sized for mating with the annular grooves or recesses 40 or 50 in the flat faces 38 and 52 of the first and second adapters 28 and 42 to enable proper centering of the rupture disk 58 with respect to the first and second adapters 28 and 42 . After the rupture disk 58 and the annular support 60 are placed between the first and second adapters 28 and 42 as shown in FIG. 6, a clamp 74 , well known in the art, is placed around the adapter flanges 36 and 54 and tightened in a well-known manner to maintain the assembly in a fluid-tight relationship. FIG. 7 illustrates a unitary package 76 for mounting between two adapters such as those shown in FIG. 5 A and FIG. 5 B. It includes a rubber or otherwise flexible material 78 that is annular in shape and has an annular recess 79 on the inside center thereof for receiving the thermoformed polymer rupture disk 80 and the support plate 82 . The thermoformed polymer rupture disk 80 has an annular score line 84 in the outer flange thereof that extends at least partially around the center domed portion thereof. The flexible gasket 78 has annular projections 86 and 88 on the sides thereof that extend into the annular recesses 40 and 50 in the adapter faces shown in FIGS. 5A and 5B thus holding the unit 76 tightly between the adapters. A fastener, well known in the art, can then be placed around the adapter flanges shown in FIG. 6 to hold the entire package 76 therebetween. FIG. 8 illustrates another embodiment of a holder for the present invention wherein the holder 90 includes a first body portion 92 and a second body portion 94 . The first body portion 92 has an inside diameter D 0 and the second body portion 94 has an inside diameter D 1 that is greater than D 0 . The novel thermoformed polymer rupture disk 98 is placed between the shoulder 100 of body portion 94 and shoulder 102 of body portion 92 to hold the flanges thereof securely in place. The difference in the diameters D 1 −D 0 forms an offset shoulder for properly positioning the thermoformed polymer rupture disk with respect to the D 0 of the first body portion 92 without the need for any annular support plate. A lock pin 104 can be used if desired to lock the first and second body portions 92 and 94 together. FIG. 9 illustrates a holder for a second embodiment of the novel polymer rupture disk. Note, in FIG. 9, that the unit 106 has the polymer rupture disk 108 with its outer flange 109 being held securely between opposing surfaces 114 and 116 . Note, that the score line 112 is on the downstream side thereof. Also note that the skirt 110 on the outer edge of the flange of the thermoformed polymer rupture disk extends generally in the vertical direction with respect to the plane of the flange but extends in the upstream side direction rather than the downstream side direction as shown previously. Therefore, orifice 118 is coupled to fluid pressure and orifice 120 is coupled to the atmosphere. The novel polymer rupture disks are formed with a thermoforming device such as that disclosed in commonly assigned copending application Ser. No. 09/512,486 filed Feb. 24, 2000 and entitled “Tension Loaded, Thermoformed, Polymer Rupture Disk”, incorporated herein by reference in its entirety. FIG. 10 is a generalized diagram for a scoring die. One method of forming the score line therein is to use a razor blade 140 either in the arcuate shape of the score line to be formed or as a single blade that could be rotated by rotating the upper portion 142 of the die to cause the score line to be cut into the downstream side of the flange of the polymer rupture disk. If the knife blade 140 is a single arcuate blade, then the die 142 can be pressed downwardly to form the score line in the flange 138 of the polymer rupture disk. Shims 144 can be placed between the die 142 and the spacer 126 to set the cut depth and enable the razor blade or knife to cut preferably at least 60% into the polymer rupture disk material. If desired to form the score line in the dome 132 of the polymer rupture disk, crossed knife blades, two blades perpendicular to each other, and arcuate in shape, would be attached to the lower end of screw 146 in a well-known manner such that, when it is pressed downwardly, it would press the knife blades into the inner side of domed center portion 132 . In such case, an anvil 154 (shown in phantom lines) could be placed in the chamber 152 to provide a support for the dome-shaped portion 132 of the polymer disk while the cutting is taking place. Of course, the cuts could be made in either side of the polymer rupture disk, either the flange or the dome, and could be made either before, during, or after the thermoforming takes place. When the score line is deformed by thinning the material in the area of the score line using the thermoforming process, then at the point where the score line is to be formed, a vacuum is applied, as shown in commonly assigned copending application Ser. No. 00/512,486 entitled “Tension Loaded, Thermoformed, Polymer Rupture Disk” incorporated herein in its entirety, to thin a particular area and form the score line. Thermoforming processes are well known in the art and need not be described in any further detail here. Thus, the novel invention disclosed herein teaches that a polymer rupture disk, preferably Teflon®, can be thermoformed into the proper shape and a score line provided therein to provide a polymer rupture disk that can be used in pressure lines where it is desired that no metal exist. The novel thermoformed polymer rupture disk has a score line that extends preferably through at least 60% of the flange or dome surface thereby enabling a controlled burst pressure and burst pressure area to be formed. The corresponding structures, materials, acts, and equivalents of all means or step plus function elements in the claims below are intended to include any structure, material, or act for performing the function in combination with other claimed elements as specifically claimed.
A thermoformed reverse buckling polymer rupture disk having an unsupported raised center portion including score lines cut in the polymer disk that creates a line of weakness to control the buckling pressure of the disk and forms a predetermined burst pattern.
8
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for detecting a nucleic acid polymer. More particularly, the present invention relates to a method which permits easy detection of an amount of a nucleic acid polymer in a sample, detection of hybridization, if any, of a probe and a nucleic acid polymer, identification of a base sequence of a nucleic acid polymer, a method for causing two-dimensional orientation of a nucleic acid polymer at the gas-water interface, and further, a novel amphiphilic intercalator used in these methods. 2. Description of Related Art Diverse and various biological functions observed in cells are effectively expressed by regular orientation of biomolecules. For nucleic acid polymers (DNA, RNA) which code genetic information of an organism, however, the effect of an orientation thereof on expression of biological functions has almost never been studied. One of the reasons is that means to control in vitro the orientation of a nucleic acid polymer has not as yet been established. As a method for retrieving a target gene sequence in a nucleic acid polymer, or for determining similarities and differences or homology of a plurality of nucleic acid polymers, on the other hand, it is conventionally known that the hybridization method using, as a probe, a single-stranded nucleic acid polymer (DNA or RNA) complementary with a portion of sequence of a target nucleic acid polymer. More specifically, the conventional hybridization method comprises the steps of fixing a single-stranded target nucleic acid polymer onto a nitrocellulose membrane or a nylon membrane, and adding an aqueous solution of a probe nucleic acid polymer labelled with a radioisotope or an enzyme onto the membrane. When the probe nucleic acid polymer is hybridized with the target nucleic acid polymer, only the hybridized probe nucleic acid polymer remains on the membrane after washing. Presence of a searched sequence in the target nucleic acid can be determined by detecting radioactivity from the radioisotope labelled on the probe nucleic acid polymer, or chemiluminescence or color of precipitate produced by the enzyme. In order to handle a radioisotope, however, it is necessary to acquire a special license, so that this technique is not popularly accepted. Labelling a single-stranded probe nucleic acid polymer with an enzyme requires much costs and labor. A nucleic acid polymer such as genomic DNA existent in chromosome has a double helix structure comprising complementary base pairs (adenine/thymine and cytosine/guanine for DNA, and adenine/uridine, cytosine/inosine and cytosine/guanine for RNA). For identifying differences in the base sequence between two different nucleic acid polymers, for example, formation of a triple helix has been believed to be effective. However, because of the difficulty to detect formation of a triple helix, this method has not as yet been put to practical use. Among properties of DNA or RNA as a nucleic acid polymer, there is known an intercalation phenomenon in which a cationic pigment is inserted between neighboring base pairs. However, detection of a nucleic acid polymer (content, hybridization, identification of base sequence, etc.) by the use of this phenomenon has not as yet been conducted. SUMMARY OF THE INVENTION The present invention has as an object to provide a method for detecting an amount of a nucleic acid polymer in an aqueous solution and the presence of hybridization of nucleic acid polymer/probe by the utilization of interaction between a pigment (intercalator) and the nucleic acid polymer, and a method for identifying the base sequence of the nucleic acid polymer. More specifically, the first invention provided by the present invention is a method for detecting an amount of nucleic acid polymer, which comprises the steps of modifying an intercalator to be amphiphilic by using a hydrophobic group, spreading the amphiphilic intercalator on an aqueous solution containing a nucleic acid polymer to form a monolayer of said nucleic acid polymer and said amphiphilic intercalator, and measuring surface pressure per unit area of said monolayer at the gas-water interface. The second invention relates to a method for detecting the presence of hybridization of a probe nucleic acid polymer and a target nucleic acid polymer, which comprises the steps of modifying an intercalator to be amphiphilic by using a hydrophobic group, spreading the amphiphilic intercalator on an aqueous solution containing a single-stranded probe nucleic acid polymer to form a monolayer of said probe nucleic acid polymer and said amphiphilic intercalator at the gas-water interface, measuring a surface pressure-area isotherm of said monolayer, then measuring a surface pressure-area isotherm of said monolayer after addition of a single-stranded target nucleic acid polymer to the aqueous solution, and comparing the two surface pressure-area isotherms. The third invention relates to a method for identifying a base sequence of a nucleic acid polymer, which comprises the steps of modifying an intercalator to be amphiphilic by using a hydrophobic group, spreading the amphiphilic intercalator on an aqueous solution containing a nucleic acid polymer to form a monolayer of the nucleic acid polymer and the amphiphilic intercalator at the gas-water interface, and measuring surface pressure-area isotherm of said monolayer. The present invention has another object to provide a method for causing two-dimensional orientation of a nucleic acid polymer at the gas-water interface. More specifically, the fourth invention is a method for orientating nucleic acid polymers at the gas-water interface, which comprises the step of modifying an intercalator to be amphiphilic by using a hydrophobic group, spreading the amphiphilic intercalator on an aqueous solution containing nucleic acid polymers to form a monolayer of said nucleic acid polymers and said amphiphilic intercalator. Furthermore, the present invention provides an intercalator modified to be amphiphilic by using a hydrophobic group and a nucleic acid polymer/intercalator monolayer comprising this intercalator and the nucleic acid polymer. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic representation illustrating a method for detecting the presence of hybridization in the present invention; FIG. 2 is a schematic representation illustrating a method for identifying a base sequence in the present invention; FIG. 3 is an NMR spectrum of an intercalator (Formula 1) of the present invention and FIG. 4 is an IR spectrum thereof; FIG. 5 illustrates the difference in surface pressure-area isotherms between the presence and absence of hybridization; FIG. 6 is an NMR spectrum of another intercalator (Formula 2) of the present invention; FIG. 7 illustrates the difference in surface pressure-area isotherms between different base sequences; FIG. 8 illustrates changes in the difference in surface pressure depending upon concentrations of a nucleic acid polymer; and FIG. 9 is an atomic force microscopic image of an intercalator/DNA monolayer deposited on a mica substrate. FIG. 10 is a schematic drawing of the microscopic image of FIG. 9. DETAILED DESCRIPTION OF THE INVENTION The present invention permits detection of a nucleic acid polymer by utilizing intercalation of a pigment, forming a monolayer of an intercalator and a nucleic acid polymer at the gas-water interface, and measuring a surface pressure of this monolayer. The method is characterized in that a surface active pigment modified by a hydrophobic group into an amphiphilic one is used as the intercalator. The individual detection methods are described below in detail. <A> Detection of nucleic acid polymer amount: First, a nucleic acid polymer (single-stranded or double-stranded DNA or RNA) is added into an aqueous subphase of an ordinary surface pressure-area isotherm measuring apparatus. A monolayer is formed by spreading the surface-active intercalator of the present invention at the gas-water interface. More specifically, since this intercalator has a positive charge, it forms a polyion complex with the nucleic acid polymer having a negative charge at the gas-water interface, thus forming a monolayer. The surface pressure of this monolayer varies, depending upon the amount of nucleic acid polymer coupled with the intercalator. By measuring the surface pressure thereof per unit area (area occupied by the monolayer), therefore, it is possible to detect the amount of the nucleic acid polymer in the aqueous solution. More particularly, the amount can be detected by determining the difference between the measured surface pressure and the surface pressure of pure water not containing a nucleic acid polymer. By previously preparing a calibration curve of differences in surface pressure by the use of nucleic acid polymer aqueous solutions having various known concentrations, furthermore, it is possible to easily detect the amount of a nucleic acid polymer of an unknown concentration. <B> Hybridization: First, as shown in FIG. 1, a single-stranded probe nucleic acid polymer (DNA or RNA) is added into an aqueous subphase of an ordinary surface pressure-area isotherm measuring apparatus. A monolayer is formed by spreading the surface-active intercalator solution onto the gas-water interface thereof. At this point, as the intercalator has a positive charge, it forms a polyion complex with the single-stranded nucleic acid polymer having a negative charge at the gas-water interface, thus forming a monolayer. The surface pressure-area isotherm (π-A isotherm) of the thus formed monolayer is measured. Then a single-stranded nucleic acid polymer which may have a target sequence to be detected is added to the aqueous subphase. When the target nucleic acid polymer has a base sequence complementary with the probe, the single-stranded probe nucleic acid polymer having formed the polyion complex with the intercalator is hybridized with the single-stranded target nucleic acid polymer, thus forming a polyion complex comprising the intercalator and double-stranded probe/target nucleic acid polymer at the gas-water interface. Because the pigment portion of the intercalator is inserted between base pairs of the double-stranded probe/target nucleic acid polymer, there is created a surface pressure-area isotherm different from that before hybridization. This difference in the surface pressure-area isotherm makes it possible to detect the presence of hybridization. <C> Identification of difference between base sequences of nucleic acid polymer: As shown in FIG. 2, for example, an aqueous solution of a target double helix nucleic acid polymer (DNA or RNA) is added into the aqueous subphase of an ordinary surface pressure-area isotherm measuring apparatus. A monolayer is formed by spreading a surface active intercalator solution at the gas-water interface thereof. At this point, since the surface-active intercalator has a positive charge, it forms a polyion complex at the gas-water interface with the nucleic acid polymer having a negative charge, thus forming a monolayer. Further, the pigment intercalator portion intercalates with the double helix nucleic acid polymer. The surface pressure-area isotherm thereof is measured. Because the surface pressure-area isotherm largely depends upon the base sequence of the double helix nucleic acid polymer, it is possible to identify, from the surface pressure-area isotherm, the kind of base sequence of a nucleic acid polymer existent in the aqueous subphase. That is, the base sequence can be identified by previously preparing surface pressure-area isotherms for nucleic acid polymers having various known sequences, and comparing a tested sequence with these isotherms. <D> Method for causing two-dimensional orientation of nucleic acid polymer: First, an aqueous solution of a nucleic acid polymer (single-stranded or double-stranded DNA or RNA) is added into an aqueous subphase of an ordinary surface pressure-area isotherm measuring apparatus. A monolayer is formed by spreading a solution of the surface-active intercalator of the present invention at the gas-water interface thereof. Because this intercalator has a positive charge, it forms a polyion complex at the gas-water interface with the nucleic acid polymer having a negative charge, thus forming a monolayer. By compressing or dispersing this monolayer, for example, while controlling the surface pressure of the monolayer, it is possible to control orientation of the nucleic acid polymer coupled with the intercalator. Now, the surface-active pigment intercalator used in the method of the present invention will be described in detail below. Intercalation is observed in pigments such as acridine orange and ethidium bromide. In the present invention which utilizes formation of a complex with a nucleic acid, any of these various pigment intercalators including these conventional ones is modified by a hydrophobic group to impart an amphiphilic surface activity. A typical hydrophobic group used here is alkyl group. The present invention proposes, as a more preferable one, a compound modified by C n H 2n+1 (n≧13) alkyl group. For example, surface-active intercalators of the following formulae, available by modifying acridine orange with octadecyl group are provided: ##STR1## The compounds expressed by Formulae 1 and 2 are surface-active intercalators so far unknown, which can easily be synthesized by reacting an octadecyl iodine or a derivative thereof with the compound skeleton of acridine orange. The compound of Formula 1 is a surface-active intercalator having one hydrophobic chain, and the compound of Formula 1 is a surface-active intercalator having two hydrophobic chains. These compounds will be described below by means of Examples of the present invention. EXAMPLE 1 The presence of hybridization was measured with the use of the compound of Formula 1 above. The compound had the following properties: (1) recrystallization from benzene:rubiginous imbricate crystal; (2) melting point: 202.5˜204.5° C.; (3) TLC:Rf=0.5 (chlorofiorm/methanol=9/1+some drops of acetic acid). In addition, the elemental analysis of this compound is that of Table 1. TABLE 1______________________________________ C H N I______________________________________Theoretical Value (%) 65.10 8.74 6.51 19.65Analytical Value (%) 63.81 8.47 6.70 21.26______________________________________ MHR and IR data are shown in FIGS. 3 and 4. The results of actual measurement of surface pressure-area isotherms for this compound are shown in FIG. 5. The subphase exchange type film balance controlled by a microprocessor (made by USI Systems Company) was employed for measurement of surface pressure-area isotherms. With a trough area of 220×100 mm 2 , the surface pressure was measured with the use of filter paper (1 cm×1 cm) by the Wilhelmy method. While measuring surface pressure-area isotherms, temperature of the aqueous subphase was kept constant (20° C.) by means of a circulator. A chloroform (special class) solution of a surface-active intercalator (10 mg/10 ml) in an amount of 15 μl was spreaded on the aqueous subphase containing a nucleic acid polymer to measure surface pressure-area isotherms at a compression rate of 0.04 nm 2 /min/molecule. In addition, the following conditions were adopted: Polyadenylic acid concentration of aqueous subphase: 10 mg/1000 ml (pure water), pH: 5.6 Inverted polyuridylic acid concentration: 10 mg/1000 ml (pure water), pH: 5.6. As a model of single-stranded nucleic acid polymer, polyadenine was used, and as a model of single-stranded target nucleic acid polymer, complementary polyuridine was employed. A large change in surface pressure-area isotherms was confirmed by the addition of polyuridine to the aqueous subphase. EXAMPLE 2 A base sequence of DNA was identified by the use of the compound of Formula 2 above. The compound was purified from silica gel column by using a solution of chloroform/methanol (=95/5) as an eluate, and TLC:Rf=0.5 (chloroform/methanol=9/1+some drops of acetic acid). NMR data are shown in FIG. 6. The results of actual measurement of surface pressure-area isotherms for this compound are shown in FIG. 7. Measurement was carried out in the same manner as in Example 1, with other conditions including a concentration of the double helix nucleic acid polymer in the aqueous subphase of 10 mg/1000 ml (pure water) and a pH of 5.6. The graph is a surface pressure-area isotherm for the case where polyadenylic acid-polyuridylic acid and polyinosinic acid-polycytidylic acid were present in the aqueous subphase as models of double helix nucleic acid polymer. More specifically, as shown in FIG. 7, the base sequence can be identified from a change in the surface pressure by adding a double helix nucleic acid polymer to the aqueous subphase if the gas-water interface has a constant surface area. EXAMPLE 3 An aqueous solution was prepared by dissolving a double helix DNA (extracted from salmon spermatozoon) in pure water, to a DNA concentration within a range of from 0.01 to 100 mg/1000 ml and a pH of 5.6. A chloroform solution of the surface-active intercalator of Formula 1 was spreaded onto the gas-water interface of this aqueous solution, and the surface pressure-area isotherm was measured by the same method under the same conditions as in Example 1. The surface pressure was measured with a molecule-occupying area of 0.8 nm 2 /molecule, and on the other hand, pressure on the pure water surface with the same area was measured to determine a difference between them for each value of DNA concentration, thus preparing a calibration curve as shown in FIG. 8. As is clear from FIG. 8, the difference in surface pressure was confirmed to exhibit a correlation with logarithm of DNA concentration within a range of DNA concentration of from 0.1 to 10 mg/1000 ml. EXAMPLE 4 An aqueous solution was prepared by dissolving a double helix DNA (extracted from salmon spermatozoon) in pure water, to a DNA concentration of 10 mg/1000 ml and a pH of 5.6. A chloroform solution of the surface-active intercalator of Formula 1 was spreaded onto the gas-water interface of this aqueous solution, and the interface was compressed while measuring the surface pressure by the same method under the same conditions as in Example 1. The compression was discontinued when the surface pressure reached 10 mN/m, and control was carried out so as to always keep this value of the surface pressure. A freshly cleaved mica substrate had previously been immersed vertically in the aqueous subphase of the apparatus. A single layer of a composite monolayer comprising the intercalator and the DNA was derposited on the substrate by pulling up this substrate vertically at a speed of 50 mm/minute. After air drying, the substrate surface was observed in AC mode (scanning area: 200×200 nm 2 ) by the use of an atomic force microscope (NV2500, made by Olympus). The result is as shown in the microscopic image of FIG. 9 and the shematic drawing thereof of FIG. 10. The monolayer is compressed from right toward left in this image. Cords having a width of from 10 to 20 nm were observed in parallel sequence with a difference of 2 to 3 Å, and DNA molecules were found to be vertically oriented relative to the compression direction in bundles. It was confirmed from these results that it was possible to control two-dimensional orientation of a nucleic acid polymer by combination with the intercalator of the present invention. In addition, thus obtained nucleic acid polymer/intercalator monolayer or the monolayer deposited on a substrate, in which polymer molecules or bundles of the molecules are oriented in the same direction. will be used for a molecule devise such as micro-conductor, sensor and a tool for studying the orientation state of DNA or RNA. Particulally, for example, Br-- which is a conventional intercalator is water-soluble because of a short hydrophobic group as C 12 H 25 , so that development thereof on a gas-liquid interface only causes dissolution into the aqueous subphase, a no rise of surface pressure is observed even by compression. In the methods of the present invention described in the above-mentioned examples, therefore, it is essential to use, not a conventional one, but a surface-active intercalator modified by a hydrophobic group into an amphiphilic one.
The present invention has an object to provide an easy method for detecting a nucleic acid polymer in aqueous phase. The present invention provides a method for detecting the amount of nucleic acid polymer, which comprises the steps of modifying an intercalator to be amphiphilic by using a hydrophobic group, spreading the amphiphilic intercalator on an aqueous solution containing a nucleic acid polymer to form a monolayer of said nucleic acid polymer and said amphiphilic intercalator at the gas-water interface, and measuring surface pressures per unit area of said monolayer.
2
CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation of PCT/EP2009/001315, filed Feb. 25, 2009, which in turn claims priority to DE 10 2008 014 841.5, filed on Mar. 7, 2008, the contents of both of which are incorporated by reference. BACKGROUND The invention relates to a gas burner module for a gas cooktop, and a gas cooktop having a plurality of such gas burner modules. Gas cooktops frequently have multiple gas burners, and each gas burner requires a supply of gas to function. Further, each gas burner must be individually controllable, as well as individually ignite gas when turned-on, and detect burning of the gas after it has been turned on. There is a need for a gas burner module that uses common components which facilitates assembly of a gas cooktop comprising said gas burner modules. SUMMARY OF INVENTION The invention is based on the problem of providing a gas burner module of the type mentioned in the introduction and also a gas cooktop of the type mentioned in the introduction, with which the problems of the prior art can be avoided and, in particular, a gas burner module which can be handled and produced in an advantageous manner can be provided. This problem is solved in one embodiment by a gas burner module or a gas cooktop having the features as claimed herein. Advantageous and preferred refinements of the invention are the subject matter of the further claims and are explained in greater detail in the text which follows. The wording of the claims is incorporated by express reference in the content of this description. The contents of German priority application DE 102008014841.5 of 7 Mar. 2008 in the name of the same applicant is also incorporated by express reference in the content of the present application. In one embodiment, provision is made for the gas burner module having a gas burner with an ignition and monitoring electrode, control electronics and ignition electronics. A flame monitoring means and a gas valve are also provided. According to one embodiment of the invention, these parts of the gas burner module, which are necessary for the functioning of said gas burner module, are combined to form a unit and are mechanically connected or fitted to one another. This unit is designed as a constructional unit such that it can be handled independently, that is to say, it can be incorporated into a gas cooktop, as it were, as a modular unit. Only a connection to a gas supply and an electrical connection have to be made. As a result, it is possible to configure and match the components for the gas burner module and the unit during production to ensure optimum interaction. Furthermore, the manufacturer of the unit or of the gas burner module can thus ensure that assembly is performed correctly and therefore also optimum functioning is ensured with a maximum level of operational reliability. In another development of the invention, the gas burner module can have a gas connection which is directly flange-mounted thereon, and therefore can be connected to a gas pipe, for example a so-called gallery pipe, which runs in the gas cooktop. In this case, the gas connection can advantageously have a fastening clip or be provided with such a fastening clip. Said fastening clip can serve to establish a firm mechanical connection to the gas pipe, so that the gas connection on the gas pipe immutably comprises a secure, gas-tight connection. A fastening clip of this type can engage over the gas pipe, for example on both sides of the gas connection, for uniform, secure fastening. In another embodiment of the invention, the gas connection for the gas pipe is provided on one side of a burner foot, with the burner foot forming, as it were, the base for the gas burner module. In this embodiment, the gas connection is formed in such a way that the gas pipe passes close by the burner foot, and therefore the gas connection, and is held against said burner foot or gas connection by the fastening clip. In this embodiment, the fastening clip can advantageously be fastened to the burner foot. In a further refinement of the invention, a centering pipe can be provided on the gas connection. It can extend, in particular, from the gas connection or the burner foot into the gas pipe in the state in which it is fastened to said gas connection or burner foot. When the gas module is fitted to a gas pipe during assembly of the gas cooktop, provision can then be made for the connection between the burner foot and the gas pipe to be gas-tight. Therefore, a gas supply can pass from the gas pipe, via the centering pipe or the gas connection and then a corresponding line, to the gas valve of the gas burner module, it also being possible for the burner foot to form part of the gas supply in this case. In yet another refinement of the invention, the control electronics can be designed to be connected to a controller of the gas cooktop and, primarily, to be actuated by said controller. To this end, the gas cooktop controller can have an operator control device with operator control elements or can be provided with such an operator control device, with the operator control elements serving as the known interface to a user. Furthermore, the control electronics of a gas burner module can be designed to be connected to and interact with further gas burner modules of the same gas cooktop or with the control electronics of said further gas burner modules which are advantageously all identical. This can advantageously be performed using an internal bus system with corresponding cabling between the gas burner modules and the gas cooktop controller. Furthermore, a power supply unit including a power supply can be provided, the operator control device being connected to said power supply unit. The actuating means for the ignition and monitoring electrode is preferably integrated in the control electronics. The gas valve can advantageously be a proportional valve. It can have a drive which is piezoelectric, magnetic or electromotive. In particular, the gas valve can be operated using a piezo bending beam, specifically generally in accordance with control commands which a user has pre-specified using the above mentioned operator control device using the operator control elements of said operator control device. The abovementioned burner foot can be formed in the manner of a base. It can either carry the gas burner module or said gas burner module can be formed on said burner foot, and said burner foot can also contain the gas valve. The gas valve can therefore be integrated in the burner foot, it preferably being incorporated in the burner foot in a gas-tight manner as an insert. A line for the gas from the gas connection, which is connected to the gas pipe, to the gas valve can be formed either using an integrally projecting short line piece which is provided on the gas connection itself or by using an integrally projecting short line piece which is provided on the gas valve. In another embodiment of the invention, a residual heat indicator can be provided on the gas burner module. To this end, a temperature sensor can be provided, said temperature sensor being mounted on the gas burner module, advantageously close to the gas burner, in order to detect the residual heat. It can even extend as far as a pot which is positioned on the gas burner. Furthermore, a pot detector can be provided, either in the same way as is known with inductive pot detection or even with mechanical pot detection, for example, by using a weight loading on a support on which a pot is placed. Further options are optical scanning from below to check whether there is a pot present over the gas burner. In the case of a gas cooktop according to the embodiment of invention which has already been described above, a single gas pipe or gallery pipe can advantageously be provided. Said pipe can be formed in a peripheral manner in such a way that it passes by the outside of gas burner modules which are arranged flat. Therefore, all the gas burner modules can be supplied with gas. A course for the gas pipe close to the outer periphery of the gas cooktop has the advantage that it can be bent with relatively large radii, this simplifying production and processing thereof. Furthermore, in the case of a gas cooktop with, for example, four distributed gas burner modules, a central area which is produced can be filled with a fifth gas burner module, to which a free end of the gas pipe is routed for supplying gas, or control units or a power supply unit. An operator control device, in particular as a unit or module with an above-mentioned gas cooktop controller, is advantageously likewise provided adjacent to an outer edge of the gas cooktop. The operator control device can also have a power supply unit and a main valve for the gas pipe which can disconnect all the gas burner modules from a gas supply. As an alternative embodiment, the power supply unit and the main valve control means for the main valve can be formed as an assembly which is separate from the pure operator control device, and can be arranged relatively freely and as close as possible to that end of the gas pipe which is provided on the outside in relation to the gas connection. These and further features are described not only in the claims, but also in the description and the drawings, it being possible for the individual features to each be implemented in their own right or in groups in the form of sub-combinations for an embodiment of the invention and in other fields, and to represent advantageous embodiments, worthy of protection in their own right, for which protection is claimed here. The subdivision of the application into individual sections and the intermediate headings do not restrict the generality of the statements made therein. BRIEF DESCRIPTION OF THE DRAWINGS An exemplary embodiment of the invention is schematically illustrated in the drawings and will be explained in greater detail in the text which follows. In the drawings: FIGS. 1 and 2 illustrate two different oblique views of a gas burner module according to one embodiment the invention from above, FIGS. 3 and 4 illustrate exploded oblique views of the gas burner module according to FIG. 1 , and FIG. 5 illustrates a gas cooktop with four gas burner modules. DETAILED DESCRIPTION FIGS. 1 and 2 are oblique illustrations of a fully assembled gas burner module 11 . It has a gas burner 13 which sits on a burner foot 15 , and therefore the burner foot 15 forms a kind of base. A gas connection 17 is provided, said gas connection having a fastening clip 18 which can be removed and screw-mounted, said gas connection and fastening clip forming a cylindrical passage. The gas burner 13 comprises a burner pot 19 and a burner cover 20 , as are known per se from the prior art. A nozzle 22 for the volumetric flow of gas in the gas burner 13 is located beneath said burner pot and burner cover on the burner foot 15 . To this end, there is a gas valve 16 beneath the nozzle 22 , as is described in detail in the introduction. Gas flows with excess pressure from the nozzle 22 into the burner pot 19 from below and exits at lateral bores and is burnt together with the combustion air as a flame. The burner cover 20 which can be held on a burner pot holder 21 in a removable manner and causes the gas stream to be deflected laterally through the bores in the burner pot 19 is provided at the top. FIG. 2 shows that an ignition electrode 24 is provided on the gas burner module 11 on the other side of the gas connection 17 . Said ignition electrode is fastened to the gas burner 13 or on the burner pot holder 21 by means of an insulating holder 25 and is formed such that it both fulfils the function of igniting the gas or mixture and also monitors the flame at the same time. To this end, said ignition electrode can have a high-voltage spark ignition means for the ignition. An ionization flame monitoring means can be used to monitor flames. In alternative embodiments, ignition can be performed by means of a glowing element and flame monitoring can be performed using a thermocouple. A controller 27 is provided on the lower face of the gas burner module 11 or of the burner foot 15 . FIGS. 3 and 4 show exploded illustrations of how the gas burner module 11 is mounted. They also show how the burner pot 19 is positioned on the burner pot holder 21 . Furthermore, these illustrations show the centering pipe 29 on the gas connection 17 , a connection to a gas pipe being established by means of said centering pipe and gas connection. In a similar way, a twin-circuit gas burner can also be formed, specifically as a complete gas burner module. Gas burners which are formed correspondingly differently are to be provided in this case, as are two nozzles and gas valves integrated in the burner foot. An ignition electrode is sufficient. FIG. 5 shows a gas cooktop 30 . It has four gas burner modules 11 a - 11 d in an arrangement with customary distribution. The gas cooktop 30 has a gas cooktop controller 31 in the front region. This gas cooktop controller 31 can correspond to a conventional control means for a conventional cooktop, for example with a cover and touch switches as operator control elements, in particular with capacitive sensor elements. Furthermore, a power supply unit 32 is illustrated in the right-hand region separately from the gas cooktop controller 31 . It also has the main valve control means for the main valve 35 . A gallery pipe 33 runs along with, or adjacent to, the outer edge of the gas cooktop 30 and in this way leads to all the gas burner modules 11 a - 11 d . In addition, said gallery pipe has, in front of its connection to the first gas burner module 11 d , a main valve 35 which is connected to the main valve control means on the power supply unit 32 . This main valve 35 can be electronically actuated and ensures that the gallery pipe 33 and therefore the gas supply are, as it were, shut off if the gas cooktop 30 is switched off. It is clear how the gas burner modules 11 c and 11 d are connected to the gallery pipe 33 by means of the respective gas connections 17 and the fastening clips 18 . In this case, the above-described centering pipes 29 extend through the corresponding openings into the gallery pipe 33 , with this connection being sealed off (gas tight). The control means 27 has the electronic components for ignition, ignition monitoring, gas valve control and communication with a superordinate control means or operator control device 31 . To this end, said control means can have at least one microcontroller, advantageously with class C software. The operator control part, the main valve control means and the gas burner modules 11 communicate by means of a bus connection which is designed to be failsafe. A LIN based protocol is preferably used for this purpose. In order to increase reliability, an additional electrical line is provided between the gas burner modules 11 and the main valve control means 32 , the main valve being supplied with power via said additional electrical line. The main valve can be disconnected from each heating element by series connection of a switching element for each gas burner module. Power is supplied to the gas burner modules 11 and the gas cooktop control means 31 via the power supply unit 32 . The lines required for this purpose are integrated in a bus plug (not illustrated). The gas burner modules 11 are designed such that they can be configured. Various parameters can be programmed via a wire-bound or wireless interface. The parameters include, for example, the geometric position within the gas cooktop 30 , the rated power of the gas burner module 11 , the type of gas, and the valve characteristics. Both the illustration of a single gas burner module 11 and the illustration of an entire gas cooktop 30 according to FIG. 5 show that a gas cooktop can be designed relatively easily together with a great degree of variability by providing gas burner modules 11 which are prefabricated in the modular manner. Specifically, it is necessary to fasten only one gas burner module 11 to the cooktop 30 and then to connect it to a gas supply by means of the gallery pipe 33 and to provide a control line including an electrical connection to the gas cooktop control means 31 . As a result, a highly variable design of a gas cooktop 30 is possible, primarily without fault sources during assembly, as long as the connection to the gallery pipe 33 is made correctly. It can also be seen that the burner pot 19 and the burner cover 20 are larger in the case of gas burner modules 11 b and 11 c . This means that they are designed for higher powers and therefore also generate a higher heating power as a result of the combustion of more gas.
A gas burner module for a gas cooktop has a gas burner with an ignition and monitoring electrode, and also ignition and control electronics, a flame monitoring device and a gas valve. A burner foot in the form of a base is provided as a supporting element of the gas burner module. These parts of the gas burner module are combined to form a unit and are mechanically connected to one another in such a way that they form a constructional unit which can be handled independently.
5
FIELD OF THE INVENTION This invention relates to control reagents useful in validating testing devices, such as test strips and dipsticks. More particularly, it relates to a non-serum based, aqueous glucose control reagent. BACKGROUND AND PRIOR ART The field of clinical chemistry and clinical analysis is concerned, inter alia, with the determination and quantification of various substances in body fluids. Many examples of the substance which are to be determined can be given, and include cholesterol, urea, cations, and glucose. These examples of analyte, as well as others, are assayed in diverse body fluids such as urine and blood. One of the most frequently used devices in clinical chemistry is the test strip or dipstick. These devices are characterized by their simplicity of use. Essentially, the device is contacted to the body fluid to be tested. Various reagents incorporated into the device react with the analyte being determined to provide a detectable signal. Generally, this is a color or a change in color. These signals are measured or determined either visually or, more preferably, by an analysis machine. The detectable signal is correlated to a standard, so as to give a value for the amount of analyte present in the sample. It will be understood that clinical analysis of the type described herein requires that any testing system be extremely accurate. In particular, when automated systems are used, it is essential to ensure that the elements of the analysis be reliable, and that the measurement taken be valid. It is for this purpose that control reagents are used. Tietz, et al., Textbook of Clinical Chemistry page 430, defines "control material" as "a specimen, or solution, which is analyzed solely for quality control purposes and is not used for calibration purposes". This standard reference work goes on to describe some of the requisites of a control material, as follows: "They need to be stable materials, available in aliquots or vials, that can be analyzed periodically over a long time. There should be little vial-to-vial variation so that differences between repeated measurements can be attributed to the analytical method alone". It must be added that the control material must be stable as well. The cited reference, at page 433, discusses how the matrix of the control material should be the same as the material being analyzed. To that end, Tietz discusses modified human serum as one type of control material. Indeed, the art now recognizes the term "control serum" as referring to control material based upon serum. This terminology will be used herein, and is different from the term "control reagent" which, as used hereafter, refers to a control material which is not based on, and does not contain, serum of any type. As has been pointed out, supra, one of the criteria which control materials have to satisfy is stability. Control materials based upon serum, however, are inherently unstable, due to the various components contained therein. Further, sera will vary from source to source, so uniformity from lot to lot cannot be guaranteed. Thus, it is sometimes desirable to have a control material based on a non-serum or serum free medium. Examples of serum free control media, or "control reagents" as used herein, are seen in U.S. Pat. Nos. 4,684,615 and 4,729,959. The '615 patent teaches an aqueous isoenzyme control reagent. The reagent contains the isoenzyme of interest, together with other materials in a water base. More pertinent to the subject invention is the '959 patent, which is directed to "a stable glucose reference control". This control contains glucose in a range of from about 40 to 500 mg/dl, together with fixed red blood cells, in an aqueous solution. The range of glucose concentrations given are sufficient to cover just about all ranges of glucose found in, e.g., blood. The '959 patent points to a problem with aqueous control reagents at column 1, lines 50-55. Briefly, erythrocytes impart a degree of viscosity to blood which is absent in water based systems. This problem was also recognized in U.S. Pat. No. 3,920,580 to Mast. This patent teaches that aqueous solutions had not been consistent, and that a lack of reproduceability was observed when dry reagent strips were used with such materials. Mast taught that suitable reagents could be prepared using an antidiffusing agent in combination with glucose and water. The antidiffusing agents include polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, dextran, and bovine serum albumin. It has now been found that a suitable glucose control reagent can be formed without using any of the material referred to in Mast as required ingredients. Rather, by combining a soluble polymer with glucose and water, with additional optional materials, a suitable glucose control reagent can be made. SUMMARY OF THE INVENTION The invention is a non-serum based glucose control reagent which comprises a predetermined known amount of glucose, water, and a soluble polymer, i.e., a polystyrene sulphonate or a soluble salt thereof. Additional materials, such as a buffer, a preservative, a surface active agent or a surfactant, or an ionic salt, either alone or in various additive combinations, may be mixed with the three required components. Another aspect of the invention is a method of making the control reagent by mixing the glucose and the polystyrene sulphonate together. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Example 1 A preferred formulation of the control reagent of the invention was prepared, as follows: ______________________________________H.sub.2 O 738.6 gNa Salt of polystyrene sulfonate 250.0 gHEPES (4-(2-hydroxyethyl-1- 7.1 gpiperazine-ethane sulfonic acid)2-phenoxyethanol 3.31 gGermall 115 3.0 gMethylparaben 1.20 gTOTAL weight: 1003.21 g______________________________________ This reagent was adjusted with 10N NaOH to have a final pH of 7.5. The formulation described here then has glucose added to the rest of the reagent in a predetermined amount. The skilled artisan will recognize that the concentration will vary, at the discretion of the maker and depending upon the particular test system involved. Ryan, U.S. Pat. No. 4,729,959, e.g., sets forth a range of from 40 to 500 mg/dl, of glucose. This range covers most of the concentrations of clinical interest, but it is assumed herein that the amount of glucose in the claimed control reagent may be both less than or more than the range recited in the Ryan patent. Example 2 The control reagent set forth in Example 1 was then tested for its efficacy. As explained supra, one of the most important features of a control reagent is its consistency, meaning that values obtained using it should be fairly uniform from run to run. With this in mind, the control reagent of Example 1 was applied to test strips containing the glucose determination system described in U.S. patent application Ser. No. 339,051, filed Apr. 14, 1989, now U.S. Pat. No. 4,929,545, the disclosure of which is incorporated by reference. Briefly, this reference describes determining glucose using a reagent containing a glucose oxidase, ferricyanide/ferric compound system. Three glucose solutions were prepared, containing 41 mg/dl, 120 mg/dl, and 174 mg/dl glucose, as measured via glucose hexokinase methodology. These solutions were then measured using the exemplified reagent, together with the reference glucose determination reagent. The results are set forth in Table 1: TABLE I______________________________________Strip Response Values at Three Glucose Levels______________________________________Strip Glucose Values 56 183 227(mg/dl) 56 182 239 63 187 248 50 181 238 63 191 243 58 185 249 53 179 224 63 191 234 63 190 235 57 174 221 56 175 238 61 182 240 51 173 238 62 186 235 60 178 245 53 172 229 65 180 250 65 184 250 186 252Mean Strip Glucose 58.7 182.0 238.5Value (mg/dl)Standard deviation 4.8 5.9 9.1CV % 8.2 3.2 3.8Hexokinase Glucose 41 120 174Value (mg/dl)______________________________________ These results show a level of consistency well within that required of a control reagent, as is indicated by the standard deviation and coefficient of variation values reported for each set of tests. While the control reagent system has been shown to be operative with respect to the glucose oxidase/ferrocyanide/ferricyanide system, it will be understood that the criteria which the control reagent must satisfy are independent of the actual test system. Thus, the control reagent will be seen to be useful in connection with any of the known glucose analysis systems. Essential to the invention are a predetermined amount glucose, water, and the recited polystyrene sulphonate. The water is used, of course, to create a reagent solution. By "predetermined" is meant that, prior to formulation of the actual reagent, a concentration of glucose has been selected. This concentration may vary, as those skilled in the art will recognize. As has been mentioned supra, the art recognizes, e.g., a range of from 40 to 500 mg/dl, but one may envision lower ranges to, e.g., about 20 mg/dl. Some typical ranges would be from about 60 to about 240 mg/dl, or from about 60 to about 300 mg/dl. The essential features of the invention, when the reagent is in the form of a solution, are the solvent (water), the predetermined amount of glucose, and the polystyrene sulphonate or a salt thereof. The polystyrene sulphonate or its salt may be present, in e.g., from about 0.5 to about 55-60 weight percent of the reagent. A preferred range is from about 0.5 to about 40 weight percent of the control reagent. In an especially preferred embodiment a range of from about 20 to 30 weight percent is used. The weight percent of the polymer will vary, depending upon factors which include molecular weight and solubility. The term "polystyrene sulphonate" refers to any and all forms of this molecule. As is known, polymers can vary in their atomic weight. In the case of polystyrene sulphonate, an atomic weight of from about 5000 to about 6,000,000 is preferred. An especially preferred embodiment uses polystyrene sulphonate at an atomic weight of from about 35,000 to about 750,000. Most preferably, the atomic weight ranges from about 70,000 to about 500,000. Optional additional components of the control reagent include buffers, preservatives, surface active agents, surfactants, and ionic salts. With respect to buffers, some preferred species are HEPES (4-(2-hydroxy ethyl-1-piperazine-ethane sulphonic acid); CHES(2-(N-cyclohexylamino) ethane sulphonic acid); MOPS(3-(N-morpholino)propane sulphonic acid), and MEPS(2-(N-morpholino) ethane sulphonic acid) and CAPS (3-(cyclohexylamino)-1-1-propane)-sulfonic acid) buffers. Preferred preservatives include imidazolidinyl urea, available under the trade name "Germall 115," methylparaben or methanol (((2-(dihydro-5-methyl-3(2H)-oxazoylyl)-1-methylethoxy)methoxy)methoxy), available as "Cosan 145", phenoxyethanol and gentamycin sulfate, both individually and in combination. Typical surfactants include "MIRANOL J2M-SF", which is capryloamphocarboxypropionate, and "DOWFAX 2Al", which is tetrapropylene diphenyloxide disulphonate sodium salt. The reagent may also contain an ionic salt, such as an ionic salt of sodium (e.g., sodium sulphate) or salts of other cations such as lithium, magnesium, calcium, and so forth. It may also be desirable to include a colored or colorable substance in the reagent. This can be desirable because body fluid samples frequently possess a color as one of their properties. As the control reagent is being used to calibrate per a body fluid sample, it can be useful to calibrate against conditions as similar to the tested fluid as possible, including color. The control reagent may also be formulated as either a kit, or in the form of a lyophilisate. "Lyophilisate" as the art recognizes, refers to the substantial absence of moisture in a formulation. The invention, in lyophilized form, most broadly comprises a predetermined amount of glucose and the polystyrene sulphonate or salt thereof. Additional components, including those listed supra, may be included in the lyophilisate, as long as moisture is substantially absent. When the reagent is present in kit form, it can include, e.g., a sample of a solution of a predetermined amount of glucose in one container means, and polystyrene sulphonate in a second one with a container means holding both the first and second containers. Additional components may also be present, as listed supra, and may be mixed with either of the first two components, or may be present in separate container means. It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
The invention relates to a non-serum based control reagent for glucose determination. Rather than using modified serum, the control reagent contains water, glucose, and the viscosity agent polystyrene sulphonate. The control reagent may also contain a buffer, preservatives, surfactants or surface active agents. A method of making the control reagent is also disclosed.
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BACKGROUND OF THE INVENTION [0001] The present invention relates to a laminated board, and more especially to a method for manufacturing laminated board and the apparatuses used on the same. [0002] In accordance with the conventional wooden laminated board, artificial stone laminated board, stone laminated board, fiberglass reinforced plastics and so on, they are widely used in decorating inner and outer of room, such as kitchens, bathrooms or wine bars and so on, among of them the description of a Chinese patent No.: 200310116851.4 reveals a method for manufacturing artificial stone laminated board, in which the stoke preparation is taken up on the worktable of the hydraulic press, such like stacking up the sheets of the laminated board on the worktable of the oil press, and pushing the oil press loaded with the stacked sheets of the laminated board into the inside of the vacuum cabinet along the track-way for vacuuming, and after releasing the oil press from the vacuum state into normal state the oil press kept in working state is pushed out from the vacuum cabinet, it will be kept in pressing state for 3˜4 hours so that the laminated board is completely solidified. Due to the carriages built on the both sides of the oil press, the stacking process will become inconvenient, and because the vacuum cabinet is used for vacuuming only and the oil press is used just for pressing, so only by pushing the oil press in or out the vacuum cabinet can the works be carried out, additionally the oil press is very heavy, so the operation is quite inconvenient as pushing in and out, and the operating efficiency is poor, additionally there is a big scale demand in the market, if there is only one oil press available, it signifies that the vacuum cabinet will be idle for 3˜4 hours in a cycle, so that this operating efficiency can not meet the requirement of the market, if increasing the number of the oil presses, the equipment investment will be increased, so how to decrease the manufacturing cost of the equipment, enlarge the production scale, fully take the advantage of the vacuum cabinet to carry out assembly line production, improve production efficiency and reduce cost are the issues expected to be solved. BRIEF SUMMARY OF THE INVENTION [0003] For overcoming the shortcomings exited in the conventional technology, the main object of the present invention is to provide a method for manufacturing laminated board and the apparatuses used on the same for reducing the equipment cost, enlarging the production scale, fully taking the advantage of the vacuum cabinet to carry out assembly line production, improving the production efficiency and reducing manufacturing cost. [0004] For archiving the objects, the method offered by the present invention includes following steps: a) The stacking sheet and coating gum processes of each laminated board are taken on the pressure block of a trailer carrier; b) Securing bolts on said pressure block, fitting on a top board over the bolts from upside, sequentially securing on nut; c) Putting the trailer carrier loaded with a set of stacked laminated boards at inside of the vacuum pressure device; d) Vacuuming air at the cavity by the vacuum pressure device; e) Under the vacuum condition, the vacuum pressure device briquettes the stacked gummed laminated board; f) Removing the vacuum condition from the vacuum pressure device; g) Securing in the fasteners on the pressure block to keep the pressure on each laminated board; h) Removing the pressure coming from the vacuum pressure device; i) Drawing out the trailer carrier from the vacuum pressure device for making the binder solidify in cold or heating; j) Securing out the fasteners and the top board from the pressure block, taking out the finished laminated board. [0015] Said stacking and gumming step operated on the pressure block of the trailer carrier includes that coating blinder over the contacting surface of the sheets of the laminated board before stacking the sheets up; also includes taking plastic film to isolate two adjacent gummed laminated board as in stacking operation so as to avoid the binder exuding to glue individual laminated boards together, or sandwiching the gummed laminated board between two conducting blocks so that the thermosetting binder emitted from the conducting blocks can be transferred the heat to the binder layers between the sheets to solidify. [0016] In this time, said bolts secured on the pressure block, the top board fit on the bolts, and the nuts secured on the bolts all are in loose configuration. [0017] Said vacuuming step processed by the vacuum pressure device includes that the vacuum degree gets −0.1 MPa shown on the vacuum gage so as to vacuum fully at the inside of the vacuum pressure device. [0018] Said step of putting the trailer carrier loaded with a set of stacked laminated boards at inside of the vacuum pressure device includes that after placing the trailer carrier loaded with a set of stacked laminated boards into the inside of the vacuum pressure device, by plugging the latches the combined base of the hydraulic actuating mechanism is connected to the guide pillars; then lift up the top board a bit via the connection by the hydraulic actuating mechanism so that the top board is apart from the top sheet of the laminated board more than 1 mm, 1 cm to 1 m in general, for avoiding the vacuum of the binder layer between the sheets of the laminated board affecting by the weight force coming from the top board. [0019] Said removing the pressure coming from the vacuum pressure device step includes when the combined base of the hydraulic actuating mechanism is connected to the guide poles of the top board by plugging the latches in, if want to disconnect the connection such as drawing the latches out, firstly the pressure force coming from the hydraulic actuating mechanism has to be removed, then draw the latches out, next separate the combined base of the hydraulic actuating mechanism out from the guide poles of the top board. [0020] To sum up, after the vacuum pressure device treats the set of laminated boards loaded on the trailer carrier in vacuuming and pressing processes, the trailer carrier is drew out from the vacuum pressure device, and the laminated boards is kept under pressure by securing in the fasters for waiting to the solidifying finishing, then next stocked trailer carrier will be placed into the inside of the vacuum pressure device, in this way, the vacuum pressure device can be used continuously in circulation for processing each set of laminated boards stacked on each trailer carrier to carry out flow-line production. [0021] The apparatuses used for carry out above-mentioned method include a vacuum pressure device and trailer carriers, in which said vacuum pressure device integrated a vacuum device and a set of hydraulic actuating mechanism into together is comprised of a vacuum device used for exhausting out air, and hydraulic actuating mechanism used to briquette the sheets of the laminated boards stacked on the trailer carrier; said trailer carrier includes wheels used for running, a carriage used for placing a pressure block on, spring-strip suspensions connecting said carriage to the wheels respectively for damping as running, when the trailer carrier is placed into the inside of the vacuum pressure device attached with a pair of vertical bearing plates built on outer places beside the both trails parallelly, and bears the pressure coming from the vacuum pressure device, the spring-strip suspensions is distorted so that the carriage is laid on the top surfaces of the bearing plates crossly to transfer the pressure on the bearing plates; on the carriage there are a pressure block bearing all sets of laminated boards and a top board pressing all sets of laminated boards set, therein said top board can be made of light material optionally, such as cast aluminum alloy, or heavy material, such as iron, cast steel and so on; there are fasteners built on the pressure block rightly upward for matching with the pressure block and the top board separately, so as to keep pressure on the all sets of laminated boards via the top board, and locate all sets of the laminated boards and the top board; said fasteners is comprised of bolts and nuts, or other mechanism bought from the market, such as screw bolts and vacuum suction-press, screw bolts and eccentric. [0022] The vacuum device of said vacuum pressure device also can be vacuum box, vacuum cabin or vacuum casing, said vacuum box, among of them, said vacuum box and vacuum cabin have a door individually for the trailer carrier entering and exiting, and windows facilitating to securing operation, and also have track-way providing the guide way for the trailer carrier entering and exiting, and a pair of bearing plates for bearing pressure coming from the vacuum pressure device, when the trailer carrier enters the inside of the vacuum pressure device, it is pressed down by the pressure coming from the hydraulic actuating mechanism, further to distort the spring-strip suspensions so that the carriage is laid on the top surfaces of the bearing plates crossly to transfer the pressure on the bearing plates; said vacuum casing has windows facilitating to the securing operation and seal loop at the bottom side for matching on the top surface of the pressure block in seal connection. [0023] Said vacuum device and the press are combined into one body integrally, said presses can be located on the top side, flank or bottom side, and extended to the outside of the vacuum pressure device so as to stretch the pressure bars into the inside of the vacuum pressure device, and the joint portions of the press and the vacuum device are sealed; in this way, the press with the preferred direction is mounted on the top side of the vacuum device exposing to the outer air, and its pressure bars pass through the top wall of vacuum device stretching into the inside, and the joint portions of the press and the vacuum device are sealed, or said press is mounted into the inside of the vacuum device, and can be located on the top side, flank or bottom side, and joined with the vacuum device; said press with the preferred direction is mounted on the top side of the vacuum device connecting to the vacuum device at inner roof; said press can be a common mechanical press, or a vacuum press, or a pneumatic press, or a hydraulic press, or a press integrated with hydraulic and vacuum presses together, or a press integrated with hydraulic and pneumatic presses, or a press integrated with hydraulic and common mechanical pressed together and so on. [0024] The pressure bars of said presses are connected to a combined base with the end for indirectly connecting to the guide pillars of the top board, said top board has said guide pillars built on the top side used for connecting to the combined base of said press, and latches used for locking or releasing the connection of the combined base and the guide pillars. [0025] The apparatuses used for manufacturing said laminated board includes conducting blocks used for heating and solidifying the thermosetting binder layer between the sheets of the laminated board, also includes the track-way used for carrying the trailer carrier; there are conduction oil-pipes built upon said conducting block for circulating hot-oil to heat the conducting block, further to transferring the heat to the binder layers between the sheets of the laminated board via the conducting block for solidifying, coordinating to the conduction oil-pipes located at the inside of the conducting block, there are connectors fixed on the outer side wall of the vacuum box for connecting the hot-oil resource into the conducting block. [0026] Comparing with the conventional technology, above-described technology project has following advantages: 1. due to the special design of the trailer carrier, the carriages built on the both sides are saved so as to facilitate to stacking sheets, meanwhile the volume of the trailer carrier reduced facilitates to transporting, so as to solve the interrupting operation problems of blocking coming from the both-side carriages and big volume, and the cooperation of the pressure block, the top board and the fasteners on the trailer carrier not only keeps the pressure exerting on the laminated boards, but also locates the top board on the stacked laminated boards. 2. due to the vacuum pressure device of the present invention integrated the vacuum device and press into one body, so the vacuum pressure device has two functions simultaneously of vacuuming and pressing so that the vacuum pressure device is utilized fully, additionally due to the cooperation of the pressure block, the top board and the fasteners on the trailer carrier, the trailer carrier has not to be equipped with a press on, so a vacuum pressure device can be equipped with many trailer carriers, it not only reduces the equipment cost, but also enlarges the manufacturing scale to carry out flow-line production. 3. in applying the method and the apparatuses offered by the present invention, after the vacuum pressure device treats the laminated boards stacked on the trailer carrier in vacuuming process and pressing process, the trailer carrier is drew out of the vacuum pressure device, taking the advantage of securing the fasteners in keeps the pressure exerting on the stacked laminated boards until the binder layers are solidified completely, in this time the next trailer carrier stocked with the stacked laminated boards can be placed into the inside of the vacuum pressure device, in this way the vacuum pressure device can be used circularly for treating each trailer carrier loaded with the stacked laminated boards in vacuuming and pressing processes; after the binder layers are solidified completely, remove the fasteners, the top board and the finished laminated boards from the trailer carrier to empty the trailer carrier being ready for stacking sheets of the laminated boards in next cycling, therefore the present invention not only can reduce the equipment cost, but also enlarge the production scale and improve production efficiency to carry out flow-line production to meet the requirement of the market. BRIEF DESCRIPTION OF THE DRAWINGS [0030] FIG. 1 is a flow chart of the present invention. [0031] FIG. 2 is a side view showing the trailer carrier stocked with the stacked sheets coated with the cold binder of the laminated boards of the present invention. [0032] FIG. 3 is a side view showing the trailer carrier stocked with the stacked sheets coated with the thermosetting binder of the laminated boards of the present invention. [0033] FIG. 4 is a front-side view showing the sealed joint of the press and the vacuum device in the vacuum pressure device of the present invention. [0034] FIG. 5 is a side view showing the sealed joint of the press and the vacuum device in the vacuum pressure device of the present invention. [0035] FIG. 6 is a front-side view showing the press located at inside of the vacuum box in the box vacuum pressure device of the present invention. [0036] FIG. 7 is a side view showing the press located at inside of the vacuum box in the box vacuum pressure device of the present invention. [0037] FIG. 8 is a front-side view showing the casing vacuum pressure device of the present invention. [0038] FIG. 9 is a side view showing the sealed joint of the hydraulic press and the vacuum device of the present invention. [0039] 1 trailer carrier, 2 wheel, 3 carriage, 4 spring-strip suspension, 5 pressure block, 6 top board, 7 guide pillar, 8 fastener, 8 . 1 bolt, 8 . 2 nut, 9 latch, 10 laminated board, 11 plastic film, 12 conducting block, 12 . 1 connector, 13 hydraulic press, 13 . 1 seal loop, 13 . 2 pressure bar, 14 vacuum box, 14 ′ casing, 14 . 1 door, 14 . 2 windows, 14 . 3 roof wall, 14 . 3 ′ roof wall, 15 combined base, 16 track-way, 17 bearing plate, 18 box vacuum pressure device, 18 ′ casing vacuum pressure device, 19 seal loop, 20 bolt DETAILED DESCRIPTION OF THE INVENTION [0040] Referring to the attached drawings, following embodiments will be described minutely, within the similar mechanical structures in the different drawings will use the same notation in their own drawings as illustrating in the description. It should be stressed that following detailed description is just only demonstration that should not be understood as a strict constraint to the claimed range of the claim of the present invention. [0041] FIG. 1 is showing the steps of the method provided by the present invention: a) stack the sheets coated with binder of the laminated board up on the pressure block of the trailer carrier; b) secure in the blots of the fasteners on the pressure block, fit the top board over the bolts, secure on nuts; c) place the trailer carrier stocked with the stacked laminated boards into the inside of the vacuum pressure device; d) exhaust out air of at the cavity by the vacuum pressure device; e) briquette the sheets coated with binder into the laminated boards by the vacuum pressure device under the vacuum condition; f) remove the vacuum condition from the vacuum pressure device; g) secure in the fasteners on the top board to keep the pressure exerting on the stacked laminated boards; h) remove the pressure coming from the press of the vacuum pressure device; i) exit the trailer carrier from the vacuum pressure device for waiting to the binder solidifying in cold or heating; j) Move out the fasteners, the top board from the top side of the trailer carrier sequentially; take the finished laminated boards out. [0052] FIG. 2 is a side view showing stacking the sheets coated with cold binder upon the trailer carrier, in which the sheets coated over the cold binder are stacked up to a laminated board 10 on the pressure block 5 of the trailer carrier 1 , the two adjacent laminated boards 10 are isolated by a plastic film 11 for preventing the binder from exuding to glue individual laminated boards 10 together; the trailer carrier 1 shown includes wheels 2 used for running, a carriage 3 used for placing a pressure block 5 on, spring-strip suspensions 4 connecting said carriage 3 to the wheels 2 respectively for damping as running, when the trailer carrier 1 is placed into the inside of the vacuum pressure device attached with a pair of vertical bearing plates 17 built on outer places beside the both trails 16 in parallel, and bears the pressure coming from the vacuum pressure device, the spring-strip suspensions 4 is distorted so that the carriage 3 is laid on the top surfaces of the bearing plates 17 crossly to transfer the pressure on the bearing plates 17 ; on the carriage 3 there are a pressure block 5 bearing all sets of laminated boards 10 and a top board 6 pressing all sets of laminated boards 10 set on, therein said top board 6 can be made of cast-iron; the top board 6 has guide pillars 7 built on the top side for connecting to the combined base 15 of the press, there are fasteners 8 built on the pressure block 5 rightly upward for matching with the pressure block 5 and the top board 6 separately, so as to keep pressure on the all sets of laminated boards 10 via the top board 6 , and locate all sets of the laminated boards 10 and the top board 6 ; said fasteners 8 is comprised of bolts 8 . 1 and nuts 8 . 2 , or other mechanism bought from the market, such as screw bolts and vacuum suction-press, screw bolts and eccentric. [0053] FIG. 3 is a side view showing the trailer carrier stocked with the stacked the sheets coated over with thermosetting binder, in which the sheets coated over the thermosetting binder are stacked up to a laminated board 10 on the pressure block 5 of the trailer carrier 1 , and conducting blocks 12 sandwiched between two adjacent laminated boards 10 are used for heating the thermosetting binder to solidify; said trailer carrier 1 shown includes wheels 2 used for running, a carriage 3 used for placing a pressure block 5 on, spring-strip suspensions 4 connecting said carriage 3 to the wheels 2 respectively for damping as running, when the trailer carrier 1 is placed into the inside of the vacuum pressure device attached with a pair of vertical bearing plates 17 built on outer places beside the both trails 16 in parallel, and bears the pressure coming from the vacuum pressure device, the spring-strip suspensions 4 is distorted so that the carriage 3 is laid on the top surfaces of the bearing plates 17 crossly to transfer the pressure on the bearing plates 17 ; on the carriage 3 there are a pressure block 5 bearing all sets of laminated boards and a top board 6 pressing all sets of laminated boards 10 set on, therein said top board 6 can be made of cast A-alloy; there are fasteners 8 built on the pressure block 5 rightly upward for matching with the pressure block 5 and the top board 6 separately, so as to keep pressure on the all sets of laminated boards via the top board 6 , and locate all sets of the laminated boards 10 and the top board 6 ; said fasteners 8 is comprised of bolts 8 . 1 and nuts 8 . 2 , or other mechanism bought from the market, such as screw bolts and vacuum suction-press, screw bolts and eccentric; in said conducting block 12 there are conduction oil-pipes built upon said conducting block 12 for circulating hot-oil to heat the conducting block 12 , further to transferring the heat to the thermosetting binder layers between the sheets of the laminated board 10 via the conducting block 12 for solidifying, coordinating to the conduction oil-pipes located at the inside of the conducting block 12 , there are connectors 12 . 1 fixed on the outer side wall of the vacuum box for connecting the hot-oil resource into the conducting block 12 . [0054] FIG. 4 and FIG. 5 are the front-side and right-side views respectively showing the sealed connection of the press and the vacuum box in the box vacuum pressure device of the present invention, they illustrate that in the box vacuum pressure device 18 of the present invention the hydraulic presses 13 are mounted on the vacuum box 14 with bolts 20 cooperating to the seal loop to combine into one body, therein the vacuum box 14 is used for exhausting air out, and the hydraulic presses 13 are used for briquette the laminated boards 10 ; the pressure bar 13 . 2 of the hydraulic press 13 passes through the roof side 14 . 3 of the vacuum box 14 so that the tip end of pressure bar 13 . 2 stretches into the inside of the vacuum box 14 to join with the combined base 15 for connecting to the guide pillars 7 of the top board 6 ; the vacuum box 14 has track-way 16 built on the inside providing the guide way for the trailer carrier 1 entering and exiting, and a pair of bearing plates 17 for bearing pressure coming from the hydraulic presses 13 , when the trailer carrier 1 enters the inside of the vacuum pressure device 18 , it is pressed down by the pressure coming from the hydraulic presses 13 , further to distort the spring-strip suspensions 4 so that the carriage 3 is laid on the top surfaces of the bearing plates 17 crossly to transfer the pressure on the bearing plates 17 ; said vacuum box 14 has windows 14 . 2 facilitating to the securing operation and seal loop at the bottom side for matching on the top surface of the pressure block in seal connection; said vacuum box 14 has a door 14 . 1 individually for the trailer carrier 1 entering and exiting, and windows 14 . 2 facilitating to securing operation; said hydraulic press 13 can be a common mechanical press, or a vacuum press, or a pneumatic press, or a hydraulic press, or a press integrated with hydraulic and vacuum presses together, or a press integrated with hydraulic and pneumatic presses, or a press integrated with hydraulic and common mechanical pressed together and so on. [0055] FIG. 6 and FIG. 7 are the front-side and right-side views respectively showing the hydraulic presses located on the inside of the vacuum box in the vacuum pressure device, they illustrate that in the box vacuum pressure device 18 the hydraulic presses 13 are mounted on the inside of the vacuum box 14 to be located on the roof wall 14 . 3 of the vacuum box 14 with bolts 20 in joint, therein the vacuum box 14 is used for exhausting air out, and the hydraulic presses 13 are used for briquette the laminated boards 10 ; said vacuum box 14 has a door 14 . 1 individually for the trailer carrier 1 entering and exiting, and windows 14 . 2 facilitating to securing operation; said hydraulic press 13 can be a common mechanical press, or a vacuum press, or a pneumatic press, or a hydraulic press, or a press integrated with hydraulic and vacuum presses together, or a press integrated with hydraulic and pneumatic presses, or a press integrated with hydraulic and common mechanical pressed together and so on. [0056] FIG. 8 is the front-side view showing the casing vacuum pressure device of the present invention, it illustrates that in the casing vacuum pressure device 18 ′ the hydraulic presses 13 are mounted on the vacuum casing 14 ′ with bolts 20 cooperating to the seal loop 13 . 1 to connecting into one body integrally, therein the vacuum casing 14 is used for exhausting out air, and the hydraulic presses 13 are used for briquette the laminated boards 10 ; the pressure bar 13 . 2 of the hydraulic press 13 passes through the roof side 14 . 3 ′ of the vacuum casing 14 ′ so that the tip end of pressure bar 13 . 2 stretches into the inside of the vacuum casing 14 ′ to join with the combined base 15 for connecting to the guide pillars 7 of the top board 6 ; said vacuum box 14 has windows 14 . 2 facilitating to the securing operation and seal loop at the bottom side for matching on the top surface of the pressure block in seal connection; said vacuum casing 14 ′ has windows 14 . 2 ′ facilitating to securing operation, and a seal loop 19 built upon the bottom engaging with the pressure block 5 for connection; said hydraulic press 13 can be a common mechanical press, or a vacuum press, or a pneumatic press, or a hydraulic press, or a press integrated with hydraulic and vacuum presses together, or a press integrated with hydraulic and pneumatic presses, or a press integrated with hydraulic and common mechanical pressed together and so on. [0057] FIG. 9 is a side view showing the sealed connection of the vacuum box and the hydraulic presses of the present invention, it illustrates that the conventional hydraulic presses 13 are mounted on the vacuum box 14 with bolts 20 cooperating to the seal loop 13 . 1 to connecting into one body integrally, the pressure bar 13 . 2 of the hydraulic press 13 passes through the roof side 14 . 3 of the vacuum box 14 so that the tip end of pressure bar 13 . 2 stretches into the inside of the vacuum box 14 to join with the combined base 15 for connecting to the guide pillars 7 of the top board 6 . THE FIRST PREFERRED EMBODIMENT [0058] Referring to FIG. 1 , FIG. 2 , FIG. 4 and FIG. 5 , the method of the present invention is described in detail as followings: [0059] Take 20 pieces of artificial stone sheets out as two in one set, firstly coat SY-21 cold binder on the contacting surfaces of said artificial stone sheets; next stack all sets of laminated boards 10 up on the top surface of the pressure block 5 isolated by the plastic film 11 between two adjacent sets of laminated boards for avoiding the binder exuding from the interstices of the sheets to glue the adjacent sets of the laminated boards 10 together; after stacking all the sets of laminated boards 10 up, secure in the bolts 8 . 1 of the fasteners 8 on the pressure block 5 of the trailer carrier 1 , sequentially put the top board 6 on the bolts 8 . 1 to press on the stacked laminated boards 10 , and secure on the nuts 8 . 2 respectively keeping in loose state in this time, said top board 6 is made of cast-iron; then place the trailer carrier 1 stocked with the stacked laminated boards 10 into the inside of the box vacuum pressure device 18 , by plugging the latches 9 in the combined base 15 of the box vacuum pressure device 18 is connected to the guide pillars 7 of the top board 6 , next lift the top board 6 up by the hydraulic presses 13 of the box vacuum pressure device 18 so that the top board 6 is kept more than 1 cm distance from the top surface of the stacked laminated boards 10 for preventing the binder layer between the sheets from affecting by the pressing force coming from the top weight of the top board 6 as vacuuming; then close the door 14 . 1 and windows 14 . 2 of the vacuum box up, the box vacuum pressure device 18 can carry out vacuuming process to get −0.1 MPa shown on the vacuum-meter taking about 13 minutes in order that the inside of the box vacuum pressure device 18 is guaranteed enough vacuum; then under the vacuum condition the hydraulic presses 13 of the box vacuum pressure device 18 stars to press the stocked laminated boards 10 coated with cold binder in the briquette process with 30 Tons pressure; after exerting pressing force, the vacuum condition can be removed in the inside of the box vacuum pressure device 18 , open the windows 14 . 2 of the box vacuum pressure device 18 , and via them the operator can secure the fasteners 8 in for keeping the pressure exerting on the stacked laminated boards 10 after removing the pressure coming from the hydraulic press 13 of the box vacuum pressure device 18 , so that the stacked laminated boards stocked on the trailer carrier 1 are exerted with pressing force by the trailer carrier 1 its own after the trailer carrier 1 is took out of the vacuum box of the box vacuum pressure device 18 , in order to guarantee the binder layers between the sheets of the laminated boards 10 are solidified under the pressure fully; after securing the fasteners 8 in, remove the latches 9 from the locking configuration to depart the combined base 15 from the guide pillars 7 of the top board 6 so that the pressing force coming from the hydraulic presses 13 can be removed; then the door 14 . 1 is opened, the trailer carrier 1 can be exited out of the box vacuum pressure device 18 for being ready to place the next stacked trailer carrier 1 in for next circulation; the trailer carrier 1 exited from the box vacuum pressure device 18 is placed in idle state for waiting for the SY-21 cold binder layers solidified completely, it will take about 3 hours; after the binder is solidified fully, secure out the fasteners 8 , remove the top board 6 , the finished artificial stone laminated boards 10 can be took out from the trailer carrier 1 for emptying the trailer carrier 1 for reloading stacked sheets of the laminated boards 10 in next circulation; the finished laminated board 10 will be cut off the solidified binder exuded out along the edges by the trim cutter to become a quantified goods for entering the storing house. [0060] Said SY-21 cold binder can be bought in the Chinese market. THE SECOND PREFERRED EMBODIMENT OF THE PRESENT INVENTION [0061] Referring to FIG. 1 , FIG. 3 , FIG. 6 and FIG. 7 , the method of the present invention is described in detail as followings: [0062] Take 15 pieces of artificial stone sheets and 15 pieces of fire-proof boards out as one artificial stone sheet and one fire-proof board in one set of the laminated board 10 , firstly coat E-7-2 thermosetting binder on the contacting surfaces of one artificial stone sheet and one fire-proof board respectively; next stack all sets of laminated boards 10 up on the top surface of the pressure block 5 within one set of the laminated board 10 is sandwiched by two conducting blocks 12 respectively; after stacking all the sets of laminated boards 10 up, secure in the bolts 8 . 1 of the fasteners 8 on the pressure block 5 of the trailer carrier 1 , sequentially put the top board 6 on the bolts 8 . 1 to press on the stacked laminated boards 10 , and secure on the nuts 8 . 2 respectively keeping in loose state in this time, said top board 6 is made of cast aluminum alloy; then place the trailer carrier 1 stocked with the stacked laminated boards 10 into the inside of the box vacuum pressure device 18 ; then close the door 14 . 1 and windows 14 . 2 of the vacuum box up, the box vacuum pressure device 18 can carry out vacuuming process to get −0.1 MPa shown on the vacuum-meter taking about 15 minutes in order that the inside of the box vacuum pressure device 18 is guaranteed enough vacuum; then under the vacuum condition the hydraulic presses 13 of the box vacuum pressure device 18 stars to press the stocked laminated boards 10 coated with thermosetting binder in the briquette process with 35 Tons pressure; after exerting pressing force, the vacuum condition can be removed in the inside of the box vacuum pressure device 18 , open the windows 14 . 2 of the box vacuum pressure device 18 , and via them the operator can secure the fasteners 8 in for keeping the pressure exerting on the stacked laminated boards 10 after removing the pressure coming from the hydraulic press 13 of the box vacuum pressure device 18 , so that the stacked laminated boards stocked on the trailer carrier 1 are exerted with pressing force by the trailer carrier 1 its own after the trailer carrier 1 is took out of the vacuum box of the box vacuum pressure device 18 , in order to guarantee the binder layers between the sheets of the laminated boards 10 are solidified under the pressure fully; after securing the fasteners 8 in, the pressing force coming from the hydraulic presses 13 can be removed; then the door 14 . 1 is opened, the trailer carrier 1 can be exited out of the box vacuum pressure device 18 to be pushed to the heating solidifying site, in there the oil-pipes of the conducting blocks 12 are connected to the connectors 12 . 1 located on the wall of the vacuum box respectively to form a hot oil loop in the conducting blocks 12 with the outer hot oil resource, in order to make the conducting blocks 12 transfer the heat power to the laminated boards 10 to solidify the thermosetting binder completely with 100° C. in temperature for 2 hours; after the trailer carrier 1 is exited from the box vacuum pressure device 18 , the vacuum box is ready to place the next stacked trailer carrier 1 in for next circulation; the trailer carrier 1 exited from the box vacuum pressure device 18 is placed in heating solidifying site for waiting the E-7-2 thermosetting binder layers solidified completely in the heating solidifying site; after the binder is solidified fully, secure out the fasteners 8 , remove the top board 6 , the finished artificial stone laminated boards 10 can be took out from the trailer carrier 1 for emptying the trailer carrier 1 for reloading stacked sheets of the laminated boards 10 in next circulation; the finished laminated board 10 will be cut off the solidified binder exuded out along the edges by the trim cutter to become a quantified goods for entering the storing house. [0063] Said E-7-2 thermosetting binder can be bought in the Chinese market. THE THIRD PREFERRED EMBODIMENT [0064] Referring to FIG. 1 , FIG. 2 and FIG. 8 , the method of the present invention is described in detail as followings: [0065] Take 5 pieces of marble sheets and 10 pieces of artificial stone sheets out as one piece of marble sheet and two pieces of artificial stone sheets in one set, firstly coat SY-21 cold binder on the contacting surfaces of said artificial stone sheets and said marble sheet in one set; next stack all sets of laminated boards 10 up on the top surface of the pressure block 5 in the way as same as the first embodiment; after stacking all the sets of laminated boards 10 up, cover the casing vacuum pressure device 18 ′ on the pressure block 5 to take sealing connection by engaging the seal loop 19 of the vacuum casing on the pressure block 5 of the trailer carrier 1 , then via opening the windows 14 . 2 of the casing vacuum pressure device 18 ′, plugging the latches 9 in connects the combined base 15 of the hydraulic presses 13 to the guide pillars 7 of the top board 6 , next close the windows 14 . 2 of the vacuum casing up, the casing vacuum pressure device 18 ′ can carry out vacuuming process as same as the steps described in the first preferred embodiment; then under the vacuum condition the hydraulic presses 13 of the casing vacuum pressure device 18 ′ stars to press the stocked laminated boards 10 coated with cold binder in the briquette process with 20 Tons pressure; after exerting pressing force, the vacuum condition can be removed in the inside of the casing vacuum pressure device 18 ′, open the windows 14 . 2 of the casing vacuum pressure device 18 ′, and via them the operator can secure the fasteners 8 in for keeping the pressure exerting on the stacked laminated boards 10 after removing the pressure coming from the hydraulic presses 13 of the casing vacuum pressure device 18 , so that the stacked laminated boards 10 stocked on the trailer carrier 1 are exerted with pressing force by the trailer carrier 1 its own after the vacuum casing of the casing vacuum pressure device 18 ′ is removed, in order to guarantee the binder layers between the sheets of the laminated boards 10 are solidified under the pressure fully; after securing the fasteners 8 in, remove the latches 9 from the locking configuration to depart the combined base 15 from the guide pillars 7 of the top board 6 , remove the casing vacuum pressure device 18 ′ and exit the trailer carrier 1 to one side for the casing vacuum pressure device 18 ′ being ready to place the next stacked trailer carrier 1 in for next circulation; the trailer carrier 1 exited from the casing vacuum pressure device 18 ′ is placed in idle state for waiting for the SY-21 cold binder layers solidified completely, it will take about 3 hours; after the binder is solidified fully, secure out the fasteners 8 , remove the top board 6 , the finished artificial stone laminated boards 10 can be took out from the trailer carrier 1 for emptying the trailer carrier 1 for reloading stacked sheets of the laminated boards 10 in next circulation; the finished laminated board 10 will be cut off the solidified binder exuded out along the edges by the trim cutter to become a quantified goods for entering the storing house. THE FOURTH PREFERRED EMBODIMENT [0066] FIG. 9 is a side view showing the sealed connection of the vacuum box and the hydraulic presses of the present invention, it illustrates that the conventional hydraulic presses 13 are mounted on the vacuum box 14 with bolts 20 cooperating to the seal loop 13 . 1 to connecting into one body integrally, the pressure bar 13 . 2 of the hydraulic press 13 passes through the roof side 14 . 3 of the vacuum box 14 so that the tip end of pressure bar 13 . 2 stretches into the inside of the vacuum box 14 to join with the combined base 15 for connecting to the guide pillars 7 of the top board 6 ; said hydraulic press 13 is a conventional hydraulic press. [0067] Obviously, above-mentioned preferred embodiments of the present invention are some special examples trying to describe the present invention, not to be used for limiting the process way of the present invention. To the common technicians involving in this field, the other changes in the structure also can be made up basing on the description further. So all the embodiments, just for this reason, can not be explained into detail or covering everything. But, based-on the base spirit of the present invention, all the deducted changes are in the claimed range of the present invention.
The present invention provides a method for manufacturing laminated board and apparatuses used on the same involving the laminated board flow-line production field, in which the method is to stack the sheets coated with binder of the laminated board up on the pressure block of the trailer carrier placed into the inside of the vacuum pressure device, to briquette the sheets coated with binder into the laminated boards by the vacuum pressure device under the vacuum condition, to secure in the fasteners on the top board to keep the pressure exerting on the stacked laminated boards after exiting the trailer carrier from the vacuum pressure device for waiting to the binder solidifying in cold or heating; to secure out the fasteners, the top board from the top side of the trailer carrier sequentially, finally take the finished laminated boards out to empty the trailer carrier for the next circulation; the apparatuses used for manufacturing the laminated board includes a vacuum pressure device for taking to briquette the laminated boards and trailer carriers comprising a pressure block, a top board, and fasteners, and conducting blocks used for heating the thermosetting binder to solidify. The present invention not only can reduce the equipment cost, but also enlarge the production scale and improve production efficiency to carry out flow-line production to meet the requirement of the market.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to machine rests for pistols and more particularly relates to a new and improved pistol rest which provides stable securement and accommodation of a variety of pistols of a compact size and effective organization for use in the testing of pistols and ammunition. 2. Description of the Prior Art The use of machine rests in the testing of firearms and associated ammunition is well known in the prior art. As may be appreciated, these devices have typically been of elaborate construction or of substantial size to require an inordinate amount of space in use, and as such their employment in the firearm testing has been somewhat limited. In this connection, there have been several attempts to develop pistol rest apparatus which may be easily and efficiently utilized when desired. For example, U.S. Pat. No. 125,743 to Lehnert provides for a pivotal table top releasably securable at a forwardmost position to enable rearward pivoting and attachment for associated firearms. While an effective securement means for a firearm, the Lehnert patent fails to provide the shock absorbency or compactness of structure required in the testing of pistols and the like. U.S. Pat. No. 2,458,608 to Lea sets forth a pistol machine rest wherein a pistol is securable to a plurality of spaced plates and said plates are in turn securable to a support surface. The Lea patent provides means for securing a pistol and further provides a modicum of adjustability but is of rudimentary form and of much more limited applicability than the instant invention. U.S. Pat. No. 2,731,829 to Wigington et al sets forth a pistol rest including shock absorbency members in the form of springs coaxially positioned about guide rails and while an improvement over the previous pistol-type machine rests, the Wigington patent fails to provide a dampening mechanism as well as a convenient organization for use in pistol testing forums. U.S. Pat. No. 2,877,689 to Pribis sets forth a further pistol rest wherein a storage compartment for a pistol has elements stored therein for positioning within a box-like portion for positioning of pistol therein. The patent is of interesting structure relative to pistol stands and the like but is of relatively remote organization and function as related to the instant invention. U.S. Pat. No. 3,343,411 to Lee sets forth a pistol rest pivotally secured at a rearwardmost position with a forwardly oriented adjusting screw threadedly secured to an elongate engagement member to secure an associated pistol. The Lee patent fails to present an effective compact organization for the provision of dampening means in the use of pistol rests and the like with various shock absorbency members. As such it may be appreciated that there is a continuing need for a new and improved pistol rest apparatus which addresses both the problem of effectiveness and stability and in this respect, the present invention substantially fulfills this need. SUMMARY OF THE INVENTION In view of the foregoing disadvantages inherent in the known types of pistol rests now present in the prior art, the present invention provides a pistol rest apparatus wherein the same is of compact construction and of effective and efficient organization to enable securement of a wide range of pistols and further permits an adjustable positioning of a pistol rest relative to intended targets as well as providing multiple shock absorbing features. As such, the general purpose of the present invention, which will be described subsequently in greater detail, is to provide a new and improved pistol rest which has all the advantages of the prior art pistol rests and none of the disadvantages. To attain this, the present invention comprises a horizontal support member including a pistol rest securement means securable proximate a first end and a shock absorbency member secured proximate a second end with a pivotal axis positioned between the first and second end and an adjustment screw enabling vertical adjustment of the horizontal member for adjusting aiming of a secured pistol. A triangulated leg support arrangement is provided to effect stability and securement of the pistol rest apparatus to an associated surface. My invention resides not in any one of these features per se, but rather in the particular combination of all of them herein disclosed and claimed and it is distinguished from the prior art in this particular combination of all of its structures for the functions specified. There has thus been outlined, rather broadly, the more important features of the invention in order 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. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto. Those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention. It is therefore an object of the present invention to provide a new and improved pistol rest which has all the advantages of the prior art pistol rests and none of the disadvantages. It is another object of the present invention to provide a new and improved pistol rest which may be easily and efficiently manufactured and marketed. It is a further object of the present invention to provide a new and improved pistol rest which is of a durable and reliable construction. An even further object of the present invention is to provide a new and improved pistol rest which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such pistol rest economically available to the buying public. Still yet another object of the present invention is to provide a new and improved pistol rest which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith. Still another object of the present invention is to provide a new and improved pistol rest wherein the same accommodates a variety of pistols. Yet another object of the present invention is to provide a new and improved pistol rest wherein the same effects shock absorption of associated impacting of a discharged pistol secured to the rest. Even still another object of the present invention is to provide a new and improved pistol rest wherein the same may be adjustable to accommodate varying distances of target and impacts of bullets. These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated preferred embodiments of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein: FIG. 1 is an isometric illustration of the pistol rest of the instant invention. FIG. 2 is a top orthographic of the pistol rest of the instant invention. FIG. 3 is an orthographic side view taken in elevation of the pistol rest of the instant invention. FIG. 4 is an orthographic view taken in elevation of the instant invention along the lines 4--4 of FIG. 2 in the direction indicated by the arrows. FIG. 5 is an orthographic view taken in elevation of the pistol rest of the instant invention along the lines 5--5 of FIG. 2 in the direction indicated by the arrows. FIG. 6 is an end orthographic view of pistol securement means of the instant invention. FIG. 7 is a side orthographic view of the pistol securement means of the instant invention. DESCRIPTION OF THE PREFERRED EMBODIMENT With reference now to the drawings, and in particular to FIGS. 1 to 7 thereof, a new and improved pistol rest embodying the principles and concepts of the present invention and generally designated by the reference numeral 10 will be described. More specifically, it will be noted that the pistol rest apparatus 10 essentially comprises a securement means 11 for the rigid securement of a pistol therein removably securable to a support plate 12. The securement means 11 includes a "U" shaped pistol mount 13 formed with a generally planar horizontal lower surface including two upwardly depending legs, essentially as illustrated. A first jaw face 15 is rigidly secured to an upstanding first leg of the "U" shaped pistol mount 13 wherein a second jaw face 16 is positionable relative to first jaw face 15 by means of its attachment to a reciprocable second jaw support 17 displaceable within the "U" shaped pistol mount 13 by a rotatable handle 14 that may rotate a first threaded member 18, as illustrated in FIG. 6, that is itself secured to reciprocable second jaw support 17 to enable the accommodation of a variety of pistol grips between the first and second jaw faces 15 and 16 respectively. The first and second jaw faces 15 and 16 are preferably formed of a polymeric-like material of memory retentent character to enable a non-marring securement of a pistol grip therebetween. The "U" shaped pistol mount 13 is securable proximate a first terminal end of support plate 12 by means of a second threaded member 19 formed with a manually manipulatable screw head 20 where essentially, as illustrated in FIG. 4, the second threaded member 19 is positionable through an opening in support plate 12 and by virtue of manually manipulatable screw head 20 clampingly engages the "U" shaped pistol mount 13 to support plate 12 at a terminal end thereof. A "U" shaped support yoke 22 remote from the pistol securement means 11 pivotally secures support plate 12 therebetween. A first pivotal rod 23 is secured between the upstanding legs of support yoke 22, essentially as illustrated in FIG. 5. Reference to FIG. 4 illustrates a third threaded adjustment member 26 threadedly securable through an opening in support plate 12 and engaging an abutment surface 30 of the support yoke 22. The adjustment member 26 enables adjustment of the secure means 11 and thereby enables a variety of pistols and ammunitions to be utilized in conjunction with pistol rest 10. The first pivot rod 23 is positioned through an opening 24 transversely of support plate 12 wherein said opening is oblong and has secured therein a leaf spring 25, as illustrated in FIG. 4, to resist horizontal displacement of support 12 upon pistol discharge and thereby reduces impact loading of the various structural elements of pistol rest 10. Integrally secured to support yoke 22 are a plurality of legs 27, 28, and 29, essentially as illustrated, formed with "L" shaped support feet 27a, 28a, and 29a respectively. The respective support feet are formed with openings therethrough for securement of the support feet and pistol rest apparatus 10 to a desired securement surface (not illustrated). With reference to FIG. 4, dampening of the effects of discharge of a pistol secured within the securement means 11 is effected by utilization of a dampener 33 secured to support plate 12 by use of a second pivoted rod 31 wherein the dampener 33 is positioned relative support plate 12 within a "U" shaped recess 32 at a second end remote from the end supportive of securement means 11. The dampener 33 is secured at its lowermost portion to a third pivot rod 34 secured to respective legs 28 and 29, as illustrated in FIG. 5. The arcuate repositioning of support plate 12 upon discharge of a pistol secured therein is limited by abutment surface 35 that will contact the associated underlying surface of support plate 12 should failure of the dampener or mountings thereof occur. As to the manner of usage and operation of the present invention, the same should be apparent from the above description. Accordingly, no further discussion relative to the manner of usage and operation will be provided. With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention. Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
A pistol machine rest is provided with a horizontal member configured for replaceable positioning of a pistol securement member proximate a first terminal end thereof and provided with a shock absorbency organization at the second end with a pivoted securement of the horizontal member between the first and second ends. The horizontal member is vertically positionable to accommodate varying targets at varying distances with a plurality of leg supports for stable securement of the pistol rest.
5
1) FIELD OF THE INVENTION [0001] The present invention relates to alkoxyalkylsilane-modified polysiloxanes, to processes for the production thereof, and to the use thereof. 2) BACKGROUND [0002] Polysiloxanes, or chemically more exactly polyorganosiloxanes, are often referred to as silicones in everyday language. They belong to a group of synthetic polymers in which silicon atoms are linked together through oxygen atoms. Because of their typically inorganic skeleton on the one hand and the organic radicals on the other, polysiloxanes take an intermediate position between inorganic and organic compounds. In some way, they are hybrids and therefore have a unique range of properties, which is based, among other things, on the heat resistance and/or cold resistance as well as the electric properties of the polysiloxanes. [0003] Processes for producing alkoxy-modified siloxanes with low viscosities are extensively described in the prior art. In these processes, triethoxy-modified siloxanes are reacted with alkoxyvinylsilanes by the direct hydrosilylation of siloxanes having a reactive Si—H group. This process is suitable, in particular, for producing polysiloxanes with low molecular weights of up to 15,000 g/mol. However, with increasing molecular weight, it becomes more difficult to achieve complete conversion of the starting materials by means of direct hydrosilylation. Polysiloxanes having a molecular weight of 50,000 g/mol or more are very difficult to produce in this way. [0004] Polysiloxanes having an average molecular weight of up to 20,000 g/mol and a viscosity at 20° C. of about 1,500 mPa·s can be produced by equilibration processes known in the prior art. However, the reaction products obtained often have a high proportion of volatile components, which are undesirable in many applications, for example, in the electrical industry, because they may deposit on contact surfaces and thus cause failures. In order to counteract this phenomenon, the volatile components are usually substantially removed by distillation. Now, it is the object of the present invention to provide an alkoxysilane-modified polysiloxane that is obtained without a distillation step for purification. Another object is to provide a process for producing alkoxyalkylsilane-modified polysiloxanes that avoids the drawbacks of the prior art. SUMMARY OF THE INVENTION [0005] The invention relates to an alkoxyalkyl silane-modified polysiloxane of Formula P and a process for producing an alkoxyalkylsilane-modified polysiloxane having high optical clearness. The polysiloxane may be an oil, a fat, or a rubber-like compound. The process calls for a first organosiloxane contacting a second organosiloxane that has a reactive SiH group, said contacting occurring in the presence of an alkoxyvinylsilane. Employing this process does not require a purification by distillation step. The process does require apparatus for determining hydrogen content, such as that shown in FIG. 1 . BRIEF DESCRIPTION OF THE DRAWING [0006] FIG. 1 shows equipment set up to demonstrate apparatus for determining the hydrogen content during the production process of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0007] In a first embodiment, the object of the present invention is achieved by an alkoxyalkylsilane-modified polysiloxane of the following general formula P: [0000] [0000] in which, independently of one another: R 1 represents R 2 or OR 5 , wherein R 5 is a hydrogen (H) atom or a linear or branched, saturated or unsaturated, optionally substituted hydrocarbon radical with 1 to 8 carbon atoms, in particular, R 5 represents a monovalent hydrocarbon radical with 1 or 2 carbon atoms; R 2 represents R 1 or an oxime radical of formula —O—N═C═R 7 , wherein R 7 is a linear hydrocarbon radical with 4 carbon atoms, or a cyclic hydrocarbon radical with 6 carbon atoms; R 3 is R 1 or R 2 or a monovalent SiC-bonded saturated hydrocarbon radical with 1 to 8 carbon atoms, or a hydrocarbon radical with a terminal carbon-carbon double bond with 2 carbon atoms; R 4 is an aliphatic hydrocarbon radical with 1 to 30 carbon atoms, a phenyl radical, and/or a polyether radical of general formula (CH 2 ) 3 O(C 2 H 4 O) w (C 3 H 6 O) x (C 4 H 8 O) y Q, in which w, x, y are independently the same or different and respectively represent a number from 0 to 50; and Q represents a hydrogen atom or an aliphatic hydrocarbon radical with 1 to 4 carbon atoms; Z is a monovalent SiC-bonded saturated hydrocarbon radical with 2 carbon atoms; m is an integer of from 1 to 200, especially from 1 to 100, especially from 1 to 50; n is an integer of from 1 to 1000, especially from 1 to 500, especially from 1 to 200; o is an integer of from 0 to 50, especially from 0 to 20, especially from 0 to 10; p is an integer of from 1 to 50, especially from 1 to 20, especially from 1 to 10; q is an integer of from 1 to 50, especially from 1 to 20, especially from 1 to 10. [0018] Surprisingly, it has been found that corresponding polysiloxanes, especially those having a viscosity of from 200 mPa·s to 1,000,000 mPa·s at 20° C., can be obtained with a high optical clearness. The alkoxyalkylsilane-modified polysiloxanes according to the present invention may be oils or fats, or even rubber-like compounds. [0019] In the polysiloxane according to the invention, the radical R 1 may have the meaning of R 2 . Further, R 1 may have the meaning of OR 5 , wherein R 5 is a hydrogen atom or a linear or branched, saturated or unsaturated, optionally substituted hydrocarbon radical with 1 to 8 carbon atoms. To the extent where they are at different positions in the molecule, the radicals R 1 indicated in formula P may independently take the respective definition. Preferably, the radical R 1 is identical within the polysiloxane of general formula P. [0020] If R 1 is a hydrocarbon radical with 1 to 8 carbon atoms, it may be linear or branched according to the invention. Also, it is possible to employ a saturated or unsaturated hydrocarbon radical. The hydrocarbon radical may be substituted. Examples of substituted radicals R 5 include haloalkyl radicals, such as a 3-chloropropyl radical. Fluorine, bromine or iodine may also be employed as halogen atoms instead of chlorine. Preferably, R 5 is a monovalent hydrocarbon radical with 1 or 2 carbon atoms. [0021] Independently of R 1 , the radical R 2 in general formula P may have the same meaning as R 1 . R 2 may also be an oxime radical of formula —O—N═C═R 7 . The radical R 3 may have the same meaning as R 1 and/or R 2 . In addition, R 3 may also represent a monovalent SiC-bonded saturated hydrocarbon radical with 1 to 8 carbon atoms, or a hydrocarbon radical with a terminal carbon-carbon double bond with 2 carbon atoms. Examples of corresponding unsaturated radicals include, in particular, alkenyl radicals, such as a vinyl radical. According to the invention, it is possible that R 2 and R 3 may independently take different meanings to the extent where the radicals occur at different positions within the molecule of general formula P, as set forth above with respect to R 1 . Preferably, the radical R 2 is the same within the polysiloxane according to the general formula P. Also, the radical R 3 preferably has the same meaning within formula P. [0022] Also R 4 , which is an aliphatic hydrocarbon radical with 1 to 30 carbon atoms, a phenyl radical, and/or a polyether radical of general formula (CH 2 ) 3 O(C 2 H 4 O) w (C 3 H 6 O) x (C 4 H 8 O) y Q, may have the same or different meanings within the molecule of general formula P. Preferably, the radical R 4 is the same radical in each occurrence in the total molecule. [0023] In another embodiment, the object of the present invention is achieved by a process for producing alkoxyalkylsilane-modified polysiloxanes, in which a first organosiloxane (a) with two or more terminal aliphatic unsaturated reactive groups and a second organosiloxane (b) with at least one reactive SiH group are contacted with one another in the presence of an alkoxyvinylsilane (c) having a terminal aliphatic unsaturated reactive group. [0024] The process according to the invention enables the production of alkoxyalkylsilane-modified polysiloxane oils or rubber-like compounds with a viscosity of from 200 mPa·s to 1,000,000 mPa·s at 20° C. In the process, three mutually different organosiloxanes are contacted with one another. Both the first organosiloxane (a) and the alkoxyvinylsilane (c) have an aliphatic unsaturated reactive group. The first organosiloxane (a) differs from the alkoxyvinylsilane (c) in that the first organosiloxane (a) has two terminal aliphatic unsaturated reactive groups. Thus, the first organosiloxane (a) serves as a chain extender in the preparation of the polysiloxane according to the invention. In contrast, the alkoxyvinylsilane (c) has only one terminal aliphatic unsaturated reactive group. By controlling the proportion of alkoxyvinylsilane (c) in the reaction mixture for producing the polysiloxane according to the invention, the chain length of the final product to be obtained can be controlled. [0025] Surprisingly, it has been found that, in particular, a ratio of aliphatic unsaturated reactive groups to the number of SiH bonds within a range of from 1.5:1 to 0.5:1, especially 1.2:1, and especially 1:1, leads to a desired product. The amount of aliphatic unsaturated reactive groups corresponds to the groups that are contained in both the first organosiloxane (a) and the alkoxyvinylsilane (c). The ratio according to the invention enables the reactive SiH bonds of the second organosiloxane (b) to react completely. Thus, a complete or at least almost complete reaction of the starting materials with one another takes place. The product obtained preferably does not contain any liquid components in the form of starting materials. [0026] Further purification by distillation of the product obtained by the process according to the invention is not necessary, especially if the ratio of aliphatic unsaturated reactive groups to SiH bonds is within the range according to the invention. At this ratio, a complete reaction of the starting materials takes place, whereby a highly viscous polysiloxane that is an optically clear product with a high proportion of solids is obtained. The solids proportion of the polysiloxane obtained is, in particular, at least 99.5% by weight, and preferably 100% by weight. The solids proportion can be determined by gravimetric infrared drying. Infrared drying can be effected in a Moisture Analyzer. Thus, for example, an empty aluminum weighing dish is placed into the sample dish holder of a Mettler Toledo Halogen Moisture Analyzer HG 53, sea sand is sprinkled over it, and the unladen weight is read. 1.0 g of product (alkoxysilane-modified polysiloxane) is uniformly applied to the dish. After start of the program, the sample is heated to 140° C. After the mass has remained constant for 30 seconds, the measuring process is complete, the sample drawer is automatically moved out, and the solids proportion as a result is indicated and can be printed. [0027] The first organosiloxane (a) is preferably an alkene-substituted polydiorganosiloxane, especially a dimethylsiloxane with terminal vinyl and/or allyl and/or hexenyl groups bonded to silicon. More preferably, it is a molecule of the following general formula A: [0000] [0000] in which R 4 is an aliphatic hydrocarbon radical with 1 to 30 carbon atoms, a phenyl radical, and/or a polyether radical of general formula (CH 2 ) 3 O(C 2 H 4 O) w (C 3 H 6 O) x (C 4 H 8 O) y Q, in which w, x, y are independently the same or different and respectively represent a number from 0 to 50; and Q represents a hydrogen atom or an aliphatic hydrocarbon radical with 1 to 4 carbon atoms; and n is a whole natural number of from 1 to 1000, especially from 1 to 500, especially from 1 to 200. [0031] The molecular weight of the first organosiloxane (a) is not limited and can be chosen freely. Preferably, it is a liquid organosiloxane with a viscosity at 20° C. within a range of from 200 mPa·s to 1,000,000 mPa·s. However, it may also be a rubber-like compound with a high viscosity at 20° C. within a range of from 200,000 mPa·s to 1,000,000 mPa·s. Such a rubber-like compound usually has a degree of polymerization of from 3,000 to 10,000. The degree of polymerization means the number of monomer units in one polymer molecule. More preferably, the first organosiloxane (a) is a dimethylsiloxane with terminal dimethylvinyl groups having a viscosity within a range of from 200 mPa·s to 50,000 mPa·s at 20° C. [0032] The alkoxyvinylsilane (c) is preferably represented by the general formula C. [0000] [0000] in which R 1 and R 2 have the same meaning as set forth with respect to formula P, and R 3 is an aliphatic unsaturated group. [0033] The second organosiloxane (b) has, in particular, one or more terminal and/or pendant reactive SiH groups. Preferably, it has two or more reactive SiH groups. In particular, it is a molecule according to the following general formula B: [0000] [0000] in which, independently of one another: R 4 is an aliphatic hydrocarbon radical with 1 to 30 carbon atoms, a phenyl radical, and/or a polyether radical of general formula (CH 2 ) 3 O(C 2 H 4 O) w (C 3 H 6 O) x (C 4 H 8 O) y Q, in which w, x, y are independently the same or different and represent a number from 0 to 50; and Q represents a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms; R 6 is a hydrogen atom or a methyl radical; m is an integer of from 1 to 200, especially from 1 to 100, especially from 1 to 50; and o is an integer of from 0 to 50, especially from 0 to 20, especially from 0 to 10. [0039] According to the invention, the second organosiloxane (b) may have one or more pendant SiH groups. Also, it is possible that it has one or more terminal SiH groups. The presence of both one or more pendant and one or more terminal SiH groups is also possible according to the invention. In this case, the selection of the position of the SiH groups determines whether the product obtained is linear or branched. [0040] The process according to the invention is preferably performed in the presence of a catalyst (d). In particular, the catalyst (d) is a hydrosilylation catalyst that includes platinum. Suitable catalysts include, for example, fluoroplatinic acid, platinum acetylacetonate, complexes of platinum halides with unsaturated compounds, such as ethylene, propylene, organovinylsiloxanes or styrene, hexamethyldiplatinum, PtCl 2 ×PtCl 3 , or Pt(CN) 3 . More preferably, the catalyst (d) includes complex compounds of platinum compounds with vinylsiloxane. [0041] Preferably, the catalyst (d) is employed in such an amount that the proportion of platinum is from 1 to 100 ppm, especially from 1 to 10 ppm. This amount is sufficient to catalyze the reaction described above, especially at room temperature. Larger amounts of catalyst (d) would only increase the cost of the process. The proportion in ppm is expressed in ppm by weight. One ppm platinum means that one gram of platinum is employed, based on one thousand kilograms of reaction mixture consisting of the first organosiloxane (a), the second organosiloxane (b), and the alkoxyvinylsilane (c). [0042] In particular, the process according to the invention is performed at a temperature within a range of from −20° C. to 200° C., especially from 10° C. to 120° C., more preferably from 40° C. to 100° C. At such temperatures, the catalyst (d) according to the invention, which may be Karstedt's catalyst, in particular, is particularly active. Therefore, the reaction according to the invention is catalyzed quickly, and the desired product, which is a colorless, optically clear polymer in the form of a polysiloxane, is obtained within a short time. [0043] Preferably, no more active hydrogen-silicon bonds are found in polysiloxanes produced according to the invention. In particular, the proportion of active hydrogen-silicon bonds is zero. In order to determine the hydrogen content from H—Si bonds in the polysiloxanes according to the invention, a particular amount of the polysiloxane is placed into a round-bottom flask and weighed. After the flask is placed below a dropping funnel with a gas line, the excess pressure produced is relaxed through a second neck by opening a stopcock. [0044] Thereafter, the stopcock is closed again. Through a dropping funnel, a 10% solution of KOH in butanol is added in excess. The following reaction ensues: [0000] [0045] The generated hydrogen is passed through a gas line bypassing the stopcock of the dropping funnel, where it produces excess pressure. This excess pressure displaces a concentrated KCl solution in a volume measuring column connected thereto, and thus the generated volume of H 2 is measured. It is to be taken care that the level in the measuring column at the beginning is exactly at zero, and that a level compensation between the meniscus in the measuring column and the meniscus in the funnel at the end of the flexible tube for filling the column is always effected when reading the volume in order not to produce any pressure difference because of the levels of the water columns. [0046] Thus, the hydrogen content is calculated as follows: [0047] The ideal gas law applies: p*V=n*R*T [0048] where [0049] p=pressure (current measured value) [Pa] [0050] V=volume (measured value) [ml] [0051] n=amount in moles=m/M=mass [g]/molecular mass [g/mole] [0052] R=ideal gas constant=8.3144621 J/(mol*K) [0053] T=temperature in K [0054] Therefrom, it follows that: [0000] [0055] FIG. 1 schematically shows an appropriate apparatus for determining the hydrogen content. The magnetic stirrer is designated by 1 . In the water bath for cooling 2 , there is the round-bottom flask 3 , which contains the polysiloxane and a stir bar. A pressure equalization can be effected through gas line 4 , which is connected to the dropping funnel 5 . The dropping funnel 5 contains a 10% KOH in butanol solution. The generated hydrogen gas is passed through a flexible tube 6 filled with concentrated KCl solution. At the volume measuring column 7 , the generated volume of H 2 can be measured. At the end of flexible tube 6 , there is a compensation vessel 8 for level compensation. [0056] The viscosity of the polysiloxanes and organosiloxanes can be determined with a Brookfield viscometer RVTDV II. The measurement is effected at 20° C. Values of viscosity stated in the present description are each based on a temperature of 20° C. unless stated otherwise. [0057] The determination of the average molecular weight of the polysiloxanes or organosiloxanes was effected by means of GPC (gel permeation chromatography). Toluene was used as the mobile phase. The flow rate was 1.0 ml per minute at a pressure of 100 bar and at a temperature of 30° C. For the determination, 3 g of the polymer or oligomer was dissolved in one liter of toluene. A polydimethylsiloxane (PDMS) standard from the company PSS in a molecular weight range of from 311 to 381,000 g/mole was employed for calibration. [0058] The polysiloxane according to the invention can be employed, in particular, in room temperature curing silicone adhesives, silicone sealants and silicone coating agents. EXAMPLES Example 1 [0059] Into a round-bottom flask with a magnetic stir bar, a thermometer and a reflux condenser, 915.66 g of a vinylsiloxane polymer with a terminal vinyl group and an average molecular weight of 31,000 g/mole, a viscosity of 1,000 mPa·s and a solids content of 99.5% was filled at 140° C. This amount of 915.66 g corresponds to 2 moles. To the vinylsiloxane polymer, there were added 79.37 g of an organosiloxane (3 moles) with terminal H—Si bonds having an average molecular weight of 816 g/mole, a viscosity of 15 mPa·s and a hydrogen content of 1,400 ppm, and 4.87 g of vinyltrimethoxysilane (2 moles) having a molecular weight of 148 g/mole. The mixture obtained was heated at 50° C. Subsequently, 3 ppm platinum in the form of Karstedt's catalyst was added. The temperature was increased to 90° C. At this temperature, the mixture was stirred for one hour. Subsequently, the reaction mixture was cooled down to room temperature. The hydrogen content of the product obtained was determined in view of H—Si bonds. The hydrogen content was zero. Thus, the hydrosilylation was complete. [0060] The polymer obtained had a molecular weight of 65,000 g/mole (determined by means of GPC), a solids content of 99.8% by weight, and a viscosity of 12,500 mPa·s at 20° C. In addition, the product obtained was clear. The polymer was in the form of a gel and corresponded to the following general formula 1: [0000] Example 2 [0061] In the same reaction set-up as described in Example 1, 916.7 g of a terminal vinylsiloxane polymer with an average molecular weight of 31,000 g/mole, a viscosity of 1,000 mPa·s at 20° C. and a solids content (determined by means of GPC at 140° C.) of 99.5%, together with 73.9 g of a third organosiloxane with terminal H—Si bonds having a molecular weight of 816 g/mole, a viscosity of 15 mPa·s and a hydrogen content of 1,400 ppm, 1.802 g of a siloxane having terminal and pendant H—Si bonds with a molecular weight of 2,110 g/mole, a viscosity of 500 mPa·s at 20° C. and a hydrogen content of 1,715 ppm, and 7.5 g of vinyltrimethoxysilane having a molecular weight of 148 g/mole were mixed together. [0062] The mixture was heated at 50° C. At this temperature, 5 ppm platinum in the form of Karstedt's catalyst was added. Subsequently, the temperature was increased to 100° C. and maintained for 2 hours. After the reaction mixture had cooled down to room temperature, the hydrogen content in the form of H—Si bonds of the product obtained was determined. The hydrogen content was zero, whereby it could be demonstrated that the hydrosilylation reaction had run to completion. The polymer obtained had a molecular weight of 49,800 g/mole (determined by means of GPC), a solids content of 99.85% by weight, and a viscosity of 5,100 mPa·s. These values correspond to the values calculated on the basis of the selected starting compounds. The product corresponds to a product of the following formula 2: [0000] [0063] In a further cross-linking reaction, the product obtained could be cured to a gel. The siloxane prepared was optically transparent. Example 3 [0064] By analogy with Example 1, 916.9 g of a siloxane polymer with terminal vinyl groups (molecular weight 31,000 g/mole, viscosity 1,000 mPa·s at 20° C., solids content 99.5% by weight at 140° C.), 78.5 g of organosiloxane with terminal hydrogen atoms (average molecular weight 816 g/mole, viscosity 15 mPa·s, hydrogen content 1,400 ppm), and 3.7 g of vinyltrimethoxysilane (molecular weight 148 g/mole) were mixed together. [0065] The mixture was heated at 50° C. At this temperature, 5 ppm platinum in the form of Karstedt's catalyst was added. After the temperature had been increased to 100° C. and the mixture stirred at this temperature for 2 hours, the mixture was cooled down to room temperature. The hydrogen content of the product obtained was determined. It was zero, so that it can be considered that the hydrosilylation had run to completion. [0066] The polysiloxane obtained had a molecular weight of 112,000 g/mol (determined by means of GPC), a solids content of 99.85% by weight, and a viscosity of 51,000 mPa·s. The values are in agreement with values calculated beforehand. [0067] The product corresponds to a product of the following formula 3: [0000] [0068] The product obtained did not show any turbidity, but was optically clear. In further cross-linking reactions, it could be processed further into a gel.
The present invention relates to alkoxyalkylsilane-modified polysiloxanes, to processes for the production thereof, and to the use thereof.
2
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS [0001] This application is a continuation of U.S. application Ser. No. 12/252,839, titled “Recyclable Blister Pack and Process of Making,” filed on Oct. 16, 2008, which claims the benefit of U.S. Provisional Application No. 60/999,329, filed Oct. 17, 2007, both of which are incorporated herein by reference in their entireties. FIELD OF THE INVENTION [0002] The present invention relates to an easily recyclable blister pack system and to the process of making DESCRIPTION OF RELATED ART [0003] Consumer packaging has evolved from simple cartons that protected the product, but which required opening the carton to view the contents, to blister/card packages that encapsulate the product while still allowing viewing the product, to thermoformed clamshell containers that allow tamper-proof viewing of the finished product. Each step in the evolution of the packaging has increased the cost of the package, the amount of hydrocarbons required for manufacture, and reduced the opportunity for recycling the packaging materials following removal of the product. [0004] In the case of card/blister packages, the product is inserted into a thermoplastic blister that is then heat-sealed (at elevated temperature and pressure) to a printed chipboard card that has been coated with a heat-sensitive adhesive. When the product is removed from the package, the adhesive and fibers bond to the blister, and prevent efficient re-cycling of the blister material. In addition, the card/blister packages are subject to size and weight limitations because the assembled package must fit into heat-sealing machines. [0005] In the case of clamshell packages, the product is inserted into a transparent thermoplastic shell that fully encloses it. The shell consists of two halves joined by a hinge made of the material found in the shell. The clamshell is folded in half to form an enclosure that completely encloses the packaged product. The two halves of the assembled clamshell can be held together by a friction-fit between the assembled halves, or by means of a mechanical fastener such as a staple. For heavy or high value products, the shell may be heat or radio frequency (RF) sealed for tamper resistance, but the heat-sealing operation frequently causes customer dissatisfaction due to the extreme difficulty in opening the pack to use the product. In addition, the clamshell package uses two to three times the hydrocarbons required for a card/blister package. The clamshell materials are not easily separable for recycling. [0006] Consumers are increasingly concerned with the excessive amounts of plastic, cardboard and paper associated with the packaging of consumer products, as are various environmental conservation groups. Some major consumer product retailers have also expressed dissatisfaction with currently available consumer product packaging options, especially those with a high impact to the environment. [0007] One such national retailer has developed a “sustainability scorecard” that measures the environmental impact of the packaging used for consumer products. The sustainability scorecard is used to reward suppliers that have developed or utilized sustainable packaging products and technology. Suppliers that do not utilize sustainable packaging will be at a competitive disadvantage. [0008] By way of example, the sustainability scorecard includes the following factors that are considered: greenhouse gasses (e.g., carbon dioxide (CO2) created per ton of packaging production, material value, product-to-package ratio, cube utilization, cost of transportation, total recycled content, recovery value, renewable energy use in production, and innovativeness. [0009] Accordingly, there is a recognized need for new packaging products and packaging manufacturing techniques that minimize impact to the environment throughout the entire life cycle of the product from manufacture through sale, use, and ultimate disposal. [0010] It is an object of the invention to provide a packaging system that meets the sustainability scorecard targets and offers significantly improved recyclability SUMMARY OF THE INVENTION [0011] The present invention provides an easily and efficiently recyclable packaging system for consumer products capable of incorporating full color graphics, tamper and theft resistance, use of recycled materials (RPET blister and post-consumer corrugate), and a dry tack cohesive adhesive. The packaging consists of three components: a die-cut substrate (a corrugate body in the preferred embodiment), a thermoformed RPET blister layer, and a dry tack cohesive adhesive. [0012] In its simplest form, the invention comprises a substrate having first and second regions, a dry tack cohesive layer applied to the first and second regions, and a blister layer for accepting a product and having a surface along its periphery capable in use of capture between the dry tack cohesive layers The adhesive properties of the cohesive layer are selected such that it is capable of forming a seal only with itself and the substrate, and so it is separable from the blister layer without leaving substrate residue to facilitate recyclability. [0013] In the preferred embodiment, the invention comprises a blister pack system including a substrate having first and second regions with at least one of the regions having an opening formed therein for receiving a product, a dry tack cohesive layer applied to the first and second regions, and a blister layer shaped to accept a product and having a surface along its periphery capable in use of capture between the dry tack adhesive layer on the first and second regions. The adhesive properties of the cohesive layer are selected such that it is capable of forming a seal only with itself and the substrate, and so that it is separable from the blister layer without leaving substrate residue to facilitate recyclability. [0014] The process for assembling the blister pack system includes the steps of forming a dry tack cohesive layer above a substrate having first and second regions, with one of the regions having an opening formed therein, the substrate is folded along a line dividing the first and second regions and the blister layer positioned between the first and second regions of the substrate so the shaped portion of the blister layer accepts a product and passes through the opening formed in the substrate, and so that its peripheral surface is between the first and second regions having the dry tack cohesive layer formed thereon. The system is sealed by applying pressure to the substrate along the peripheral surface of the first and second regions. The cohesive adhesive adheres to itself thereby holding the blister layer securely in place. The adhesive properties of the cohesive layer are selected such that it is capable of forming a seal only with itself and the substrate, and so it is separable from the blister layer without leaving substrate residue to facilitate recyclability. BRIEF DESCRIPTION OF THE DRAWINGS [0015] FIG. 1 is a top view of the die-cut substrate or corrugate body. [0016] FIG. 2 depicts the thermoformed RPET blister layer. [0017] FIG. 3 is a schematic representation of the bottom single roll coating process. [0018] FIG. 4 shows an assembled blister pack system with the products installed in the blister layer, and the blister layer installed in the corrugate body. DETAILED DESCRIPTION OF THE INVENTION [0019] FIG. 1 shows a planar substrate 10 , which in the preferred embodiment is corrugate body having a generally rectangular shape, but which can also be a chipboard material. Although not shown in FIG. 1 , substrate 10 may be pre-printed with a color graphic label describing the product (also not shown). The substrate is generally divided into two halves or regions 12 and 14 separated by a centerline 16 which, to facilitate folding of the substrate, may be formed by scoring or perforation. A pair of die-cut openings 18 and 20 are formed, respectively, in regions 12 and 14 of the substrate. While two openings 18 and 20 are shown in FIG. 1 , not all packaging applications require both openings. The die-cut openings generally approximate the outline of the product being packaged. Substrate 10 is sized to allow approximately a one inch sealing area 22 along the perimeter of the substrate and surrounding the die cut openings, as suggested by dotted line 24 . The width and shape of sealing area 22 can be varied to suit the size and weight of the product to be packaged. Larger, heavier products typically require a wider sealing area to ensure integrity of the package. [0020] The thermoformed blister layer 30 , shown in FIG. 2 , is produced preferably from recycled polyethylene terephthalate (RPET) resin with a nominal thickness of 10-15 mils (0.010-0.015 in.). The blister layer is produced in a well known manner by placing RPET film into a forming die (not shown) under heat and pressure. In the preferred embodiment, the die closely approximates the shape of the product or products to be packaged and forms regions or volumes 32 for receiving the product. The blister layer design incorporates a flange 34 disposed generally between perimeter 36 of the blister layer and edges 38 of regions 32 . In the preferred embodiment, flange 34 is approximately 0.38 in. wide. The flange serves to contain the blister layer and product(s) within the substrate lamination formed when the corrugate body is folded along line 16 ( FIG. 1 ) and sealed as described hereinafter. In those instances when it is desirable that the packaged product be viewable from both sides, a second blister layer (a mirror image of the first) needs to be formed. One blister layer is installed into substrate openings 18 and 20 ( FIG. 1 ). [0021] The unique properties of the dry tack adhesive are a critical element of the package. The adhesive is a formulated latex rubber product that is applied in aqueous (water-based) liquid form, but which dries as a dry tack adhesive (also referred to as a cohesive) which adheres to itself and the substrate, but not to most other surfaces such as the blister layer. This selective adherence property enables the blister layer to be removed or separated for recycling without adhesive residue or fibrous residue material from the substrate, especially a corrugate substrate, remaining on it. This facilitates efficient recycling of the RPET material. The adhesive properties are carefully controlled to create an environmentally acceptable adhesive with unique cohesive properties that also enable handling and transportation of the coated, unsealed substrates without blocking (i.e., the sticking of substrates to one another). [0022] In the preferred embodiment, the physical properties of the adhesive are: aqueous solution; solids 66% by weight viscosity (dry aged) of approximately 4000 CPS (Centipoise) in 3 months; rheology-highly pseudo-plastic and thixotropic, with a ratio of viscosity at one RPM (revolution per minute) to viscosity at 50 RPM of approximately 14:1; pH-alkaline approximately 10.5 ammonical; viscosity (liquid form)-1330 CPS. The viscosity is controlled at application by thinning with water. [0023] The adhesive is applied to the substrate using a conventional roll coating machine. In the preferred embodiment, the single bottom roller coating process is utilized. FIG. 3 shows a typical arrangement. Substrate 10 is positioned for linear movement between rollers 38 and 40 . Adhesive is dispensed onto unprinted substrate surface 42 and is spread uniformly by roller 38 , as the substrate advances in the direction indicated by arrow 48 . The single bottom roll coating process is used to ensure a uniform coating on the unprinted side 42 of the substrate. Care must be taken to prevent transfer of the cohesive to the printed (finished) side 46 of the substrate. Once the substrate has been coated, it is air-dried or heat-dried to produce a tack-free surface. Finished adhesive-coated substrates should be stored in a dry, temperature controlled area maintained at between 40-100 degrees Fahrenheit, and protected from dust and light, especially ultraviolet (UV) light. [0024] Actual packaging of products using the blister pack system is relatively straight forward and typically occurs at a location different from where the substrate coating and blister layer operations occurred. Referring now to FIGS. 1-4 , the products 50 to be packaged and blister layers 30 (assuming the products are to be viewed from both sides) are placed into die-cut openings 18 and 20 of the substrate, and the substrate folded along line 16 . Substrate body 10 is folded so that the cohesive-coated surfaces 42 on each substrate region 12 and 14 are brought together in sealing area 52 ( FIG. 4 ) lying generally outside blister layer perimeter 36 and the outside edges of the substrate 10 and hold flange 34 there-between. Once the substrate has been folded to contain the blister layers and products, area 52 must be pressure-sealed to ensure a complete bond between the two substrate surfaces along area 52 to firmly hold flange 34 of the blister layer in place. Adequate pressure is required to develop the bond. This pressure can be produced by the use of a manual or mechanical weighted roller, or other mechanical means (including commercially available card/blister sealing machines), as long as the resulting pressure is sufficient to bond the cohesive, thereby producing a finished laminated package which contains the products and blisters between the substrate, as shown in FIG. 4 . [0025] It will be appreciated that utilization of perimeter sealing of the substrate, as disclosed, results in a tamper-resistant package and enables packaging of heavy products. [0026] The invention has been disclosed with reference to its preferred embodiment. It will be recognized, however, that variations are possible. For example, different types of substrate materials such as corrugate or chipboard may be used. Similarly, substrates of different thicknesses may be used based upon the size and weight of the product to be packaged. Different printing techniques may also be used to create the graphics on the substrate. Different adhesive formulations may be used instead of the specific cohesive formulation disclosed herein, but the selective adherence properties and ability to handle and ship coated substrates prior to assembly is a critical element of the package. [0027] The foregoing description of one of the embodiments of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above description, without fundamentally deviating from the essence of the present invention. It is intended that the scope of the invention not be limited by this description.
A recyclable blister pack system is provided, including a substrate having a dry tack cohesive adhesive layer deposited on one of its surfaces and a blister layer for receiving a product. The properties of the dry tack cohesive are selected so the blister layer is separable from the substrate without leaving substantial substrate residue on the blister layer. This improves the recyclability of the blister layer.
8
FIELD OF THE INVENTION The present invention generally relates to a microwave heating chamber for use in a vending machine and more particularly, relates to a microwave heating chamber for use in a vending machine that is cylindrically shaped allowing objects to be heated at maximum energy level such that only a short heating time is required. BACKGROUND OF THE INVENTION The technology of using microwave energy for heating an object to a higher temperature has been used for many years. It is especially popular in the food service industry where microwave ovens are widely used. Most microwave ovens are designed with a heating chamber of a rectangular shape and a large volume. The microwave energy is dispersed inside the heating chamber and therefore is not available in a concentrated form. As a result, the time required for heating an object, even though shorter than a conventional convection oven, is still quite appreciable. For instance, most food items, even of a small size, require a heating time of between two to five minutes. The lengthy heating time prohibits the use of microwave ovens in vending machines. In a typical fast food vending machine, after a consumer deposits money into the machine and makes a selection, the selected item is immediately delivered to a discharge chute to the consumer. If a conventional microwave oven is used in such a machine, the heating time required even for a small food item would not be acceptable. A general survey indicates that a consumer demands that a food item to be heated and delivered to him in a very short period of time, i.e., less than 30 seconds. It is therefore an object of the present invention to provide a microwave heating chamber for use in a vending machine that does not have the drawback of conventional microwave heating chambers which require long heating time. It is another object of the present invention to provide a microwave heating chamber for use in a vending machine that is in a cylindrical shape to enable the formation of a maximum microwave energy zone inside the chamber. It is a further object of the present invention to provide a cylindrically shaped microwave heating chamber for use in a vending machine capable of holding a food item at a predetermined position inside the chamber for exposure to maximum microwave energy. It is another further object of the present invention to provide a cylindrically shaped microwave heating chamber for use in a vending machine equipped with an object holding plate such that an object may be heated in a short period of time. It is still another object of the present invention to provide a cylindrically shaped microwave heating chamber for use in a vending machine equipped with an object holding plate such that an object may be heated to a desirable temperature in a time period of less than 30 seconds. SUMMARY OFT HE INVENTION In accordance with the present invention, a microwave heating chamber for use in a vending machine that is in a cylindrical shape and equipped with an object holding plate such that an object can be heated in a very short period of time to a desirable temperature is provided. In the preferred embodiment, a microwave heating chamber for use in a vending machine is provided in a cylindrical shape and mounted vertically with retractable upper and lower end plates for completely sealing the chamber. The chamber wall and the end plates are made of a microwave non-transmissive and non-absorptive material. A retractable object holding plate is inserted in between the two end plates for holding the object to be heated. The plate is mounted at such a position that the object is exposed to the maximum microwave energy. This enables a quick heating of the object to a desirable temperature in a short period of time, i.e., less than 30 seconds. It is more preferred, in the case of a food item, to be heated to a suitable serving temperature in less than 20 seconds. A microwave generator is mounted in a mounting means which includes a circulator for preventing the back flow of microwave energy and possible damage to the microwave generator. The mounting means further includes a wave guide to facilitate the transmission of microwave energy into the heating chamber. The retractable upper and lower end plates and the retractable holding plate are controlled by a control means such that each plate can be withdrawn at a predetermined time. For instance, at the beginning of the operation, the upper end plate retracts to allow an object to fall onto the object holding plate. The upper end plate then returns to its original position to seal the chamber. The passing of the object is sensed by a sensing device in the wall which activates the microwave generator to generate microwave and sending into the chamber cavity for heating the object. After a preset time has passed, the object holding plate and the lower end plate are withdrawn to allow the object to fall into a discharge chute for picking up by the consumer. The novel heating chamber allows an object to be heated in a shorter period of time which makes it suitable for vending machine applications. The present invention is further directed to a method of heating an object in a microwave chamber installed in a vending machine. The method utilizes a cylindrically shaped heating chamber such that microwave energy can be effectively concentrated at certain position inside the chamber cavity. The selection of a heating position for maximum microwave exposure allows a shorter heating time for heating the object to a desirable temperature. BRIEF DESCRIPTION OF THE DRAWINGS Other objects, features and advantages of the present invention will become apparent upon consideration of the specification and the appended drawings, in which: FIG. 1 is a perspective cut-away view of the present invention microwave heating chamber with the microwave generator attached thereto. FIG. 2 is a top view of the present invention microwave heating chamber. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention describes a microwave heating chamber for use in a vending machine that has a small cylindrical shape such that microwave energy can be concentrated at a central location inside the chamber cavity to more efficiently and quickly heating an object. Referring initially to FIG. 1, wherein a perspective view of the present invention microwave heating chamber 10 is shown. The microwave heating chamber 10 has a cylindrically shaped chamber body 12 with a chamber wall 14 and a longitudinal axis 16. The cylindrically shaped chamber body 12 is equipped with an upper mounting flange 18 at the upper extremity 20 of the chamber body 12. The chamber body 12 is also equipped with a lower mounting flange 22 at the lower extremity 24 of the chamber body 12. The upper mounting flange 18 is adapted to receive an object (not shown) transported from a storage compartment (not shown) for admittance into chamber 10. The lower mounting flange 22 is adapted to deliver a heated object to a discharge chute (not shown) of the vending machine. The upper mounting flange 18 and the lower mounting flange 22 are each equipped with mounting means 26 for mounting mechanically to a vending machine. The elongated cylindrically shaped chamber 12 is further equipped with a retractable upper end plate 30 and a retractable lower end plate 32 for sealingly engaging the inside peripheral area of the chamber body 12. The upper end plate 30 and the lower end plate 32 are positioned perpendicular to the longitudinal axis 16 of the chamber. The upper end plate 30 is controlled and positioned by a first mounting means (not shown) and a first retracting means (not shown) through a first slot opening 34 in the chamber wall 12 such that when the end plate 30 is fully extended into slot 28 cut into the inside surface 38 of chamber wall 14, it substantially seals off the upper end of chamber 12. Similarly, the lower end plate 32 is controlled and positioned by a second mounting means (not shown) and a second retracting means (not shown) through a second slot opening 36 in the chamber wall 12 such that when the lower end plate 32 is fully extended into slot 46 cut into the inside surface 38 of chamber wall 14, it substantially seals off the lower end of the chamber 10 and forms a substantially sealed chamber cavity 40 when the upper end plate 30 is also in a fully extended position. The first and second mounting means and the first and second retracting means enable the upper end plate 30 and the lower end plate 32 to move horizontally into and out of chamber 10 in a horizontal sliding motion. The Chamber wall 12 and the upper retractable end plate 30, the lower retractable end plate 32 are made of a material that is substantially not transmissive or absorptive to microwave energy. For instance, materials such as stainless steel, aluminum or any other suitable metal can be used. The microwave heating chamber 10 is further equipped with a retractable object holding plate 42 for supporting an object to be heated by microwave energy. The holding plate 42 is mounted parallel to the upper end plate 30 and the lower end plate 32 and is controlled and positioned by a third mounting means (not shown) and retracting means (not shown) through a third slot opening 44 in the chamber wall 12. The holding plate 42 is arranged in such a way that when it is in a fully extended position, it holds an object to be heated at a position of maximal microwave energy. The elongated cylindrical shaped chamber body 12 allows a more uniform distribution of the microwave energy inside the chamber and furthermore, allows a higher concentration of microwave energy at approximately the center position of the chamber cavity 40. It is believed that at a electromagnetic wave frequency of 2,450 MHz, a TM mode of microwave distribution exists inside chamber 10 which allows maximal heating efficiency. The retractable object holding plate 42 is made of a material that is microwave transmissive but not absorptive. This allows the microwave energy to penetrate through the plate to reach the object to be heated. The object holding plate 42 can be made of glass, teflon or any other high heat endurance plastic material. The object holding plate 42 is situated at a predetermined distance from the lower end plate 32 such that any object resting on the holding plate 42 is exposed to maximal microwave energy. In the preferred embodiment, the distance is approximately one-third of the distance between the two end plates. A microwave generator 50 such as a Magnetron is mounted to a mounting means 52 which sealingly engaging the chamber wall 12. The generator 50 is in microwave transmissible communication with the chamber cavity 40 through connecting flanges 54, 56, circulator 58 equipped with a dummy load 60, a wave guide 62 and protective lens 64. The circulator 58 equipped with a dummy load 60 constructed of heat-dissipating metallic foil 74 is positioned between the microwave generator 50 and the heating chamber 10 to prevent any back flow microwave to damage the generator 50. The circulator 58 acts as a one-way valve for protecting the generator 50. The dummy load 60 is normally made of a ferrite material for absorbing back flow microwave energy. The wave guide 62 situated between the heating chamber 10 and the circulator 58 is used to facilitate the transmission of microwave energy. A protective lens 64 is used at the boundary of the chamber wall 12 and the wave guide 62 such that both the chamber cavity 40 and the mounting means 52 are protected from the intrusion of foreign objects. The protective lens 64 can be made of either glass or teflon type plastic materials. A control means (not shown) of the conventional type is used to control the first, the second and the third retracting means and the microwave generator to enable the supply of microwave energy to the chamber cavity 40 for heating an object on demand. The retractable end plate 30 and the lower end plate 32 may alternatively include a seal (not shown) integrally attached to their peripheral edges made of a microwave non-transmissive material to seal the chamber from the outside environment when the two end plates are in fully extended position. Furthermore, the first, second and third slot openings 34, 36 and 44 also include sealing means 72 installed between the slot openings and the retractable plates. This ensures that substantially no microwave can leak to the outside of the chamber wall 12 during the operation of the microwave heating process. The inside diameter of the microwave heating chamber 10 is generally less than about 25 cm, and preferably less than 20 cm. The length of the elongated cylindrical chamber wall 12 is generally less than 30 cm, and preferably less than 25 cm. It should be recognized that the smaller the chamber interior, the shorter is the heating time required for an object since microwave energy is more concentrated in a smaller chamber. The heated object can be a food item, a health maintenance item such as a heat wrap, or any other suitable items to be heated. In the heating of a relatively small food item, such as a sandwich, a 20 cm diameter heating chamber can be used which efficiently heats the sandwich in approximately 10 seconds at a microwave power of 600 Watt. FIG. 2 is a top view of the microwave heating chamber 10 shown in FIG. 1. The upper end plate 30 is shown in a fully extended position engaging slot 28 cut into the inside surface 38 of chamber wall 14. The operation of the present invention microwave heating chamber installed in a vending machine can be described as follows. When a user deposits money and makes a selection, the upper end plate 30, shown in FIG. 1, is retracted by a retracting means (not shown) controlled by a controller (not shown) to allow an object (not shown) to be heated to fall onto the object holding plate 42. The upper end plate 30 then returns to a fully extended position to seal the chamber cavity 40. The microwave generator 50 is already turned-on to a warm-up mode prior to the retraction of plate 30 when a selection button is activated on the vending machine by a user. The closing of the upper end plate 30 turns on the microwave generator 50 so that microwave energy is sent through the circulator 58, the wave guide 62 and the protective lens 64 into the chamber cavity 40 to heat the object situated on the holding plate 42. After a preset time which is determined based on the nature of the object to be heated, i.e. between 5 to 120 seconds, the object is heated to its desired temperature. The microwave generator 50 is then turned-off to stop the generation of microwave. The object holding plate 42 and the lower end plate 32 are retracted simultaneously to allow the heated object to fall by gravity into a discharge chute (not shown) of the vending machine. While the present invention has been described in an illustrative manner, it should be understood that the terminology used is intended to be in a nature of words of description rather than of limitation. Furthermore while, while the present invention has been described in terms of a preferred embodiment, it is to be appreciated that those skilled in the art will readily apply these teachings to other possible variations of the invention. The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows.
A microwave heating chamber for use in a vending machine including a cylindrically shaped chamber, retractable upper and lower end plates for defining a chamber cavity, a retractable object holding plate for supporting an object to be heated at a position of maximum microwave energy, and a microwave generator for generating the microwave energy wherein the heating chamber allows the rapid heating of an article positioned in the chamber due to its small chamber volume and its cylindrically shaped cavity.
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BACKGROUND OF THE INVENTION Conventional computing systems may include a discrete graphics processing unit (dGPU) or an integral graphics processing unit (iGPU). The discrete GPU and integral GPU are heterogeneous because of their different designs. The integrated GPU generally has relatively poor processing performance compared to the discrete GPU. However, the integrated GPU generally consumes less power compared to the discrete GPU. A heterogeneous graphics processing computing system attempts to utilize the discrete and integral computing devices to improve overall performance. In the conventional art, the operating system handles all input/output request packets (IRP) for graphics devices. Accordingly, in a graphics co-processing computing system, handling of IRPs is limited by any restrictions imposed, intentionally or unintentionally, by the operating system. Such restrictions may limit the overall performance. Therefore, there is a need to enable IRP handling techniques that are not limited by the operating system. SUMMARY OF THE INVENTION The present technology may best be understood by referring to the following description and accompanying drawings that are used to illustrate embodiments of the present technology. Embodiments of the present technology are directed toward input/output request packet (IRP) handling techniques by a device specific kernel mode driver. In one embodiment, the technique includes receiving by a device specific kernel mode driver a dispatch table including a plurality of input/output manager function pointers from an input/output manager. The dispatch table including the plurality of input/output manager function pointers is sent from device specific kernel mode driver to an operating system kernel mode driver. A dispatch table including the plurality of input/output manager function pointers and a plurality of operating system function pointers is receiving by the device specific kernel mode driver from the operating system kernel mode driver. The dispatch table including the plurality of input/output manager function pointers and the plurality of operating system function pointers is stored by the device specific kernel mode driver. The device specific kernel mode driver also creates a dispatch table including the plurality of input/output manager function pointers and the plurality of operating system functions wherein one or more of the operating system function pointers are replaced by one or more device specific kernel mode driver function pointers. The dispatch table including the plurality of input/output manager function pointers and the plurality of operating system functions wherein one or more of the operating system function pointers are replaced by one or more device specific kernel mode driver function pointers are sent by the device specific kernel mode driver to an input/output manager. Thereafter, input/output request packets are received by a device specific kernel mode driver. The device specific kernel mode driver determines if any of the input/output request packets should receive a given handling. If an input/output request packet should receive the given handling, the input/output request packet is dispatched to a device specific dispatch IRP handler. If the input/output request packet should not receive the given handling the input/output request packet is redirected to an operating system dispatch IRP handler. In another embodiment, the technique includes passing a dispatch table including a plurality of input/output manager function pointers from an input/output manager to a device specific kernel mode driver. The dispatch table including the plurality of input/output manager function pointers is passed from the device specific kernel mode driver to an operating system kernel mode driver. A dispatch table including the plurality of input/output manager function pointers and a plurality of operating system function pointers is passed from the operating system kernel mode driver to the device specific kernel mode driver. The dispatch table including the plurality of input/output manager function pointers and the plurality of operating system function pointers is stored in a dispatch table of device specific kernel mode driver. A dispatch table including the plurality of input/output manager function pointers and the plurality of operating system functions wherein one or more of the operating system function pointers are replaced by one or more device specific kernel mode driver function pointers is passed from the device specific kernel mode driver to the input/output manager. Thereafter, input/output request packets are passed from an input/output manager to a dispatch function of the device specific kernel mode driver. The dispatch function determines if the input/output request packet should receive a given handling. The input/output request packet is dispatched from the dispatch function to a device specific dispatch IRP handler if the input/output request packet is to receive the given handling. Otherwise, the input/output request packet is redirected from the dispatch handler to an operating system dispatch IRP handler if the input/output request packet is not to receive the given handling. BRIEF DESCRIPTION OF THE DRAWINGS Embodiments of the present technology are illustrated by way of example and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which: FIG. 1 shows a graphics co-processing computing platform, in accordance with one embodiment of the present technology. FIG. 2 shows a technique for initializing input/output request packet (IRP) handling, in accordance with one embodiment of the present technology. FIG. 3 shows a technique for IRP handling, in accordance with one embodiment of the present technology. DETAILED DESCRIPTION OF THE INVENTION Reference will now be made in detail to the embodiments of the present technology, examples of which are illustrated in the accompanying drawings. While the present technology will be described in conjunction with these embodiments, it will be understood that they are not intended to limit the invention to these embodiments. On the contrary, the invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present technology, numerous specific details are set forth in order to provide a thorough understanding of the present technology. However, it is understood that the present technology may be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail as not to unnecessarily obscure aspects of the present technology. Embodiments of the present technology enable the ability to hook one or more IRPs and decide how to handle the IRPs. Embodiments may be utilized to provide a given handling for one or more hooked IRPs. Referring to FIG. 1 , a graphics co-processing computing platform, in accordance with one embodiment of the present technology is shown. The exemplary computing platform may include one or more central processing units (CPUs) 105 , a plurality of graphics processing units (GPUs) 110 , 115 , volatile and/or non-volatile memory (e.g., computer readable media) 120 , 125 , one or more chip sets 130 , 135 , and one or more peripheral devices 115 , 140 - 160 communicatively coupled by one or more busses. The GPUs include heterogeneous designs. In one implementation, a primary GPU may be an integral graphics processing unit (iGPU) and a secondary GPU may be a discrete graphics processing unit (dGPU). The chipset 130 , 135 acts as a simple input/output hub for communicating data and instructions between the CPU 105 , the GPUs 110 , 115 , the computing device-readable media 120 , 125 , and peripheral devices 115 , 140 - 165 . In one implementation, the chipset includes a northbridge 130 and southbridge 135 . The northbridge 130 provides for communication between the CPU 105 , system memory 120 and the southbridge 135 . In one implementation, the northbridge 130 includes an integral GPU. The southbridge 135 provides for input/output functions. The peripheral devices 115 , 140 - 165 may include a display device 140 , a network adapter (e.g., Ethernet card) 145 , CD drive, DVD drive, a keyboard, a pointing device, a speaker, a printer, and/or the like. In one implementation, the secondary GPU is coupled as a discrete GPU peripheral device 115 by a bus such as a Peripheral Component Interconnect Express (PCIe) bus. The computing device-readable media 120 , 125 may be characterized as primary memory and secondary memory. Generally, the secondary memory, such as a magnetic and/or optical storage, provides for non-volatile storage of computer-readable instructions and data for use by the computing device. For instance, the disk drive 125 may store the operating system (OS), applications and data. In one implementation, the operating system may be a Windows Operating System from Microsoft Corporation in Redmond, Wash., U.S.A. The primary memory, such as the system memory 120 and/or graphics memory, provides for volatile storage of computer-readable instructions and data for use by the computing device. For instance, the system memory 120 may temporarily store a portion of the operating system, a portion of one or more applications and associated data that are currently used by the CPU 105 , GPU 110 and the like. Generally, the GPU attached to the display 140 is designated as the primary GPU 110 and the other GPU is designated as the secondary GPU 115 . However, the secondary GPU 115 may be the primary computational unit. In other implementation, the computation workload may be dynamically switched between the primary and secondary GPU 110 , 115 based on processing performance, power consumption, and the like parameters. Referring now to FIG. 2 , a technique for initializing IRP handling, in accordance with one embodiment of the present technology, is shown. During initialization of the graphics co-processing computing system, an input/output (I/O) manager 210 loads and initializes a device specific kernel mode driver (e.g., nvlddmkm.sys) 220 for a secondary GPU (e.g., dGPU) 115 . In one implementation, the I/O manager 210 calls a driver entry point (e.g., DriverEntry) to load the device specific kernel mode driver 220 . When calling the driver specific kernel mode driver 220 , the I/O manager 210 passes a dispatch table 224 - 1 in a driver object 222 - 1 to the device specific kernel mode driver 220 . The dispatch table 224 - 1 passed to the device specific kernel mode driver 220 includes pointers to one or more functions of the I/O manager 210 . The device specific kernel mode driver 220 , for the secondary GPU 115 , calls the OS graphics driver subsystem. In one implementation, the device specific kernel mode driver 220 calls an operating system (OS) kernel mode driver (e.g., dxgkrnl.sys) 230 . In one implementation, the device specific kernel mode driver 220 calls a driver entry point (e.g., DxgkInitialize) of the OS kernel mode driver 230 . The device specific kernel mode driver 220 passes a dispatch table 224 - 2 in a driver object 222 - 2 to the OS kernel mode driver 230 . The dispatch table 224 - 2 passed to the OS kernel mode driver 230 includes the I/O manager function pointers. After receiving the dispatch table 224 - 2 , the OS kernel mode driver 230 returns back to the device specific kernel mode driver 220 . When returning back to the device specific kernel mode driver 220 , the dispatch table 224 - 3 , passed in a driver object 222 - 3 , includes a plurality of pointers to functions of the OS kernel mode driver 230 and may also include the I/O manager function pointers. The plurality of functions pointers of the OS kernel mode driver 230 includes function pointers to OS dispatch IRP handlers 236 . The device specific kernel mode driver 220 stores a copy of the dispatch table 224 - 3 received from the OS kernel mode driver 230 as dispatch table 224 - 4 . The device specific kernel mode driver 220 also creates a dispatch table 224 - 5 by replacing one or more OS function pointers with one or more pointers to a dispatch handler in the device specific kernel mode driver 220 . The replaced function pointers are for calls that are to receive a given handling. In one implementation, the given handling may be a power control function. In one implementation, the function pointer to the OS dispatch IRP handler 236 in the OS dispatch table 224 - 3 that is for turning on or off the GPU, is replaced with a function pointer to the device specific kernel mode driver dispatch IRP handler 226 local to the device specific kernel mode driver 220 . The device specific kernel mode driver 220 for the secondary GPU 115 then returns back to the I/O manager 210 . When returning back to the I/O manager 210 , the dispatch table 224 - 5 , passed in a driver object 222 - 4 , includes a plurality of pointers to functions of OS kernel mode driver and the device kernel mode driver 220 . The function pointers to the device specific kernel mode driver 220 include pointers to the dispatch IRP handlers 226 of the device specific kernel mode driver 220 , and the dispatch table 224 - 4 . Accordingly, the I/O manager 210 , device specific kernel mode driver and OS kernel mode driver 230 pass around a dispatch table 224 in the driver object 222 . The I/O manager 210 , device specific kernel mode driver and OS kernel mode driver 230 each fill the dispatch table with their respective function pointers. The device specific kernel mode driver 220 , however, replaces one or more OS kernel mode driver 230 function pointers with pointers to the device specific kernel mode dispatch IRP handlers 226 . Referring now to FIG. 3 , a technique for IRP handling, in accordance with one embodiment of the present technology, is shown. The I/O manager 210 , after creating an IRP in response to an I/O request for the user mode, plug-and-play manager, power manager, driver, or other system component, calls the dispatch function 228 of the device specific kernel mode driver 220 using function pointer in the dispatch table 224 - 5 stored by the I/O manager 210 . When calling the dispatch function 228 , the I/O manager passes a pointer to the IRP. The IRP is a data structure, including arguments and parameters such as buffer address, buffer size, I/O function type and/or the like, that describes the I/O request. The dispatch function 228 looks at the content of the IRP to determine whether or not to hook the IRP. If the dispatch function 228 determines that the IRP is to receive a given handling, the dispatch function 228 routes the IRP to the device specific dispatch IRP handler 226 local to the device specific kernel mode driver 220 . In one implementation, the dispatch function 228 may determine that a power control IRP, plug-and-play IRP or the like needs special handling and routs the power control IPR to the device specific dispatch IRP handler 226 local to the device specific kernel mode driver 220 . The device specific dispatch IRP handler 226 calls a function local to the device specific kernel mode driver 220 to handle the IRP and/or routes the IRP to a lower level driver, such as a bus filter driver 240 and/or bus driver 250 , if needed. For example, the dispatch function may determine that a start, set power, or go to sleep type I/O request for the secondary GPU 115 needs a given handling by the device specific dispatch IRP handler 226 of the device specific kernel mode driver 220 , instead of by the OS dispatch IRP handler 236 of the OS kernel mode driver 230 . If the IRP is completed through the device specific kernel mode driver 220 , the device specific kernel mode driver 220 reports completion back to the I/O manager 210 . If the IRP is not to receive the given handling, the dispatch function 228 redirects the IRP back to the OS dispatch IRP handler 236 of the OS kernel mode driver 230 using an OS function pointer in the dispatch table 224 - 4 stored by the device specific kernel mode driver 220 . In response, the OS dispatch IRP handler 236 of the OS kernel mode driver 230 calls a function of the OS kernel mode driver and/or routes the IRP to a lower driver, if needed. If the IRP is completed through the OS kernel mode driver 230 , the OS kernel mode driver 230 reports completion back to the I/O manager 210 . The given handling may be provided by the functions of the device specific kernel mode driver 220 , instead of the OS kernel mode driver 230 . Accordingly, embodiments of the present technology enable IRP handling techniques that are not limited by the operating system. The foregoing descriptions of specific embodiments of the present technology have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the present technology and its practical application, to thereby enable others skilled in the art to best utilize the present technology and various embodiments with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
The input/output request packet (IRP) handling technique includes determining if a received input/output request packet should receive a given handling. If the input/output request packet should receive the given handling, the input/output request packet is dispatched to a device specific dispatch input/output request packet handler. Otherwise, the input/output request packet is redirected to an operating system dispatch input/output request packet handler.
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CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority of Provisional Patent Application Ser. No. 61/866,223, filed on Aug. 15, 2013, the contents of which is hereby incorporated by reference. FIELD [0002] One embodiment is directed generally to a computer system, and in particular to a computer system that compiles software instructions. BACKGROUND INFORMATION [0003] For all types of computer systems, memory can be a limited resource. No matter how fast computing systems become, there is always a dependence on a finite amount of memory in which to run software applications. As a result, software developers typically consider available memory resource when writing and developing software applications. [0004] The JAVA programming language presents several features that appeal to developers of large-scale distributed systems, such as write once, run anywhere portability, portable support for multithreaded programming, and support for distributed programming, including remote method invocation and garbage collection. However, JAVA differs from many traditional programming languages in the way in which memory is allocated and de-allocated. Many programming languages, such as C and C++, explicitly allow for the allocation and de-allocation of memory by the application programmer/developer. In contrast, JAVA virtual machines (“VM”s) manage memory via structures which are deliberately opaque to programmers of JAVA applications. This opacity is problematic when running scripts in a shared user environment, such as a server VM, as one thread running out of memory has the potential of corrupting other running threads. This cross-thread contamination can cause the entire JAVA VM to be shut down. SUMMARY [0005] One embodiment is a system that implements a memory management policy at runtime when receiving a syntax tree in response to initiating the compiling of software code. The system identifies a plurality of calls within the syntax tree and modifies each the plurality of calls with a corresponding memory-modified call to create a plurality of memory-modified calls. Each memory-modified call is linked with a memory management class and the modifying occurs during the compiling of the software code. Following modification of each of the plurality of calls, the system compiles the plurality of memory-modified calls to generate a bytecode. BRIEF DESCRIPTION OF THE DRAWINGS [0006] FIG. 1 is a block diagram of a computer server/system in accordance with an embodiment of the present invention. [0007] FIG. 2 is a flow diagram of the functionality of the memory throttling module of FIG. 1 when throttling memory at runtime in accordance with one embodiment. [0008] FIG. 3 is a flow diagram of the functionality of the memory throttling module of FIG. 1 when throttling memory at runtime in accordance with another embodiment. [0009] FIG. 4 is a flow diagram of the functionality of the memory throttling module of FIG. 1 for executing bytecode created using a syntax tree that was modified during compilation in accordance with another embodiment. DETAILED DESCRIPTION [0010] One embodiment, while compiling a program in memory, intercepts all calls that create a new object and determines, based on a memory policy, whether the new object can be created in view of JAVA VM memory considerations/restrictions. If the creation of the new object does not negatively impact memory, the object can be created. By blocking the inadvertent run-away creation of in-memory objects, embodiments significantly enhance the stability and performance of systems which allow an end user to enter scripts to be run on multi-user servers. [0011] FIG. 1 is a block diagram of a computer server/system 10 in accordance with an embodiment of the present invention. Although shown as a single system, the functionality of system 10 can be implemented as a distributed system. Further, the functionality disclosed herein can be implemented on separate servers or devices that may be coupled together over a network. Further, one or more components of system 10 may not be included. For example, for functionality of a user client, system 10 may be a smartphone that includes a processor, memory and a display, but may not include one or more of the other components shown in FIG. 1 . [0012] System 10 includes a bus 12 or other communication mechanism for communicating information, and a processor 22 coupled to bus 12 for processing information. Processor 22 may be any type of general or specific purpose processor. System 10 further includes a memory 14 for storing information and instructions to be executed by processor 22 . Memory 14 can be comprised of any combination of random access memory (“RAM”), read only memory (“ROM”), static storage such as a magnetic or optical disk, or any other type of computer readable media. System 10 further includes a communication device 20 , such as a network interface card, to provide access to a network. Therefore, a user may interface with system 10 directly, or remotely through a network, or any other method. [0013] Computer readable media may be any available media that can be accessed by processor 22 and includes both volatile and nonvolatile media, removable and non-removable media, and communication media. Communication media may include computer readable instructions, data structures, program modules, or other data in a modulated data signal such as a carrier wave or other transport mechanism, and includes any information delivery media. [0014] Processor 22 is further coupled via bus 12 to a display 24 , such as a Liquid Crystal Display (“LCD”). A keyboard 26 and a cursor control device 28 , such as a computer mouse, are further coupled to bus 12 to enable a user to interface with system 10 . [0015] In one embodiment, memory 14 stores software modules that provide functionality when executed by processor 22 . The modules include an operating system 15 that provides operating system functionality for system 10 . The modules further include a memory throttling module 16 for throttling memory at runtime, and all other functionality disclosed herein. System 10 can be part of a larger system. Therefore, system 10 can include one or more additional functional modules 18 to include the additional functionality, such as additional GROOVY or JAVA related functionality. A database 17 is coupled to bus 12 to provide centralized storage for modules 16 and 18 . [0016] One embodiment uses a programming language that allows for modification of the syntax tree during the compilation process, and implements one or more memory throttling rules (referred to herein as a “memory policy”). As an example, a user may submit code to a server from a remote computer system for compilation and execution. This server may be operated by a third-party that is distinct from the user, and the third-party may desire to enforce a memory policy that prevents certain actions from being performed by the user's code. While the code submitted by the user (either remote or local to the server) may not contain memory policy functions, the server may modify method calls in a syntax tree based on the code supplied by the user. Once the syntax tree has been created based on the code, an analysis of the syntax tree may be performed. The analysis can identify various methods, constructor access, and/or property access that are strictly prohibited in accordance with the memory policy. These violations of the memory policy may prevent the code from being compiled into bytecode and may result in an exception being output. An indication of the exception can be provided to the user. [0017] In one embodiment, the programming language is the “GROOVY” programming language, or some other programming language that permits access to the syntax tree during the compiling process before bytecode (or machine code) has been generated. GROOVY is an object-oriented programming language for the JAVA platform. Generally, GROOVY is a superset of JAVA and therefore JAVA code may likely be syntactically valid in GROOVY. GROOVY includes additional syntax and features in addition to what is available in JAVA. Similar to JAVA, GROOVY code can be compiled into bytecode. This bytecode can be translated by a virtual machine (“VM”) into machine code. [0018] When GROOVY code is being compiled, prior to the bytecode being generated, an abstract syntax tree (“AST”) is created based on the code. While in the form of a syntax tree, embodiments edit the AST before the bytecode is created. Therefore, various modifications can be made to the AST that will affect creation of the bytecode and how the bytecode will execute at runtime. Instead of using GROOVY, other embodiments can use any programming language that allows for editing of code at the syntax tree level prior to being compiling into bytecode (or machine code). [0019] In general, embodiments that use GROOVY includes the following functionality: (1) An annotation, placed on GROOVY code (either automatically or manually); (2) an AST manipulation class, which does rewriting of method and property access; and (3) an optional Quota Policy class, which enforces the memory constraints at runtime. All three parts can have multiple, overlapping implementations to allow for differences in usage (for instance, embedded vs. standalone use). [0020] The annotation in one embodiment is a standard GROOVY AST annotation. It is used to notify the GROOVY compiler (either called via the command line, or via GroovyShell.parse( )) that the GROOVY AST manipulation class should be called. For instance, one type of annotation could be used for GROOVY Script code, while another could be used for GROOVY Class code. [0021] The Groovy AST manipulation intercepts all loop code, and wraps it with new code, which is responsible for determining if the loop has exceeded some allowed memory quota (i.e., the memory policy). Similarly, all collection classes and Strings are monitored for size, and additional checks may be added to count the number of memory intensive objects created, again subject to a quota. Additional checks may be added as well, for other operations which may consume undue amounts of system resources, such as combinations of otherwise innocuous objects. Once the AST manipulation is complete, the class can be accessed with some assurance against memory exhaustion in the same manner as any other class in the Java VM. [0022] Quotas may be determined by system-wide specified properties, by the use of a Quota Policy class, by metadata associated with the script, by variables placed into the script by the end user, or by some other method or combination of methods. [0023] FIG. 2 is a flow diagram of the functionality of memory throttling module 16 of FIG. 1 when throttling memory at runtime in accordance with one embodiment. In one embodiment, the functionality of the flow diagram of FIG. 2 , and FIGS. 3 and 4 below, is implemented by software stored in memory or other computer readable or tangible medium, and executed by a processor. In other embodiments, the functionality may be performed by hardware (e.g., through the use of an application specific integrated circuit (“ASIC”), a programmable gate array (“PGA”), a field programmable gate array (“FPGA”), etc.), or any combination of hardware and software. [0024] At 210 , calls within a syntax tree are identified. The syntax tree may be an abstract syntax tree that was created based on code written or otherwise provided by a user. The syntax tree may be created as part of the process of compiling the code. In some programming languages it is possible to edit code after the syntax tree has been generated. For example, compiling GROOVY code may allow for modification of code after a syntax tree has been generated but before bytecode has been generated. The user may have added one or more annotations to the code that indicate that one or more syntax tree manipulation classes should be called. In addition to identifying method calls, constructor calls and/or property access calls may be identified. Identification of method calls, constructor calls, and/or property access calls (“calls”) may be accomplished by parsing the syntax tree. [0025] At 220 , for each method call identified, a memory-modified call is substituted. In addition to being for method calls, constructor calls and/or property access calls may also be substituted with memory-modified calls. A memory-modified call causes a check for permission of the call based on a memory policy, as disclosed in detail below. Substituting a memory-modified call for a call may involve associating the call with a memory class such that the memory class is evaluated to determine whether permission is granted prior to the call being executed. For example, substituting a method call with a memory-modified method call may involve the method call being wrapped in a memory class call or otherwise modified so that the method call is checked against a memory policy. The method call may become a parameter of the memory class, thus creating a memory-modified method call. The method call may only be executed if the memory check results in the method call being identified as permissible. As such, the memory class that is based on a memory policy will be checked for permission to perform the method call before the method call has been performed. Similar association and/or wrapping may occur for constructor calls and/or property access calls. [0026] At 230 , following substitution, the syntax tree, which now may contain one or more memory-modified method calls, memory-modified constructor calls, and/or memory-modified property access calls (“memory-modified calls”), is compiled. The compilation of the modified syntax tree results in the creation of bytecode configured to be interpreted into machine code for execution. When executed, each memory-modified call is checked against the memory policy using the memory class. If a memory-modified call fails to pass the memory policy, the bytecode is ceased being executed and an exception is generated. The exception can be stored and/or output to a user. In some embodiments, it may be possible to skip the offending memory-modified call and attempt to continue executing the bytecode. [0027] FIG. 3 is a flow diagram of the functionality of memory throttling module 16 of FIG. 1 when throttling memory at runtime in accordance with another embodiment. [0028] At 310 , a memory policy is received. The memory policy can include one or more memory rules that identify a type of method call, constructor call, and/or property access call that may not be allowed during execution of compiled code, due to excessive memory usage, and may be detected during static analysis. The memory policy may be a default memory policy provided by or to the entity that is compiling code and/or may be a customized memory policy. The memory policy in one embodiment uses knowledge of the size of the existing memory array in the JAVA VM or its libraries, and determines whether the size can be made larger, or limits all new object creation to a single array. The restrictions of memory size can be dynamically tuned and changed. [0029] The memory policy in one embodiment is stored by the system that is compiling code for execution. In some embodiments, the memory policy may be stored remotely but may be accessible to the system that is compiling code for execution. [0030] At 320 , uncompiled code is received. This code may be received in the form of a user writing code or providing one or more files containing code. In some embodiments, a user, via a user computer system, may submit code through a web-based interface to a remote server to be compiled and executed. The remote server may receive the uncompiled code, compile it, and execute the code remote from the user computer system. Code may be received from other sources besides a remote user computer system. [0031] At 325 , one or more memory management annotations are added to the uncompiled code. The memory management annotations serve as an indication to the compiler that a manipulation class (such as a GROOVY AST manipulation class) should be called. An annotation for script code (e.g., GROOVY script code) and/or an annotation for class code (e.g. GROOVY class code) can be added. Such memory management annotations can be added manually by a user or automatically. In embodiments that use GROOVY, the memory management annotations may be added as either global or local transformations, and may be triggered at the compilation step, which may be from the command line, or from a GROOVY application programming interface (“API”) such as GroovyShell.parse( ). In some embodiments, instead of an annotation, some other triggering mechanism can be used, such as a configuration switch, a properties file, or an environment variable. [0032] At 330 , the compilation of the code is initiated, which causes an abstract syntax tree to be created based on the uncompiled code received at 320 . The AST is a tree representation of the uncompiled code received at 320 written in a programming language, such as GROOVY. Each node of the AST corresponds to an element in the uncompiled code in one embodiment. The programming language used for some embodiments, such as GROOVY, permits editing of the syntax tree prior to the syntax tree being used to compile bytecode (or machine code). [0033] At 335 , calls within the syntax tree created at 330 are identified by parsing the syntax tree. This may include method calls, constructor calls, and/or property access calls. [0034] At 340 , the memory policy received at 310 is used to perform a static analysis of the syntax tree. Static analysis identifies one or more constructor calls, method calls, and/or property access calls that will violate the memory policy (i.e., are not permitted under the memory policy). For example, when reading an Extensible Markup Language (“XML”) file known to be large, using Document Object Mod& (“DOM”) methods which hold the entire document in memory could result in disallowing the script to compile. As another example, creating an array of very large static String objects could also result in disallowing the script to compile, as could reading those Strings from a file or database where they are known to be large. [0035] If one or more constructor calls, method calls, and/or property access calls fail to be permissible in accordance with the memory policy, the functionality continues to 390 . [0036] At 390 , a memory exception is generated and output based on the one or more failed calls at 340 . In one embodiment, if the uncompiled code received at 320 was received from a user via a web interface, the web interface can be used to provide the user with an indication of the one or more failed calls. Compiling of the syntax tree into bytecode may be blocked, at least until the memory exceptions are corrected in the uncompiled code. [0037] If the static analysis at 340 does not identify any memory exceptions in accordance with the memory policy, the functionality continues to 370 . At 370 , for each method call identified at 335 , a memory-modified method call is substituted by modifying method calls, constructor calls and/or property access calls. Substituting a memory-modified method call for a method call includes associating the method call with a memory class such that the memory class is evaluated to determine if the method call is permitted to be executed. The method call may only be executed if the memory check results in the method call being identified as permissible. Substituting a method call with a memory-modified method call may involve the method call being wrapped in a memory class call. As such, the memory class is used to check for permission to perform the method call before the method call has been performed. Similar association and/or wrapping may occur for constructor calls and/or property access calls. In some embodiments, the functionality of 335 and 370 are performed together as a syntax tree is parsed. For example, a first method call may be identified and substituted with a memory-modified method call before a second method call is identified. [0038] At 380 , following substitution being completed at 370 , the syntax tree, which now contains one or more memory-modified method calls, memory-modified constructor calls, and/or memory-modified property access calls, is compiled. The compilation of the modified syntax tree results in bytecode configured to be interpreted by a virtual machine into machine code for execution. In some embodiments, machine code may be created directly by the compiler. [0039] FIG. 4 is a flow diagram of the functionality of memory throttling module 16 of FIG. 1 for executing bytecode created using a syntax tree that was modified during compilation in accordance with another embodiment. The bytecode could have been created using the functionality of FIG. 3 . The functionality of FIG. 4 may also be executed by a system separate from system 10 of FIG. 1 . [0040] At 410 , a first memory-modified call of the bytecode is attempted to be executed. The call can be a memory-modified method call, a memory-modified constructor access call or a memory-modified property access call. When executed, rather than directly executing the call, a memory class associated with the call may be used. [0041] At 420 , the memory check for the memory-modified call is performed based on the memory policy and existing quotas. If the call fails to pass the memory policy, the functionality continues at 430 . At 430 , a memory exception is generated and output. The bytecode may be prevented from being executed further, and the user is notified of the exception. [0042] If the call satisfies the memory policy at 420 , at 440 , the call is executed. Therefore, if a first call was used to create a memory-modified call at 370 of FIG. 3 , the first call will be executed at 440 if the method call is in accordance with the memory policy. Following successful execution of 440, functionality continues to 410 when another memory-modified call is executed. This will continue until the bytecode has completely been executed. [0043] As disclosed, embodiments intercept compilation calls and either allows the call or disallows the call based on the memory policy during compilation. By blocking the inadvertent run-away creation of in-memory objects, embodiments can significantly enhance the stability and performance of systems which allow the end user to enter scripts to be run on multi-user servers, such as GROOVY with a JAVA VM. Since embodiments do not rely on changes to the JAVA VM, it can be used with currently implemented JAVA VMs. [0044] Several embodiments are specifically illustrated and/or described herein. However, it will be appreciated that modifications and variations of the disclosed embodiments are covered by the above teachings and within the purview of the appended claims without departing from the spirit and intended scope of the invention.
A system that implements a memory management policy at runtime when receiving a syntax tree in response to initiating the compiling of software code identifies a plurality of calls within the syntax tree and modifies each the plurality of calls with a corresponding memory-modified call to create a plurality of memory-modified calls. Each memory-modified call is linked with a memory management class and the modifying occurs during the compiling of the software code. Following modification of each of the plurality of calls, the system compiles the plurality of memory-modified calls to generate a bytecode.
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RELATED APPLICATIONS [0001] This application claims the benefit of the filing date of U.S. Provisional Patent Application 61/734,921, filed Dec. 7, 2012. The entire teaching of this application is incorporated by reference herein. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] This invention was made with government support under 1R43HL110725-01A1 and 1R43AI092989-01 awarded by NIH. The government has certain rights in the invention. BACKGROUND [0003] Hematopoietic stem cell and progenitor cells (HSPCs) have been used clinically for more than 50 years. HSPC transplants are routinely used to treat patients with cancers and other disorders of the blood and immune systems, with approximately 50,000 HSPC transplants performed annually worldwide according to the Worldwide Network for Blood and Marrow Transplantation (WBMT) 1 . HSPCs are being used in an increasing number of experimental therapies as well, including therapeutic angiogenesis to treat myocardial ischemia 2 and gene therapy in an attempt to cure inherited blood disorders 3 and increase resistance to HIV 4 . Additionally, HSPCs are being investigated as a cell source for generating terminally differentiated blood cell types including erythrocytes, natural killer cells, and platelets, after directed differentiation. [0004] HSPCs can be obtained from bone marrow (BM), mobilized peripheral blood (MPB), and umbilical cord blood (UCB), although each source differs significantly in the number of HSPCs obtainable and their regenerative capacity 5,6 . In the transplant setting, MPB has become a preferred source of HSPCs due to the relative ease (in most cases) of obtaining therapeutic doses of cells 7 . However, a subset of patients termed “poor mobilizers” do not respond well to plerixafor and other drugs normally used to mobilize HSPCs to peripheral blood, reducing the number of HSPCs collected and increasing the chances that an autologous HSPC transplant will fail 8 . Allogeneic HSPC transplants are a treatment option for such patients, but are considerably more complicated due to the need for identifying human leukocyte antigen (HLA)-matched grafts. UCB is an alternative source of HSPCs for allogeneic transplants that has been used in the clinic for more than twenty years 9 . UCB can be utilized in allogeneic transplants with more HLA discordance than BM and MPB 10-12 , and UCB-derived HSPCs possess a greater proliferative capacity. Unfortunately, each unit of UCB contains a relatively low absolute number of total nucleated cells (TNCs) and HSPCs, which has limited its use primarily to pediatric transplant patients to date. Typically, the total CD 34 + cell count from UCB is only about 10% of that from MPB 13 . [0005] Regardless of the application, clinicians repeatedly see that administering larger numbers of cells increases the chances of achieving a long-term therapeutic benefit in patients versus delivering fewer cells. In the transplant setting for instance, most groups aim for an HSPC dose of at least 2.5×10 6 CD34+ cells per kg to assure complete hematologic recoveryl 4,15 , but several studies have shown that doses of more than 5×10 6 CD34+ cells per kg are associated with faster engraftment and a reduced incidence of graft failure 16,17 . [0006] To overcome the challenges associated with insufficient HSPC doses and expand the use of HSPCs to a greater number of patients, numerous advancements are needed in the collection, processing, and delivery of HSPCs to patients. Ex vivo expansion of HSPCs is one strategy for overcoming the cell dose limitations of HSPC-based therapies that offers tremendous promise for improving clinical outcomes. The basic concept is that small numbers of HSPCs collected from patients can be expanded in culture without significant loss of HSPC phenotype and in vivo functionality. Increasing knowledge regarding the biology of HSPCs and improved methods for assaying the presence of primitive HSPCs have led to a plethora of new ex vivo expansion strategies. For instance, several groups have demonstrated improved expansion of primitive HSPCs via media addition of proteins and other molecules, including growth factor cocktails 18-20 , transcriptional inhibitors 21-25 , transcriptional activators 26,27 , and copper chelating-compounds 28-30 , that modulate important HSPC signaling pathways. Other groups have demonstrated that culturing HSPCs directly on mesenchymal stem cell (MSC) feeder layers improves ex vivo expansion of primitive HSPCs 31-33 , although human studies utilizing MSC feeder layers have not been convincing 34 . Of note, researchers at the Fred Hutchinson Cancer Research Center (FHCRC) have recently developed an ex vivo expansion protocol in which UCB-derived HSPCs are cultured on a surface presenting immobilized Notch ligand Delta-1 in combination with a fibronectin fragment. The FHCRC group demonstrated that Delta-1-expanded cells, when combined with an non-manipulated UCB graft, could rapidly reconstitute myeloid cells in humans; however, the expanded cells did not achieve long-term engraftment 35 . [0007] One likely reason why existing strategies have fallen short in efficiently expanding primitive HSPCs is that they rely on culturing the cells directly on flat plastic surfaces (standard plastic dishes or culture bags) that are very different from the BM niche where HSPCs reside in vivo. Alternatively, electrospun nanofibers can mimic important features of the BM niche by providing a three dimensional culture surface with a very high density of surface bound functional groups that promote increased cell adhesion, among other things. Electrospun nanofibers have previously been shown to promote significant proliferation of UCB-derived HSPCs 36,37 , but heretofore have only been available to the market in multi-well culture plates that are more suitable for research settings. The technology disclosed herein incorporates electrospun nanofibers into a closed culture system that combines the HSPC expansion benefits of the nanofibers with the sterility and convenience of a closed culture system better suited for clinical use. BRIEF SUMMARY OF THE INVENTION [0008] In certain aspects, the invention provides a system for expansion, differentiation, and/or maintenance of functional cells comprising a core of one or more electrospun polymers enclosed within a closed culture device. [0009] In certain aspects, the invention provides improved compositions and methods for the expansion and differentiation of HSPCs within a closed system. In one aspect, the inventors have found a way to mimic the natural environment where HSPCs exist within a closed system. For example, the inventors have found a way to mimic the natural bone marrow environment wherein HSPC exist naturally. [0010] Accordingly, in one aspect, the invention provides nanofiber compositions for the expansion or differentiation of HSPCs comprising one or more electrospun polymers. In a related embodiment, an additional polymer is grafted onto the one or more electrospun polymers. In a related embodiment, the grafted polymer is derivatized. In one embodiment the polymer is derivatized with carboxylic, hydroxyl or amino groups. In another embodiment, the polymer is derivatized with a positively charged moiety. In another embodiment, the polymer is derivatized with a protein, polypeptide, peptide, or glycosaminoglycan e.g., a cell adhesion peptide or polypeptide or heparin. [0011] In another embodiment, the polymer or polymers are selected from the group consisting synthetic polymers, natural polymers, protein engineered biopolymers or combinations thereof. [0012] In a particular embodiment, the grafted polymer is poly(acrylic acid) (PAAc). In another particular embodiment, the electrospun polymers comprises polyethersulfone (PES). [0013] In another embodiment, the composition of the invention has a spacer between the grafted nanofiber and the derivatized moiety. Exemplary spacers are ethylene, butylenes or hexylene moieties. [0014] In particular embodiments of the invention, the compositions of the invention are useful for expanding or differentiating neural stem cells and embryonic stem cells in addition to HSPCs. [0015] In other embodiments, the grafted electrospun nanofiber compositions of the invention have a diameter between 10 nm to 10 μm, preferably between 100-700 nm. In a specific embodiment, the grafted electrospun nanofiber composition of the invention comprises poly(acrylic acid) grafted on to a polyethersulfone core. In a further embodiment, this composition is derivatized. In particular embodiments the composition is derivatized by amination, with peptides or polypeptides, e.g., laminin, heparin, or cell adhesion peptides or polypeptides. [0016] In a further embodiment, the electrospun fibers are made from a synthetic polymer, natural polymers, and random fibers and aligned fibers. In a further embodiment, the fibers can have a range of diameters, including from 10 nanometers to 10 micrometers. [0017] In another embodiment, the electrospun composition comprises spacers between the electrospun fiber and the derivatized moiety. In exemplary embodiments, the spacers comprise ethylene, butylene or hexylene moieties. [0018] In one particular embodiment, the grafted electrospun nanofiber composition comprises poly(acrylic acid) grafted on to a polyethersulfone core, wherein the poly (acrylic acid) is aminated. [0019] In particular embodiments the electrospun fiber compositions are useful for the expansion or differentiation of stem cells, e.g., hematopoietic stem/progenitor cells, neural stem cells, or embryonic stem cells. In certain embodiments of the invention, the electrospun nanofiber composition of the invention has randomly oriented fibers. In alternate embodiments, the electrospun nanofiber composition of the invention has aligned fibers. In further embodiments, the grafted electrospun is produced uniaxial electrospinning, coaxial, or multi axial electrospinning. [0020] In another embodiment, the electrospun nanofiber composition is attached directly to a culture container. In further embodiments, the nanofiber composition is attached to a flexible substrate (la poly-acrylate like PMMA, a poly-acetate like EVA, a polyester like PET, or a multi layer combination of the same) prior to incorporation within the culture container. In alternate embodiments, the nanofiber composition with substrate is attached to a rigid culture container prior to incorporation within the culture container. In these embodiments, the nanofiber composition is attached to the culture container or a substrate through chemical (e.g., adhesive) or non-chemical (e.g., thermal bonding) means. [0021] In another embodiment of the invention, the culture container is composed of gas permeable materials. In an alternate embodiment, the culture container is composed of non-permeable materials. [0022] In a further embodiment of the invention, the culture container has one inlet/outlet valve (in the form of tubing, spike connector, luer fittings, etc.) for culture medium and reagents injection, as well as cell harvesting. In alternate embodiments, the culture container has two, three or four inlet/outlet valves (in the form of tubing, spike connector, luer fittings, etc.) for culture medium and reagents injection, as well as cell harvesting. [0023] In another embodiment, the nanofiber surface can be further modified through chemical or biological means to coat the surface with surface groups and/or proteins. In further embodiments, the nanofibers can be conjugated with functional molecules including amine groups, carboxyl groups, hydroxyl groups, peptides, proteins, glycosaminoglycans and carbohydrates. [0024] In a further embodiment of the invention, the nanofiber composition is bonded to a substrate prior to attachment to the culture container. In this embodiment, the substrate can come from a number of substrates including synthetic polymers such as polystyrene. In this embodiment, the substrate can be bonded through chemical or non-chemical means. [0025] In another embodiment of the invention, the material for cell culture container can come from classes of materials that allow for high rate of gas exchange (e.g., EVA, EVO) or minimal gas exchange (e.g., polystyrene, FEP). [0026] In further embodiments of the invention, expanded cells can be used either directly or after further processing for research and therapeutic purposes in a variety of disease conditions where use of the expanded cells are useful, including but not limited to, bone marrow transplantation for patients with disease conditions like leukemia, anemia, and bone marrow failure. In an alternate embodiment, the expanded cells can be used directly, or further processed by cell selection, differentiation, and gene modification for research and therapeutic applications. [0027] In another embodiment of the invention, the expanded cells can go through further differentiation processes in the system or in another system. One example of this is for the cells to differentiate into reticulocytes, which may be used for research or as an alternate for blood transfusion. [0028] In alternate embodiments, a number of cells types can be used such as embryonic stem cells, fat cells, induced pluripotent stem cells, neural stem cells, liver primary cells, hematopoietic stem cells, progenitor cells, and mesenchymal stem cells. BRIEF DESCRIPTION OF THE DRAWINGS [0029] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawings will be provided by the Office upon request and payment of the necessary fee. [0030] FIG. 1A depicts adhesion of UCB-derived CD34+ cells to NANEX™ scaffold. FIG. 1B depicts TNC and CD34+ cell expansion after 10-day serum-free culture on NANEX™ and control substrates. This figure is adapted from Reference 12. [0031] FIG. 2 depicts engraftment efficiency in bone marrow of NOD-SCID mice of unexpanded UCB-derived CD34+ cells and progeny from 600 cells expanded on NANEX™ and control substrates. This figure is adapted from Reference 12. [0032] FIG. 3 depicts a culture bag embodiment of the invention. [0033] FIG. 4 depicts the inside of a culture bag embodiment of the invention. [0034] FIG. 5 depicts expansion of CD34+ cells in culture bag embodiment of the invention compared to traditional culture flask (TCPS) and a commercially available culture bag (VueLife® AC, American Fluoroseal Corp). [0035] FIG. 6 depicts expansion of colony forming unit (CFU) cells in culture bag embodiment of the invention compared to traditional culture flask (TCPS). [0036] FIG. 7 depicts a schematic of how nanofiber expansion of HSPCs is incorporated into a step-wise process for generating large numbers of differentiated erythrocytes. [0037] FIG. 8 shows expansion results and flow cytometry analysis of cells at various time points during the erythroid differentiation stage (post-expansion in nanofiber-coated bag). [0038] FIG. 9 shows enucleation of erythrocytes at various time points during the erythroid differentiation stage (post-expansion in nanofiber-coated bag). DETAILED DESCRIPTION OF THE INVENTION Overview [0039] Stem cells have the potential to cure numerous disease and disorders. However, the sources of stem cells are limited. A representative example of the problem with obtaining stem cells is illustrated by human umbilical cord blood (UCB) hematopoietic stem/progenitor cells (HSPCs). HSPCs are multipotent cells that have the capacity to self-renew and differentiate into all mature blood cell types. However, a low number of HSPCs is available from sources like umbilical cord blood which limits the use of these cells to pediatric populations. Therefore, several approaches have been explored to expand HSPCs in ex vivo expansion systems, so that UCB could serve as a readily viable source of transplantable HSPCs for adult patients for the treatment of various disorders. In conventional ex vivo expansion culture, HSPCs are generally regarded as suspension cells and numerous protocols implement HSPC suspension cultures in flasks or bags in the presence of various combinations of early acting cytokines. These protocols do not produce enough HSPCs to be of clinical significance. Similar problems exist with the expansion of other types of stem cells. Accordingly, the need exists for improved methods and compositions for the expansion and differentiation of stem cells, particularly within closed culture devices that enable sterile processing of the cells for use in clinical applications. [0040] In certain aspects, the disclosure provides a nanofiber surface within a closed culture device to mimic the human stem cell niche and promote improved expansion of functional HSPCs. By greatly increasing the number of transplantable cells, the system can overcome the limitation of the low cell numbers, and improve the clinical outcomes. [0041] In certain aspects, the disclosure provides a fully closed system with its inner surfaces coated with one or more electrospun polymer-based scaffold. It is designed for expansion of a variety of cell lines including but not limited to, HSPCs which can be injected into patients with various disease conditions (e.g. leukemia, bone marrow failure). The system may be used for large-scale culture and expansion of other cell types for clinical or research purposes. Definitions [0042] For convenience, certain terms employed in the specification, examples, and appended claims, are collected here. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. [0043] The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element. [0044] The term “including” is used herein to mean, and is used interchangeably with, the phrase “including but not limited” to. [0045] The term “or” is used herein to mean, and is used interchangeably with, the term “and/or,” unless context clearly indicates otherwise. [0046] The term “such as” is used herein to mean, and is used interchangeably, with the phrase “such as but not limited to”. Closed Culture Device [0047] The invention pertains to the development of a novel closed culture device for sterile expansion and differentiation of stem cells as well as methods and compositions for the expansion and differentiation of stem cells using nanofiber scaffolds incorporated within the closed culture device. Existing closed culture devices largely consist of flat plastic culture surfaces (e.g., tissue culture treated polystyrene) that do not adequately mimic the native environments where stem cells reside in vivo. The current invention represents a significant advancement in the field by providing a closed culture device that incorporates a culture substrate capable of better mimicking the native stem cell niche. [0048] In one embodiment, an electrospun nanofiber composition is attached directly to a culture container. In further embodiments, the nanofiber composition is attached to a flexible substrate (a poly-acrylate like PMMA, a poly-acetate like EVA, a polyester like PET, or a multi layer combination of the same) prior to incorporation within the culture container. In alternate embodiments, the nanofiber composition with substrate is attached to a rigid culture container prior to incorporation within the culture container. In these embodiments, the nanofiber composition is attached to the culture container or a substrate through chemical (e.g., adhesive) or non-chemical (e.g., thermal bonding) means. [0049] In one embodiment of the invention, the culture container is composed of gas permeable materials. In an alternate embodiment, the culture container is composed of non-permeable materials. [0050] In a further embodiment of the invention, the culture container has one inlet/outlet valve (in the form of tubing, spike connector, luer fittings, etc.) for culture medium and reagents injection, as well as cell harvesting. In alternate embodiments, the culture container has two, three or four inlet/outlet valves (in the form of tubing, spike connector, luer fittings, etc.) for culture medium and reagents injection, as well as cell harvesting. [0051] In another embodiment of the invention, the material for cell culture container can come from classes of materials that allow for high rate of gas exchange (e.g., EVA, EVO) or minimal gas exchange (e.g., polystyrene, FEP). [0052] In certain embodiments, said device can allow for automated control of oxygen levels, carbon dioxide levels, temperature, pH levels, and the level of cell waste including ammonia or other ammonia related waste products referred to as ammoniac. In this embodiment, said device allows probes to be inserted within the device for continuous monitoring of oxygen, carbon dioxide, temperature, pH and accumulation of culture waste. Such probes are additionally connected to a computer terminal that analyzes the incoming data and outputs signals that control operation of pumps and valves to inject appropriate reagents into the device. Reservoirs of culture media, gas, and pH control reagents are connected via closed loops to the culture device to maintain sterile conditions during injection. [0053] In certain embodiments of the invention, HSPCs are expanded within said device. In other embodiments, HSPCs are expanded and terminally differentiated within said device. In still other embodiments, HSPCs are expanded within said device and terminally differentiated in a separate device (e.g., standard culture bag) connected to the said device via a closed loop. Nanofiber Compositions [0054] The present invention incorporates an electrospun nanofiber mesh within a novel closed culture system. In certain embodiments, the nanofiber mesh is that described in US Patent Application Publication No. 20080153163, herein incorporated by reference in its entirety. [0055] In other embodiments, the electrospun nanofibers used in the methods and compositions of the invention can be natural or synthetic. In one embodiment, the electrospun nanofibers are comprised of natural polymers. Exemplary natural polymers include cellulose acetate (CA), chitin, chitosan, collagen, cotton, dextran, elastin, fibrinogen, gelatin, heparin, hyaluronic acid (HA), poly 3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), regenerated cellulose (RC), silk, and zein. [0056] In one embodiment, the electrospun nanofibers are made of degradable or non-degradable synthetic polymer material. Exemplary degradable polymers include poly(c-caprolactone) (PCL), poly(ε-caprolactone-co-ethyl ethylene phosphate) (PCLEEP), poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA), poly(lactic acid-co-ε-caprolactone) (PLACL), and polydioxanone (PDO). Exemplary non-degradable polymers include poly acrylamide (PAAm), poly acrylic acid (PAA), poly acrylonitrile (PAN), poly amide (Nylon) (PA, PA-4,6, PA-6,6), poly aniline (PANI), poly benzimidazole (PBI), poly bis(2,2,2-trifluoroethoxy) phosphazene, poly butadiene (PB), poly carbonate (PC), poly ether amide (PEA), poly ether imide (PEI), poly ether sulfone (PES), poly ethylene (PE), poly ethylene-co-vinyl acetate (PEVA), poly ethylene glycol (PEG), poly ethylene oxide (PEO), poly ethylene terephthalate (PET), poly ferrocenyldimethylsilane (PFDMS), poly 2-hydroxyethyl methacrylate (HEMA), poly 4-methyl-1-pentene (TpX), poly methyl methacrylate (pMMA), poly p-phenylene terephthalamide (PPTA), poly propylene (PP), poly pyrrole (PPY), poly styrene (PS), polybisphenol-A sulfone (PSF), poly sulfonated styrene (PSS), Styrene-butadiene-styrene triblock copolymer (SBS), poly urethane (PU), poly tetrafluoro ethylene (PTFE), poly vinyl alcohol (PVA), poly vinyl carbazole, poly vinyl chloride (PVC), poly vinyl phenol (PVP), poly vinyl pyrrolidone (PVP), and poly vinylidene difluoride (PVDF). A preferred synthetic polymer is polyethersulfone (PES). [0057] The electrospun nanofiber compositions of the invention can be made of any one of polymers identified herein. The electrospun nanofiber compositions of the invention can also be made of any combination of the polymers identified herein. [0058] Electrospun matrices can be formed of electrospun fibers of synthetic polymers that are biologically compatible. The term “biologically compatible” includes copolymers and blends, and any other combinations of the forgoing either together or with other polymers. The use of these polymers will depend on given applications and specifications required. A more detailed discussion of these polymers and types of polymers is set forth in Brannon-Peppas, Lisa, “Polymers in Controlled Drug Delivery,” Medical Plastics and Biomaterials, November 1997, which is incorporated herein by reference. [0059] The compounds to be electrospun can be present in the solution at any concentration that will allow electrospinning. In one embodiment, the compounds may be electrospun are present in the solution at concentrations between 0 and about 1.000 g/ml. In another embodiment, the compounds to be electrospun are present in the solution at total solution concentrations between 10-30 w/v % (100-300 mg/ml). [0060] The compounds can be dissolved in any solvent that allows delivery of the compound to the orifice, tip of a syringe, under conditions that the compound is electrospun. Solvents useful for dissolving or suspending a material or a substance will depend on the compound. [0061] By varying the composition of the fibers being electrospun, it will be appreciated that fibers having different physical or chemical properties may be obtained. This can be accomplished either by spinning a liquid containing a plurality of components, each of which may contribute a desired characteristic to the finished product, or by simultaneously spinning fibers of different compositions from multiple liquid sources, that are then simultaneously deposited to form a matrix. The resulting matrix comprises layers of intermingled fibers of different compounds. This plurality of layers of different materials can convey a desired characteristic to the resulting composite matrix with each different layer providing a different property, for example one layer may contribute to elasticity while another layer contributes to the mechanical strength of the composite matrix. These methods can be used to create tissues with multiple layers such as blood vessels. [0062] The electrospun nanofiber has an ultrastructure with a three-dimensional network that supports cell expansion, growth, proliferation, and/or differentiation. This three dimensional network is similar to the environment where many of these HSPCs naturally occur, e.g., in bone marrow. The spatial distance between the fibers plays an important role in cells being able to obtain nutrients for growth as well as for allowing cell-cell interactions to occur. Thus, in various embodiments of the invention, the distance between the fibers may be about 50 nanometers, about 100 nanometers, about 150 nanometers, about 200 nanometers, about 250 nanometers, about 300 nanometers, about 350 nanometers, about 600 nanometers, about 750 nanometers, about 800 nanometers, about 850 nanometers, about 900 nanometers, about 950 nanometers, about 1000 nanometers (1 micron), 10 microns, 10 microns, 50 microns, about 100 microns, about 150 microns, about 200 microns, about 250 microns, about 300 microns, about 350 microns, about 400 microns, about 450 microns, or about 500 microns. In various embodiments the distance between the fibers may be less than 50 nanometers or greater than 500 microns and any length between the quoted ranges as well as integers. [0063] Additionally, in various embodiments of the invention, the fibers can have a diameter of about 50 nanometers, about 100 nanometers, about 150 nanometers, about 200 nanometers, about 250 nanometers, about 300 nanometers, about 350 nanometers, about 600 nanometers, about 750 nanometers, about 800 nanometers, about 850 nanometers, about 900 nanometers, about 950 nanometers, about 1000 nanometers (1 micron), 50 microns, about 100 microns, about 150 microns, about 200 microns, about 250 microns, about 300 microns, about 350 microns, about 400 microns, about 450 microns, or about 500 microns, or the diameter may be less than 50 nanometers or greater than 500 microns and any diameter between the quoted ranges as well as integers. A preferred fiber diameter is between 100-700 nm. [0064] The pore size in an electrospun matrix can also be controlled through manipulation of the composition of the material and the parameters of electrospinning. In some embodiments, the electrospun matrix has a pore size that is small enough to be impermeable to one or more types of cells. In one embodiment, the average pore diameter is about 500 nanometers or less. In another embodiment, the average pore diameter is about 1 micron or less. In another embodiment, the average pore diameter is about 2 microns or less. In another embodiment, the average pore diameter is about 5 microns or less. In another embodiment, the average pore diameter is about 8 microns or less. Some embodiments have pore sizes that do not impede cell infiltration. In another embodiment, the matrix has a pore size between about 0.1 and about 100 μm. In another embodiment, the matrix has a pore size between about 0.1 and about 50 μm. In another embodiment, the matrix has a pore size between about 1.0 μm and about 25 μm. In another embodiment, the matrix has a pore size between about 1.0 μm and about 5 μm. [0065] The mechanical properties of the matrix or core will depend on the polymer molecular weight and polymer type/mixture. It will also depend on the orientation of the fibers (preferential orientation can be obtained by changing speed of a rotating or translating surface during the fiber collection process), fiber diameter and entanglement. The cross-linking of the polymer will also effect its mechanical strength after the fabrication process. The electrospun nanofiber core can be comprised of parallel or randomly oriented fibers. [0066] In certain embodiments of the invention, a polymer is grafted onto the electrospun nanofiber core. Exemplary polymers that can be grafted onto the electrospun core include, but are not limited to, polymers having functional groups which can be initiated by free radicals, e.g., free radicals formed on the surface of the electrospun core. Exemplary grafted polymers include poly(acrylic acid) and derivatives and copolymers thereof, e.g., polymethacrylic acid and poly(acrylic acid-co-hydroxyethylmethacrylic acid), polyallylamine and derivatives and copolymers thereof. [0067] In further embodiments of the invention the polymers grafted on the electro spun nanofiber core are derivatized. In general, the polymers are derivatized so that cells, e.g., HSPCs, are better able to interact with the compositions of the invention. In one embodiment, the polymers are derivatized to have a positive charge. In another embodiment, the polymers are derivatized to have a negative charge. Exemplary derivatives include carboxylic, hydroxyl and amino moieties. [0068] In other embodiments, the polymers are derivatized with a biological agent, e.g., a nucleic acid, protein, polypeptide, peptide. In exemplary embodiments, the derivatized moiety is a cell adhesion peptide or heparin. In other exemplary embodiments, the derivatized moiety is a cytokine or growth factor. In certain embodiments, the polymer bound moiety will mimic the native presentation pattern of these molecules in the bone marrow niche during early hematopoiesis. [0069] In certain embodiments, derivatized moieties are directly conjugated to the polymer fibers. In certain embodiments, multiple derivatized moieties are conjugated to the same set of fibers. In certain embodiments, multiple derivatized moieties are conjugated to different fibers. In certain embodiments, the fibers are arranged into defined patterns. [0070] In yet further embodiments, the compositions of the invention comprise a spacer molecule between the electrospun nanofiber and the derivatized moiety. The spacer molecule can allow for improved functionality of the compositions of the invention. In exemplary embodiments, the spacer is an ethylene, propylene, butylene, or hexylene moiety. Expansion of HSPCs [0071] In certain embodiments, the present invention discloses methods and processes to obtain large numbers of functional HSPCs through the ex vivo expansion of the cells within the disclosed device. [0072] The instant methods rely on the isolation of stem cells from any of a number of sources and the subsequent use of the compositions and methods of the instant invention to expand these stem cells. Stem cells can be isolated from any of a number of sources using techniques known to those of skill in the art. For example, U.S. Pat. No. 5,061,620 describes a substantially homogeneous human hematopoietic stem cell composition and the manner of obtaining such composition. [0073] In certain embodiments, there is at least a 200-fold expansion of HSPCs within the closed culture device. In certain embodiments, there is at least a 200-fold expansion of HSPCs in about a 10-day expansion within the closed culture device. [0074] In certain embodiments, expansion occurs in less than 10 days of culture. In certain embodiments, expansion occurs after 10 days of culture. In certain embodiments, expansion occurs in about 10 days of culture. In certain embodiments, expansion occurs in about 12, 16, 18 20, 22, 24, 26 or 28 days of culture. In certain embodiments, expansion occurs between 1 to 10 days of culturing. In certain embodiments, expansion occurs between 2 to 10 days, 3 to 10 days, 4 to 10 days, 5 to 10 days, 6 to 10 days, 7 to 10 days, 8 to 10 days, or 9 to 10 of culturing. In certain embodiments, expansion occurs between 10-28 days of culturing. In certain embodiments, expansion occurs between 10-28 days, 10-12 days, 10-14 days, 10-16 days, 10-18 days, 10-20 days, 10-22 days, 10-24 days, or 10-26 days of culturing. In certain embodiments, expansion occurs on a scaffold. In certain embodiments, expansion occurs in culture on a nanofiber mesh and/or film. In certain embodiments, expansion occurs in a bioreactor. [0075] In certain embodiments, cells expanded within the device demonstrate larger numbers of CD34+ cells in the final product than cells cultured using standard cultureware. In certain embodiments, cells expanded within the device demonstrate larger numbers of colony forming unit (CFU) cells than cells cultured using standard cultureware. In certain embodiments, expanded cells successfully reconstitute hematopoiesis at efficiency rates higher than cells cultured using standard cultureware. Differentiation of HSPCs [0076] In certain embodiments, the present invention discloses methods and processes to obtain terminally differentiated blood cell types through the ex vivo expansion and differentiation of HSPCs. [0077] One embodiment of the invention is to isolate HSPCs from a biologic source such as peripheral blood, umbilical cord blood, bone marrow, and embryonic fluid. Said HSPCs are applied to said device and are allowed to expand for a period of time. HSPCs expanded within the device are then terminally differentiated. [0078] In certain embodiments, cultured cells according to the methods of the application have a significant differentiation commitment towards the myeloblast / monoblast lineage. In certain embodiments, cultured cells according to the methods of the application have a significant differentiation commitment towards the erythrocyte lineage. In certain embodiments, cultured cells according to the methods of the application have a significant differentiation commitment towards platelets. [0079] In certain embodiments, 80% or more of nanofiber expanded cells are differentiated to erythrocyte phenotype in about 26 days in liquid culture. In certain embodiments, 80% or more, 90% or more, or 95% or more of nanofiber expanded cells are differentiated to erythrocyte phenotype in about 10, 12, 14, 16, 18, 20, 22, 24 or 28 days in liquid culture. In certain embodiments, HSPCs expanded within the device are differentiated using published methods such as those described in Koury et al. In vitro maturation of nascent reticulocytes to erythrocytes. Blood. 2005 Mar. 1; 105(5):2168-74. Epub 2004 Nov. 4; Fujimi et al. Ex vivo large-scale generation of human red blood cells from cord blood CD34+ cells by co-culturing with macrophages. Int J Hematol. 2008 May; 87(4):339-50; Neildez-Nguyen et al. Human erythroid cells produced ex vivo at large scale differentiate into red blood cells in vivo. Nat Biotechnol. 2002 May; 20(5):467-72; or Giarratana et al. Ex vivo generation of fully mature human red blood cells from HSPCs. Nat Biotechnol. 2005 January; 23(1):69-74. Epub 2004 Dec. 26, all of which are herein incorporated by reference in their entirety. Exemplification [0080] The invention now being generally described, it will be more readily understood by reference to the following examples, which are included merely for purposes of illustration of certain aspects and embodiments of the present invention, and are not intended to limit the invention, as one skilled in the art would recognize from the teachings hereinabove and the following examples, that other stem cell sources and selection methods, other culture media and culture methods, other dosage and treatment schedules, and other animals and/or humans, all without limitation, can be employed, without departing from the scope of the invention as claimed. EXAMPLE 1 Closed Cell Culture Bag Incorporating a Sheet of Electrospun Nanofibers [0081] An example of this invention is to incorporate the electrospun nanofibers into a closed culture bag (see FIGS. 3 and 4 ). To construct such a culture bag, large sheets of electrospun polyethersulfone (PES) nanofibers were prepared and mounted onto a supportive backing material of 7.5 mil polystyrene (PS) using thermal bonding techniques. These supported PES nanofiber sheets were functionalized with a high density of amine groups. Using an adhesive, the aminated sheets were then bonded to the lower half of a sheet of gas-permeable, USP Class VI polymer in which inlet and outlet ports are embedded. The polymer sheet was then folded over and thermally sealed on three sides such that the inlet and outlet ports were located at one end of the enclosed culture bag. Transfer of media and cells into and out of the nanofiber culture bag was performed using syringes via Leur-Lok™-style connections or by sterile welding to other bags. EXAMPLE 2 Expansion of Human Hematopoietic Stem and Progenitor Cells Using Electrospun Nanofiber Coated Culture Bags [0082] A nanofiber-coated bag of the invention can be used to expand human derived hematopoietic stem and progenitor cells (HSPCs) using various media formulations for various culture times. Human cord blood derived CD34+ cells were isolated and purified. The cells were seeded into the nanofiber cell culture bag. Cells were cultured at temperatures and atmospheric conditions that are appropriate for the type of cell being cultured. For example, CD34+ cells were cultured at a temperature of 37 degrees Celsius with an atmospheric CO 2 concentration of 5%. The cells were cultured for a number of days without medium change. In this particular example, cells were cultured for 7 days; however the culture time can be shortened or extended based on the desired ending cell population. At the end of the culture period, the culture bag was gently rocked back and forth to dislodge cells and the medium containing cells was collected. To remove remaining cells, the bags were rinsed consecutively with an appropriate rinsing agent (i.e. PBS and EDTA-based cell dissociation buffer). All the cell suspensions were combined and the cells were concentrated through centrifugation. Typically in such a culture, an expansion of at least 30-fold was achieved for CD34+ cells, with a percentage of CD34+ cells, in the final population harvested, of at least 30%. In comparison, the same CD34+ cells cultured using the same media but in a standard tissue culture polystyrene flask (TCPS Flask) or a commercially available culture bag (VueLife® AC, American Fluoroseal Corp) expand nearly 2-fold less (see FIG. 5 ). Additionally, total colony forming unit (CFU) cells were typically expanded about 50% more using the present invention compared to TCPS flasks (see FIG. 6 ). [0083] In this particular example, human cord blood derived CD34+ cells were used. However, CD133+ cells and other hematopoietic stem and progenitor cell phenotypes can also be cultured and expanded using such nanofiber bags. In addition to human cord blood, cells derived from human bone marrow, mobilized peripheral blood, fat tissue, and fetal liver can also be cultured on such bags. EXAMPLE 3 Differentiation of Nanofiber Culture Bag Expanded HSPCs Towards Erythroid Lineage. [0084] A nanofiber-coated bag of the invention can be used to expand human derived hematopoietic stem and progenitor cells (HSPCs) that can subsequently be differentiated towards various blood cell lineages. HSPCs expanded in nanofiber-coated culture bags are differentiated towards the erythroid lineage. Although several erythroid differentiation protocols are available in the literature, those protocols involving controlled feeding of particular growth factors without the need for feeder cells have been found to be particularly effective 38,39 . A schematic of the preferred protocol is shown in FIG. 7 . As shown, the first step in the process is a 7-day expansion of the HSPCs using the nanofiber-coated culture bag (referred to here as NANEX™) [0085] Using this approach, massive expansion of cord blood cells that appropriately expressed both early and late stage erythroid markers was achieved ( FIG. 8 ). After 7 days of expansion using the NANEX™ system and 18-21 days of erythroid differentiation, more than 60% of cells expressed CD235a (a marker for the human erythrocyte membrane), 70% expressed CD71, and 20% expressed CD36, indicating a reticulocyte phenotype. Additionally, nearly 80% of cells were enucleated after 21 days of culture ( FIG. 9 ). [0086] All publications and patents mentioned herein, including those items listed below, are hereby incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control. References [0000] 1 Gratwohl, A. et al. Hematopoietic stem cell transplantation: a global perspective. JAMA: the journal of the American Medical Association 303, 1617-1624, doi:10.1001/jama.2010.491 (2010). 2 Losordo, D. W. et al. Intramyocardial transplantation of autologous CD34+ stem cells for intractable angina: a phase I/IIa double-blind, randomized controlled trial. Circulation 115, 3165-3172, doi:10.1161/CIRCULATIONAHA.106.687376 (2007). 3 Gaspar, H. B. et al. Hematopoietic stem cell gene therapy for adenosine deaminase-deficient severe combined immunodeficiency leads to long-term immunological recovery and metabolic correction. Science translational medicine 3, 97ra80, doi:10.1126/scitranslmed.3002716 (2011). 4 Mitsuyasu, R. T. et al. Phase 2 gene therapy trial of an anti-HIV ribozyme in autologous CD34+ cells. Nature medicine 15, 285-292, doi:10.1038/nm.1932 (2009). 5 da Silva, C. L. et al. Differences amid bone marrow and cord blood hematopoietic stem/progenitor cell division kinetics. Journal of cellular physiology 220, 102-111, doi:10.1002/jcp.21736 (2009). 6 Wang, J. C., Doedens, M. & Dick, J. E. Primitive human hematopoietic cells are enriched in cord blood compared with adult bone marrow or mobilized peripheral blood as measured by the quantitative in vivo SCID-repopulating cell assay. Blood 89, 3919-3924 (1997). 7 Gertz, M. A. Current status of stem cell mobilization. British journal of haematology 150, 647-662, doi:10.1111/j.1365-2141.2010.08313.x (2010). 8 To, L. B., Levesque, J. P. & Herbert, K. E. How I treat patients who mobilize hematopoietic stem cells poorly. Blood 118, 4530-4540, doi:10.1182/blood-2011-06-318220 (2011). 9 Gluckman, E. et al. Hematopoietic reconstitution in a patient with Fanconi's anemia by means of umbilical-cord blood from an HLA-identical sibling. The New England journal of medicine 321, 1174-1178 (1989). 10 Liao, C. et al. Indiscernible benefit of high-resolution HLA typing in improving long-term clinical outcome of unrelated umbilical cord blood transplant. Bone marrow transplantation 40, 201-208 (2007). 11 Takahashi, S. et al. Comparative single-institute analysis of cord blood transplantation from unrelated donors with bone marrow or peripheral blood stem-cell transplants from related donors in adult patients with hematologic malignancies after myeloablative conditioning regimen. Blood 109, 1322-1330 (2007). 12 Majhail, N. S. et al. Reduced-intensity allogeneic transplant in patients older than 55 years: unrelated umbilical cord blood is safe and effective for patients without a matched related donor. Biology of blood and marrow transplantation: journal of the American Society for Blood and Marrow Transplantation 14, 282-289 (2008). 13 Soiffer, R. J. in Contemporary Hematology (ed J.E. Karp) (Humana Press, Totowa, N.J., 2008). 14 Siena, S., Schiavo, R., Pedrazzoli, P. & Carlo-Stella, C. Therapeutic relevance of CD34 cell dose in blood cell transplantation for cancer therapy. Journal of clinical oncology: official journal of the American Society of Clinical Oncology 18, 1360-1377 (2000). 15 Mavroudis, D. et al. CD34+ cell dose predicts survival, posttransplant morbidity, and rate of hematologic recovery after allogeneic marrow transplants for hematologic malignancies. Blood 88, 3223-3229 (1996). 16 Shpall, E. J., Champlin, R. & Glaspy, J. A. Effect of CD34+ peripheral blood progenitor cell dose on hematopoietic recovery. Biology of blood and marrow transplantation: journal of the American Society for Blood and Marrow Transplantation 4, 84-92 (1998). 17 Schulman, K. A., Birch, R., Zhen, B., Pania, N. & Weaver, C. H. Effect of CD34(+) cell dose on resource utilization in patients after high-dose chemotherapy with peripheral-blood stem-cell support. Journal of clinical oncology: official journal of the American Society of Clinical Oncology 17, 1227 (1999). 18 Zhang, C. C. et al. Angiopoietin-like proteins stimulate ex vivo expansion of hematopoietic stem cells. Nature medicine 12, 240-245, doi:10.1038/nm1342 (2006). 19 Tursky, M. L., Collier, F. M., Ward, A. C. & Kirkland, M. A. Systematic investigation of oxygen and growth factors in clinically valid ex vivo expansion of cord blood CD34(+) hematopoietic progenitor cells. Cytotherapy 14, 679-685, doi:10.3109/14653249.2012.666851 (2012). 20 Mohamed, A. A. et al. Ex vivo expansion of stem cells: defining optimum conditions using various cytokines. Laboratory hematology: official publication of the International Society for Laboratory Hematology 12, 86-93, doi:10.1532/LH96.05033 (2006). 21 Milhem, M. et al. Modification of hematopoietic stem cell fate by 5aza 2′deoxycytidine and trichostatin A. Blood 103, 4102-4110 (2004). 22 Araki, H. et al. Expansion of human umbilical cord blood SCID-repopulating cells using chromatin-modifying agents. Exp Hematol 34, 140-149 (2006). 23 Boitano, A. E. et al. Aryl hydrocarbon receptor antagonists promote the expansion of human hematopoietic stem cells. Science 329, 1345-1348, doi:10.1126/science.1191536 (2010). 24 Trowbridge, J. J., Xenocostas, A., Moon, R. T. & Bhatia, M. Glycogen synthase kinase-3 is an in vivo regulator of hematopoietic stem cell repopulation. Nature medicine 12, 89-98 (2006). 25 Nishino, T. et al. Ex vivo expansion of human hematopoietic stem cells by garcinol, a potent inhibitor of histone acetyltransferase. PloS one 6, e24298, doi:10.1371/journal.pone.0024298 (2011). 26 Aguila, J. R. et al. SALL4 is a robust stimulator for the expansion of hematopoietic stem cells. Blood 118, 576-585, doi:10.1182/blood-2011-01-333641 (2011). 27 Huang, C. H. et al. Purified recombinant TAT-homeobox B4 expands CD34(+) umbilical cord blood and peripheral blood progenitor cells ex vivo. Tissue engineering. Part C, Methods 16, 487-496, doi:10.1089/ten.TEC.2009.0163 (2010). 28 Peled, T. et al. Cellular copper content modulates differentiation and self-renewal in cultures of cord blood-derived CD34+ cells. Br J Haematol 116, 655-661 (2002). 29 Peled, T. et al. Pre-clinical development of cord blood-derived progenitor cell graft expanded ex vivo with cytokines and the polyamine copper chelator tetraethylenepentamine. Cytotherapy 6, 344-355 (2004). 30 de Lima, M. et al. Transplantation of ex vivo expanded cord blood cells using the copper chelator tetraethylenepentamine: a phase I/II clinical trial. Bone marrow transplantation 41, 771-778 (2008). 31 Robinson, S. N. et al. Superior ex vivo cord blood expansion following co-culture with bone marrow-derived mesenchymal stem cells. Bone marrow transplantation 37, 359-366, doi:10.1038/sj.bmt.1705258 (2006). 32 da Silva, C. L. et al. Dynamic cell-cell interactions between cord blood haematopoietic progenitors and the cellular niche are essential for the expansion of CD34+, CD34+CD38- and early lymphoid CD7+ cells. Journal of tissue engineering and regenerative medicine 4, 149-158, doi:10.1002/term.226 (2010). 33 Andrade, P. Z., dos Santos, F., Almeida-Porada, G., da Silva, C. L. & J M, S. C. Systematic delineation of optimal cytokine concentrations to expand hematopoietic stem/progenitor cells in co-culture with mesenchymal stem cells. Molecular bioSystems 6, 1207-1215, doi:10.1039/b922637k (2010). 34 De Lima, M. e. a. in Blood Vol. 116 (American Society for Hematology, Annual Meeting, Orlando, Fla., 2010). 35 Delaney, C. et al. Notch-mediated expansion of human cord blood progenitor cells capable of rapid myeloid reconstitution. Nature medicine 16, 232-236. 36 Chua, K. N. et al. Functional nanofiber scaffolds with different spacers modulate adhesion and expansion of cryopreserved umbilical cord blood hematopoietic stem/progenitor cells. Experimental hematology 35, 771-781 (2007). 37 Chua, K. N. et al. Surface-aminated electrospun nanofibers enhance adhesion and expansion of human umbilical cord blood hematopoietic stem/progenitor cells. Biomaterials 27, 6043-6051, doi:10.1016/j.biomaterials.2006.06.017 (2006). 38 Giarratana, M. C. et al. Ex vivo generation of fully mature human red blood cells from hematopoietic stem cells. Nature biotechnology 23, 69-74, doi:10.1038/nbt1047 (2005). 39 Douay, L. & Giarratana, M. C. Ex vivo generation of human red blood cells: a new advance in stem cell engineering. Methods Mol Biol 482, 127-140, doi:10.1007/978-1-59745-060-7 — 8 (2009). [0126] This application herein incorporates by reference the entire teachings of U.S. Patent Publication Nos. 2004/0258670, 2005/0069527 and 2009/0285892. [0127] The practice of the present invention will employ, where appropriate and unless otherwise indicated, conventional techniques of cell biology, cell culture, molecular biology, transgenic biology, microbiology, virology, recombinant DNA, and immunology, which are within the skill of the art. Such techniques are described in the literature. See, for example, Molecular Cloning: A Laboratory Manual, 3rd Ed., ed. by Sambrook and Russell (Cold Spring Harbor Laboratory Press: 2001); the treatise, Methods In Enzymology (Academic Press, Inc., N.Y.); Using Antibodies, Second Edition by Harlow and Lane, Cold Spring Harbor Press, New York, 1999; Current Protocols in Cell Biology, ed. by Bonifacino, Dasso, Lippincott-Schwartz, Harford, and Yamada, John Wiley and Sons, Inc., New York, 1999.
The invention provides, among other things, methods and compositions for expanding stem cells. The invention further provides methods, devices and systems for directing differentiation of expanded stem cells. The invention further provides methods, devices and systems for treating a subject with differentiated cells in a subject in need thereof.
2
This application is a continuation of application Ser. No. 07/544,864, filed Jun. 28, 1990, abandoned. BACKGROUND OF THE INVENTION The present invention relates to a bus lock control apparatus required for semaphore management in a multiprocessor system having a common bus. A conventional bus lock control apparatus has the following arrangement. A bus use request from each agent is sent to a bus arbiter, and the bus arbiter arbitrates the bus use requests of all agents. As a result of arbitration, the arbiter selects one of the agents which have sent the bus use requests, and sends a bus transmission enable signal to the selected agent. The selected agent reserves the right of bus use as a master agent until bus transmission is completed. During this transmission, the bus arbiter does not send a bus transmission enable signal to any other agent. Upon completion of the bus transmission by the master agent, the master agent loses the right of bus use. The bus arbiter performs bus arbitration again to determine a new master agent. In this manner, the bus arbiter and each agent repeat the above operation, so that a system having a common bus can be properly operated. An operation performed when the master agent sends a bus lock request to the bus arbiter will be described below. When the bus arbiter sends a transmission enable signal in response to a bus lock request, the arbiter immediately interlocks the bus. In this interlocked state, bus arbitration is interrupted, and a bus transmission enable signal is sent back to only the master agent. The master agent does not lose the right of bus use upon completion of transmission of the bus lock request and keeps occupying the bus. After the master agent outputs a bus lock release request and this bus cycle is completed, the bus arbiter releases the bus interlocked state and restarts bus arbitration. That is, use of the bus by only the master agent is allowed during the bus interlocked period. In the conventional bus lock apparatus, the bus lock request is used as a lock read signal, and the bus lock release request is used as an unlock write signal. During an interval from the lock read signal to the unlock write signal, the bus is interlocked. When the master agent checks a memory content read out by the lock read signal and determines if the memory content is write-accessible, predetermined data is written again in a memory. However, if the memory content is not write-accessible, read data is written in the memory by the unlock write signal. This data is used to manage the semaphore in the memory. In the multiprocessor system, in order to prevent a plurality of processors from using the same semaphore, a use/nonuse state of the semaphore is represented by a semaphore header. Contention of the plurality of processors for this semaphore header is controlled such that the bus is interlocked using the lock read and unlock write signals to assure a sequence from a memory read operation to a memory write operation of each independent processor, thereby performing exclusive control. A common bus system having a higher speed and a larger capacity than those of a conventional common bus system is proposed. In these bus arbitration systems, a plurality of bus cycles which overlap each other are generated in response to a bus cycle from the first initial resource use request transmission to response status reception in each bus arbitration system described above, thereby increasing the bus transfer speed. When a lock control system using a bus interlock scheme in such a bus arbitration system, the bus cycles cannot overlap each other, thus resulting in a contradiction. When semaphore management is taken into consideration, the lock read and unlock write signals must always be used to access the semaphore header by OS address management, and normal read/write access is not performed. However, since the bus is interlocked, even a read/write bus cycle free from a semaphore influence cannot be sent out, and a bus throughput is decreased. SUMMARY OF THE INVENTION The present invention eliminates the conventional drawbacks described above, and has as its object a bus lock control apparatus which does not interlock a bus to increase a bus throughput. In order to achieve the above object of the present invention, there is provided a bus lock control apparatus comprising a bus arbiter having register means for storing bus lock enable information in correspondence with a plurality of agents, and lock acknowledging means for acknowledging an OR signal of all pieces of information of the register means to agents connected to the common bus, wherein the lock acknowledging means is latched after a lapse of a predetermined period of time when a bus lock request or bus lock release request is enabled in the bus arbiter. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram showing an embodiment of the present invention; FIGS. 2A to 2F are timing charts showing a sequence for shifting a state from a locked state to an unlocked state, and FIGS. 3A to 3F are timing charts of a lock disable sequence. DESCRIPTION OF THE PREFERRED EMBODIMENT An embodiment of the present invention will be described hereinafter with reference to the accompanying drawings. FIG. 1 shows an embodiment of the present invention. Referring to FIG. 1, a bus arbiter 1 includes a port manager 4, a busy manager 5, a monitor manager 6, a register 2 and an OR gate 3. The port manager 4 receives initial resource use requests 24-1 to 24-n from a plurality of agents connected to a common bus and performs control until bus use enable signals 23-1 to 23-n are output. The busy manager 5 controls set a busy time for an agent which has received a bus use enable signal and busy times of other agents in accordance with an agent which is in actual operation. The monitor manager 6 checks a first initial resource use request code corresponding to the bus use enable signal and a resource which is actually requested to be used via an address command line 21. The register 2 sets/resets one bit corresponding to a request source agent from the monitor manager 6 by using control lines 30-1 to 30-m when a lock read request or an unlock write request is sent through the address command line 21. The register 2 then stores a locked state of the common bus. The OR gate 3 is arranged to output an OR signal of all bits of the register 2. An agent 10 connected to the common bus includes a prerequest controller 13, a request controller 14, a delay circuit 12, a lock indicator means 11, and a reply discrimination controller 15. The prerequest controller 13 outputs an initial resource use request to the bus arbiter 1, and the request controller 14 outputs the resource use request to the address command line 21. The delay circuit 12 delays a bus use enable signal 23-1 from the bus arbiter 1 by a predetermined period (e.g., 3T). The lock indicator means 11 latches the OR signal from the OR gate 3, i.e., a lock acknowledging means 20 on the common bus after a lapse of the predetermined period (3T) when the bus use enable signal 23-1 is enabled by an output 41 from the delay circuit 12 and a signal line 42 for discriminating lock read transmission from the request controller 14 from unlock write transmission therefrom. The reply discrimination controller 15 discriminates a relay response line 22 to acknowledge a bus transfer state from a slave agent to a master agent, when the agent 10 serves as the master agent and other agents serve as the slave agents. Bus lock control processing of the bus lock control apparatus having the above arrangement will be described with reference to timing charts in FIGS. 2A to 2F and 3A to 3F. A control sequence in FIGS. 2A to 2F shows a change in state from the unlocked state to the locked state, and vice versa, and the control sequence in FIGS. 3A to 3F is a lock disable sequence. When a lock read operation of a memory by the agent connected to the common bus is to be performed, an initial resource use request (FIG. 2A) is sent from the prerequest controller 13 to the bus arbiter 1 through the control line 24-1. The bus arbiter 1 causes the port manager 4 to detect a bus busy state and initial resource use requests from other agents and selects an appropriate agent. For example, the agent 10 is selected, and a bus use enable signal 23-1 (FIG. 2B) is supplied from the arbiter 1 to the agent 10. When the bus use enable signal 23-1 is supplied from the port manager 4 to the agent 10, the request controller 14 in the agent 10 outputs a lock read command CMD (FIG. 2C) to the address command line 21 of the bus. The monitor manager 6 in the bus arbiter 1 always monitors this address command line 21 and sets one bit of the register 2 at a bit position corresponding to the agent 10 by using the control lines 30-1 to 30-m when the lock read command CMD is output. The content of the register 2 is acknowledged to each agent connected to the bus by using the signal line lock acknowledging means 20 via the OR gate 3 (FIG. 2E). When the lock acknowledging means 20 is set at "0", the bus is set in an unlocked state. However, when the lock acknowledging means 20 is set at "1", the bus is set in the locked state. The lock acknowledging means 20 is changed after a lapse of 3T when the lock read request or unlock write request is output to the address command line 21, and this timing is kept constant. The agent 10 which requested the lock read operation latches the state of the lock acknowledging means 20 after a lapse of 3T when the bus use enable signal 23-1 is set at "1" by the signal 41 from the delay circuit 12 and a signal 42 representing the lock read request. At this time, the complement of the content of the lock acknowledging means 20 is locked by the lock indicator means 11 to synchronize the state of change in the lock acknowledging means 20 with that of the lock indicator means 11 (FIGS. 2E and 2F). When the agent 10 refers to the state of the lock indicator means 11, the agent 10 can check if it is during locking (FIG. 2D). Since the bus arbiter 1 does not completely interrupt bus arbitration, it is possible for any other agent to use the bus. An operation for changing the state from the locked state to the unlocked state by a write unlock request will be described. When the agent 10 connected to the common bus is to perform an unlock write operation of the memory, the agent 10 sends an initial resource use request 24-1 (FIG. 2A) from the prerequest controller 13 to the bus arbiter 1 via the control line 24-1. The bus arbiter 1 causes the port manager 4 to detect a bus busy state and initial resource use requests from other agents and selects an appropriate agent. For example, the agent 10 is selected, and a bus use enable signal 23-1 (FIG. 2B) is supplied from the bus arbiter 1 to the agent 10. When the bus use enable signal 23-1 is supplied from the port manager 4 to the agent 10, the request controller 14 in the agent 10 sends out an unlock write command CMD (FIG. 2C) to the address command line 21. The monitor manager 6 in the bus arbiter 1 always monitors the address command line 21 and resets one bit of the register 2 to "0" at a position corresponding to the agent 10 by using the control lines 30-1 to 30-n along which the unlock write command is output. The content of the register 2 is sent to each agent connected to the common bus by using the signal line lock acknowledging means 20 on the bus through the OR gate 3 (FIG. 2E). When the lock acknowledging means 20 is set at "0", the bus unlocked state is represented. However, when the lock acknowledging means 20 is set at "1", the bus locked state is represented. The lock acknowledging means 20 is changed after a lapse of 3T when the lock read or unlock write request is output to the address command line 21. This timing is kept unchanged. The agent 10 which requested the lock read operation latches the state of the lock acknowledging means 20 after a lapse of 3T when the bus use enable signal 23-1 is set at "0" by the signal 41 from the delay circuit 12 and the signal 42 representing the lock read request. At this time, the complement of the content of the lock acknowledging means 20 is locked by the lock indicator means 11 to synchronize the state of change in the lock acknowledging means 20 with that of the lock indicator means 11 (FIGS. 2E and 2F). When the agent 10 refers to the state of the lock indicator means 11, the agent 10 can check if it is during locking (FIG. 2D). A maximum of one bit of the register 2 in the bus arbiter 1 is set. Since the agent corresponding to the set bit can be set, the number of agents which can acquire the lock command detected by the bus arbiter 1 is a maximum of one agent. Only one agent is available to change the state from the unlocked state to the locked state, and only one agent is also available to be released by the unlock write command. An operation performed upon the output of a read lock request from a given agent in the locked state of the lock acknowledging means 20 will be described with reference to FIGS. 3A to 3F. As shown in FIGS. 3A to 3C, a sequence between the bus arbiter 1 and the master agent 10 is the same as that described with reference to FIGS. 2A to 2F. The relationship between the lock acknowledging means 20 and the lock indicator means 11 will be described below. When an agent other than the agent 10 acquires the locked state, the content of the register 2 is kept unchanged, and the lock acknowledging means 20 is kept at "1" (FIG. 3E). The agent 10 causes an inverter to invert the content of the bus acknowledging means 20 after a lapse of 3T from when a bus transmission request in the lock read mode is received, and sets the inverted content in the lock indicator means 11. At this time, the content of the lock indicator means 11 is kept at "0", which represents the unlocked state (FIG. 3F). Therefore, the agent 10 cannot acquire the locked state (FIG. 3D). In this embodiment, the agent itself can detect whether the locked state is set or not. The amount of hardware can be reduced, and bus adjustment need not be interrupted. Therefore, bus throughput can be increased. According to the present invention as has been described above, since the agent itself can detect whether the locked state is set, bus adjustment need not be interrupted and a bus throughput can be increased.
A bus lock control apparatus including a bus arbiter having a register for storing bus lock enable information in correspondence with a plurality of agents, and a lock acknowledging means for acknowledging an OR signal of all pieces of information of the register to agents connected to the common bus. The lock acknowledging means is latched after a lapse of a predetermined period of time when a bus lock request or bus lock release request is enabled in the bus arbiter.
6
TECHNICAL FIELD [0001] The present invention relates to a method of producing an optical member, in which an optical substrate having a light shielding portion and another optical substrate are bonded to each other, and the use of an ultraviolet curable resin composition for the method. BACKGROUND ART [0002] In recent years, a display device capable of screen input by bonding a touch panel to a display screen of the display device such as a liquid crystal display, a plasma display, or an organic EL display is widely used. This touch panel has a structure, in which glass plates or resin films having a transparent electrode formed thereon are bonded to one another with a slight gap, and if necessary, a transparent protective plate of glass or resin is bonded onto the touch surface. [0003] There is a technique, in which a pressure sensitive adhesive double coated sheet is used to bond a glass plate or film having a transparent electrode formed thereon to a transparent protective plate of glass or resin in a touch panel, or to bond a touch panel to a display unit. However, there is a problem that air bubbles are easily generated when a pressure sensitive adhesive double coated sheet is used. A technique, in which a glass plate or film having a transparent electrode formed thereon is bonded to a transparent protective plate of glass or resin with an ultraviolet curable resin composition having flexibility, or a touch panel is bonded to a display unit with an ultraviolet curable resin composition having flexibility, has been suggested as an alternative technique to a pressure sensitive adhesive double coated sheet. [0004] Meanwhile, a light shielding portion of belt shape is formed at the outermost edge of a transparent protective plate in order to improve the contrast of a display image. In a case in which the transparent protective plate having a light shielding portion formed thereon is bonded with an ultraviolet curable resin composition, insufficient ultraviolet rays reach the ultraviolet curable resin in the light shielded region, which corresponds to the shade of the light shielding portion, because of the light shielding portion, and thus the curing of the resin in the light shielded region is not sufficient. If the curing of resin is not sufficient, problems such as display unevenness in the display image near the light shielding portion occur. [0005] As a technique to improve the curing of resin in a light shielded region, Patent Literature 1 discloses a technique, in which an organic peroxide is contained in an ultraviolet curable resin, and the resin thus obtained is irradiated with ultraviolet rays and then heated, whereby the resin in a light shielded region is cured. However, it is concerned that a heating process causes damage to a liquid crystal display device and the like. Moreover, there is a problem of poor productivity since the heating process requires generally 60 minutes or longer time to secure sufficient curing of resin. In addition, Patent Literature 2 discloses a technique, in which the resin in a light shielded region is cured by irradiating with ultraviolet rays from the outer side surface of the light shielding portion forming surface. However, there is limitation in this technique since it is sometimes difficult to irradiate the resin with ultraviolet rays from the side surface depending on the shape of a liquid crystal display device. In addition, Patent Literature 3 discloses a technique, in which slow acting property of a cationically polymerizable ultraviolet curable resin is used, but the resin after curing is poor in flexibility. CITATION LIST Patent Literatures [0000] Patent Literature 1: JP 4711354 B1 Patent Literature 2: JP 2009-186954 A Patent Literature 3: JP 2010-248387 A SUMMARY OF INVENTION Technical Problem [0009] An object of the invention is to provide a method of producing an optical member using an ultraviolet curable resin composition capable of providing an optical member such as a touch panel or a display body unit causing little damage to an optical substrate and favorable in productivity, and an optical member exhibiting high cure extent of resin composition and high reliability. Solution of Problem [0010] The inventors have conducted intensive investigations in order to solve the problems described above, and as a result, have found out the following fact, thereby completing the invention. The problems described above is solved by producing an optical substrate having a light shielding portion and another optical substrate to be bonded thereto by a method including specific Processes 1 to 3 using an ultraviolet curable resin composition. In other words, the invention relates to the following (1) to (21). [0011] (1) [0012] A method of producing an optical member including at least a pair of optical substrates, in which both of a transparent optical substrate having a light shielding portion on a surface thereof and another optical substrate to be bonded to the transparent optical substrate having a light shielding portion on a surface thereof are bonded to each other through a procedure including the following Processes 1 to 3 using an ultraviolet curable resin composition, the method including: [0013] Process 1: a process of forming a coating layer by coating the ultraviolet curable resin composition on at least either of bonding surfaces of a transparent optical substrate having a light shielding portion on a surface thereof and another optical substrate to be bonded to the transparent optical substrate having a light shielding portion on a surface thereof, and then allowing the coating layer to have a light shielded region selectively cured and the other part uncured by selectively irradiating the light shielded region, to be described below, in the coating layer thus obtained with ultraviolet rays, in which the light shielded region described above means a part of coating layer where ultraviolet rays do not reach since the part is shielded from ultraviolet rays by a light shielding portion when the two optical substrates are bonded to each other and the coating layer is irradiated with ultraviolet rays through the transparent optical substrate having a light shielding portion on the surface thereof; [0014] Process 2: a process of bonding the two optical substrates to each other by interposing the coating layer obtained in Process 1 between the bonding surfaces of the two optical substrates; and [0015] Process 3: a process of curing the uncured coating layer, which is interposed between the two optical substrates, by irradiating a laminated body having at least a pair of optical substrates bonded to each other by Processes 1 and 2 with ultraviolet rays through the transparent optical substrate having a light shielding portion. [0016] (2) [0017] The method of producing an optical member according to (1) described above, the method further including the following Process 4 after Process 3; [0018] Process 4: a process of applying pressure with respect to the optical substrates bonded to each other. [0019] (3) [0020] The method of producing an optical member according to (1) or (2) described above, in which the part, which is a part other than the light shielded region of the coating layer and is to remain as uncured, is masked with an ultraviolet shielding plate and irradiation with ultraviolet rays is performed when the light shielded region is cured in Process 1. [0021] (4) [0022] The method of producing an optical member according to any one of (1) to (3) described above, in which an irradiation dose of ultraviolet rays in Process 1 is at least 200 mJ/cm 2 . [0023] (5) [0024] The method of producing an optical member according to any one of (1) to (4) described above, in which the ultraviolet curable resin composition is coated at least either a surface provided with a light shielding portion of the optical substrate having a light shielding portion on a surface thereof or a display surface of a display unit that is the optical substrate to be bonded to the optical substrate having a light shielding portion on a surface thereof, and the optical substrate having a light shielding portion on a surface thereof and the display unit are bonded to each other such that a surface of the side having a light shielding portion of the optical substrate having a light shielding portion on a surface thereof and the display surface of the display unit face each other by interposing a coating layer thus obtained in Process 1. [0025] (6) [0026] The method of producing an optical member according to any one of (1) to (5) described above, in which the optical substrate having a light shielding portion on a surface thereof is at least one selected from the group consisting of a transparent glass substrate having a light shielding portion, a transparent resin substrate having a light shielding portion, a glass substrate having a light shielding portion and a transparent electrode formed thereon, and the optical substrate to be bonded to the optical substrate having a light shielding portion on a surface thereof is at least one selected from the group consisting of a liquid crystal display unit, a plasma display unit, and an organic EL display unit. [0027] (7) [0028] The method of producing an optical member according to any one of (1) to (6) described above, in which the ultraviolet curable resin composition is an ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator. [0029] (8) [0030] The method of producing an optical member according to (7) described above, in which (A) the (meth)acrylate is at least one selected from the group consisting of a urethane (meth)acrylate, a (meth)acrylate having a polyisoprene backbone, and a (meth)acrylate monomer. [0031] (9) [0032] The method of producing an optical member according to (7) or (8) described above, in which both of (i) a urethane (meth)acrylate or a (meth)acrylate having a polyisoprene backbone, and (ii) a (meth)acrylate monomer are included as (A) the (meth)acrylate. [0033] (10) [0034] The method of producing an optical member according to (8) or (9) described above, in which (A) the (meth)acrylate is a urethane (meth)acrylate having a polypropylene oxide structure or a (meth)acrylate monomer. [0035] (11) [0036] The method of producing an optical member according to any one of (8) to (10) described above, in which the urethane (meth)acrylate is a urethane (meth)acrylate obtained by reacting polypropylene glycol, polyisocyanate, and a hydroxyl group-containing (meth)acrylate. [0037] (12) [0038] The method of producing an optical member according to (8) or (9) described above, in which a weight average molecular weight of the urethane (meth)acrylate is from 7000 to 25000, and a number average molecular weight of the (meth)acrylate having a polyisoprene backbone is from 15000 to 50000. [0039] (13) [0040] The method of producing an optical member according to any one of (8) to (12) described above, in which the ultraviolet curable resin composition contains other components other than (A) the (meth)acrylate (B) and the photopolymerization initiator, and contains a urethane (meth)acrylate at from 20 to 80% by weight and a (meth)acrylate monomer at from 5 to 70% by weight with respect to the total amount of the ultraviolet curable resin composition as (A) the (meth)acrylate, and (B) the photopolymerization initiator at from 0.2 to 5% by weight with respect to the total amount of the ultraviolet curable resin composition, and the balance is other components. [0041] (14) [0042] An optical member obtained by the method of producing an optical member according to any one of (1) to (13) described above. [0043] (15) [0044] A touch panel obtained by the method of producing an optical member according to any one of (1) to (13) described above. [0045] (16) [0046] A display device, which is obtained by the method of producing an optical member according to (5) described above and has an optical substrate having a light shielding portion on a surface thereof on a display screen of a display unit. [0047] (17) [0048] Use of an ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator for the method of producing an optical member according to any one of (1) to (6) described above. [0049] (18) [0050] The use of an ultraviolet curable resin composition according to (17) described above, in which (A) the (meth)acrylate is at least one selected from the group consisting of a urethane (meth)acrylate, a (meth)acrylate having a polyisoprene backbone, and a (meth)acrylate monomer. [0051] (19) [0052] The use of an ultraviolet curable resin composition according to (17) described above, in which both of (i) a urethane (meth)acrylate or a (meth)acrylate having a polyisoprene backbone and (ii) a (meth)acrylate monomer are contained as (A) the (meth)acrylate. [0053] (20) [0054] The use of an ultraviolet curable resin composition according to (18) or (19) described above, in which the urethane (meth)acrylate is a urethane (meth)acrylate obtained by reacting polypropylene glycol, polyisocyanate, and a hydroxyl group-containing (meth)acrylate. [0055] (21) [0056] An ultraviolet curable resin composition to be used in the method of producing an optical member according to any one of (1) to (13) described above, the composition including (A) a (meth)acrylate and (B) a photopolymerization initiator. [0057] (22) [0058] The ultraviolet curable resin composition according to (21) described above, in which (A) the (meth)acrylate is at least one selected from the group consisting of a urethane (meth)acrylate, a (meth)acrylate having a polyisoprene backbone, and a (meth)acrylate monomer. [0059] (23) [0060] The method of producing an optical member according to (7) described above, in which the ultraviolet curable resin composition is an ultraviolet curable resin composition further containing a softening component. [0061] (24) [0062] The ultraviolet curable resin composition according to (21) described above, the composition further including a softening component. Advantageous Effects of Invention [0063] According to the invention, a bonded optical member causing little damage to an optical substrate and exhibiting favorable productivity and excellent curability and adherence, for example, a touch panel or a display body unit having an optical substrate having a light shielding portion can be obtained. Moreover, an optical member exhibiting high cure extent of resin at a light shielding portion and high reliability, and not causing a problem such as display unevenness of the display image near a light shielding portion can be provided. BRIEF DESCRIPTION OF DRAWINGS [0064] FIGS. 1( a ) to 1 ( c ) are process diagrams illustrating an embodiment (first embodiment) of the producing method according to the invention. [0065] FIGS. 2( a ) to 2 ( c ) are process diagrams illustrating another embodiment (second embodiment) of the producing method according to the invention. [0066] FIGS. 3( a ) to 3 ( c ) are process diagrams illustrating a producing process according to Comparative Example 1. [0067] FIG. 4 is a schematic drawing of an optical member obtained by the invention. DESCRIPTION OF EMBODIMENTS [0068] First, the producing process of an optical member using an ultraviolet curable resin composition of the invention will be described. [0069] In the method of producing an optical member of the invention, a transparent optical substrate having a light shielding portion on the surface thereof and another optical substrate to be bonded to the transparent optical substrate having a light shielding portion on the surface thereof are bonded to each other by the following Processes 1 to 3 using an ultraviolet curable resin composition. [0070] Process 1: a process of forming a coating layer by coating an ultraviolet curable resin composition on at least either of bonding surfaces of a transparent optical substrate having a light shielding portion on a surface thereof and another optical substrate to be bonded thereto, and then allowing the coating layer to have a light shielded region selectively cured and the other part uncured by selectively irradiating the light shielded region, to be described below, in the coating layer thus obtained with ultraviolet rays, [0071] Process 2: a process of bonding the two optical substrates to each other by interposing the coating layer obtained in Process 1 between the bonding surfaces of the two optical substrates, and [0072] Process 3: a process of curing the coating layer, which is interposed between the two optical substrates and uncured, by irradiating a laminated body having at least a pair of optical substrates bonded to each other by Processes 1 and 2 with ultraviolet rays through the transparent optical substrate having the light shielding portion. [0073] In the present specification, the term “light shielded region” or “light shielded region at the time of bonding” means a part of coating layer, where ultraviolet rays do not reach since the part is shielded from ultraviolet rays by the light shielding portion when the two optical substrates are bonded to each other and the coating layer is irradiated with ultraviolet rays through the transparent optical substrate having a light shielding portion on the surface thereof. [0074] Hereinafter, specific embodiments of the method of producing an optical member through Process 1 to Process 3 of the invention will be described by exemplifying a case, in which a liquid crystal display unit and a transparent substrate having a light shielding portion are bonded to each other, with reference to drawings. First Embodiment [0075] FIGS. 1( a ) to 1 ( c ) are process diagrams illustrating the first embodiment of the method of producing an optical member using an ultraviolet curable resin composition according to the invention. [0076] This first embodiment is a method of obtaining an optical member (a liquid crystal display unit having a light shielding portion) by bonding a liquid crystal display unit 1 to a transparent substrate 2 having a light shielding portion. [0077] The liquid crystal display unit 1 is a liquid crystal display unit prepared by enclosing a liquid crystal material between a pair of substrates having an electrode formed thereon and then equipping the pair of substrates with a polarizing plate, a driving circuit, a signal input cable, and a backlight unit. [0078] The transparent substrate 2 having a light shielding portion is a transparent substrate prepared by forming a light shielding portion 4 of black frame shape on the surface of the bonding surface of a transparent substrate 3 such as a glass plate, a polymethyl methacrylate (PMMA) plate, a polycarbonate (PC) plate, or an alicyclic polyolefin polymer (COP) plate. [0079] Here, the light shielding portion 4 is formed by gluing tape, coating a coating, printing, or the like. [0080] (Process 1) [0081] First, as illustrated in FIG. 1( a ), an ultraviolet curable resin composition is coated on the surface of the display surface of the liquid crystal display unit 1 and the surface provided with a light shielding portion of the transparent substrate 2 having a light shielding portion, respectively. As the coating method, a method using a slit coater, a roll coater, a spin coater, or a screen printing method is exemplified. Here, the ultraviolet curable resin compositions coated on the surface of the liquid display unit 1 and the surface of the transparent substrate 2 having a light shielding portion may be the same as each other, or different ultraviolet curable resin compositions may be used. It is generally preferable that the ultraviolet curable resin compositions used for both surfaces be the same as each other. [0082] The film thickness of the cured product of each of the ultraviolet curable resin compositions is adjusted such that the cured product layer of resin 7 after bonding is from 50 to 500 μm, preferably from 50 to 350 μm, and further preferably from 100 to 350 μm. [0083] The light shielded region (the part of coating layer, which is in the light shielded region shielded from ultraviolet rays by the light shielding portion when the laminated body including the liquid crystal display unit 1 and the transparent substrate 2 having a light shielding portion bonded to each other is irradiated with ultraviolet rays from the side of the transparent substrate 2 having a light shielding portion) at the time of bonding in a coating layer 5 of ultraviolet curable resin composition after coating is selectively irradiated with ultraviolet rays, thereby obtaining a coating layer 7 of ultraviolet curable resin composition having the light shielded region at the time of bonding selectively cured. At this time, the region exposed to light at the time of bonding is masked with an ultraviolet shielding plate when the coating layer is irradiated with ultraviolet rays such that the region exposed to light (the part of coating layer exposed to ultraviolet rays when the laminated body including the two optical substrates bonded to each other is irradiated with ultraviolet rays from the side of the transparent substrate 2 having a light shielding portion) at the time of bonding is not cured. [0084] The irradiation dose of ultraviolet rays at this time is preferably 200 mJ/cm 2 or more, and particularly preferably 1000 mJ/cm 2 or more. If the irradiation dose is too little, insufficient cure extent of the part of light shielding portion of the optical member bonded in the end is concerned. The upper limit of the irradiation dose of ultraviolet rays is not particularly limited, but is preferably 4000 mJ/cm 2 or less, and more preferably 3000 mJ/cm 2 or less. [0085] With regard to the light source used in the irradiation with ultraviolet rays from ultraviolet to near-ultraviolet, any kind of light source may be used if a light source is a lamp emitting a light beam of from ultraviolet to near-ultraviolet. Examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, or an extra-high pressure mercury lamp, a metal halide lamp, a (pulse)xenon lamp, or an electrodeless lamp. [0086] Here, the technique, in which only the resin composition in the light shielded region is selectively irradiated with ultraviolet rays but the region exposed to light at the time of bonding is not irradiated, is explained by exemplifying a technique, in which the region exposed to light is masked with an ultraviolet shielding plate in the present embodiment, but the technique to selectively irradiate the light shielded region with ultraviolet rays is not limited to the present technique. The method is not particularly limited but any method can be adopted as long as a method is capable of selectively curing the light shielded region. For example, a method, in which the shape of the light source of the ultraviolet irradiator is the same as the shape of the light shielding portion, or a method (a method using spot UV), in which light source is designed such that the ultraviolet rays are concentrated at a specific position through an optical fiber and the light shielded region is scanned with the concentrated ultraviolet rays, can be adopted. The method using an ultraviolet shielding plate is more preferable from the viewpoint of being simple. [0087] In Process 1, the irradiation with ultraviolet rays is performed from the surface of the upper side (the opposite side to the liquid crystal display unit side or the opposite side to the transparent substrate side when seen from the ultraviolet curable resin composition) (generally the surface of the atmosphere side) of the coating layer. The irradiation with ultraviolet rays can be performed in the air, or depending on the purpose, the irradiation with ultraviolet rays may be performed in a vacuum, or in the presence or absence of a curing inhibitory gas such as oxygen or ozone under reduced pressure or normal pressure. In addition, depending on the purpose, the irradiation with ultraviolet rays may be performed while spraying a curing inhibitory gas or an inert gas upon the upper surface of the coating layer after evacuating. The opposite side to the liquid crystal display unit side or the opposite side to the transparent substrate side is the atmosphere side in a case in which the resin composition in the light shielded region is cured in the air. [0088] The irradiation with ultraviolet rays is preferably performed on the upper surface of the coating layer in the air or in the presence of a curing inhibitory gas such as oxygen and ozone from the viewpoint of preserving the stickiness and improving adhesiveness of the surface of the coating layer in the light shielded region. [0089] (Process 2) Next, the liquid crystal display unit 1 and the transparent substrate 2 having a light shielding portion are bonded to each other as illustrated in FIG. 1 ( b ) in the form that the coating layers 7 (coating layer of the ultraviolet curable resin composition having a light shielded region at the time of bonding selectively cured) face each other. The bonding can be performed in the air or in a vacuum. [0090] Here, it is suitable to perform bonding in a vacuum in order to prevent air bubbles from being generated at the time of bonding. [0091] As described above, the improvement in adhesive force can be expected if a coating layer 7 of the ultraviolet curable resin composition having a light shielded region cured for each of the liquid crystal display unit 1 and the transparent substrate 2 is prepared, and then the liquid crystal display unit 1 and the transparent substrate 2 are bonded to each other. [0092] (Process 3) [0093] Next, as illustrated in FIG. 1 ( c ), the ultraviolet curable resin composition layer (coating layer) is cured by irradiating the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 to each other with ultraviolet rays 9 from the side of the transparent substrate 2 having a light shielding portion. [0094] The irradiation dose of ultraviolet rays is preferably about from 100 to 4000 mJ/cm 2 , and particularly preferably about from 200 to 3000 mJ/cm 2 in Process 3. With regard to the light source used for curing by the irradiation with light beam of from ultraviolet to near-ultraviolet, any kind of light source may be used if a light source is a lamp emitting a light beam of from ultraviolet to near-ultraviolet. Examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, or an extra-high pressure mercury lamp, a metal halide lamp, a (pulse)xenon lamp, or an electrodeless lamp. [0095] In this manner, an optical member as illustrated in FIG. 4 can be obtained. [0096] (Process 4) [0097] Moreover, if necessary, the adhesion of the optical member thus obtained can be increased by applying pressure thereto as the (Process 4). The adhesive force of the cured product layer in the light shielded region at the time of bonding is improved if pressure is applied. By virtue of this, at the time of bonding the liquid crystal display unit 1 and the transparent substrate 2 , the effect that the separation at the interface between the coating layers 7 , which are adhered to each other, by external pressure or an environmental change is prevented can be expected. In addition, the adhesive force of the cured product layer of resin 8 with respect to the liquid crystal display unit 1 or the transparent substrate 2 having a light shielding portion is also further increased. [0098] Hence, it is preferable to include Process 4. Second Embodiment [0099] FIGS. 2( a ) to 2 ( c ) are process diagrams illustrating the second embodiment of the method of producing an optical member using an ultraviolet curable resin composition according to the invention. [0100] Meanwhile, the same reference numerals in the figures refer to the same elements as the constitutional elements in the first embodiment described above, and the explanation thereof will not be repeated here. [0101] (Process 1) [0102] First, as illustrated in FIG. 2 ( a ), an ultraviolet curable resin composition is coated on the surface provided with a light shielding portion 4 of a transparent substrate 2 having a light shielding portion. Thereafter, a coating layer 7 of the ultraviolet curable resin composition having a light shielded region at the time of bonding cured is obtained by irradiating the light shielded region at the time of bonding with ultraviolet rays. Here, the region exposed to light at the time of bonding is masked with an ultraviolet shielding plate 6 , whereby the resin composition in the region exposed to light is not cured when irradiation with ultraviolet rays is performed. [0103] (Process 2) [0104] Next, as illustrated in FIG. 2 ( b ), the liquid crystal display unit 1 and a transparent substrate 2 having a light shielding portion are bonded to each other in the form that the coating layer 7 of the transparent substrate 2 having a light shielding portion and the display surface of a liquid crystal display unit 1 face each other. The bonding can be performed in the air or in a vacuum. [0105] (Process 3) [0106] Next, as illustrated in FIG. 2 ( c ), the ultraviolet curable resin composition in the region exposed to light at the time of bonding is cured by irradiating the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 to each other with ultraviolet rays 9 from the side of the transparent substrate 2 having a light shielding portion. [0107] In this manner, an optical member illustrated in FIG. 4 can be obtained. Third Embodiment [0108] The optical member of the invention can be produced according to the third embodiment modified as follows in addition to the first embodiment and the second embodiment. [0109] (Process 1) [0110] First, an ultraviolet curable resin composition is coated on the display surface of a liquid crystal display unit 1 , and then a coating layer 7 of the ultraviolet curable resin composition having a light shielded region at the time of bonding cured is obtained by irradiating the light shielded region at the time of bonding with ultraviolet rays. Here, the region exposed to light at the time of bonding is masked with an ultraviolet shielding plate 6 , whereby the resin composition in the region exposed to light is not cured when irradiation with ultraviolet rays is performed. [0111] (Process 2) [0112] Next, a liquid crystal display unit 1 and the transparent substrate 2 having a light shielding portion are bonded to each other in the form that the coating layer 7 of the liquid crystal display unit 1 and the surface provided with a light shielding portion 4 of the transparent substrate 2 having a light shielding portion face each other. The bonding can be performed in the air or in a vacuum. [0113] (Process 3) [0114] Next, the ultraviolet curable resin composition in the region exposed to light at the time of bonding is cured by irradiating the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 to each other with ultraviolet rays 9 from the side of the transparent substrate 2 having a light shielding portion. [0115] In this manner, an optical member illustrated in FIG. 4 can be obtained. Fourth Embodiment [0116] The optical member of the invention can be produced according to the fourth embodiment modified as follows in addition to the first embodiment, the second embodiment, and the third embodiment. [0117] (Process 1) [0118] First, an ultraviolet curable resin composition is coated on each of the display surface of a liquid crystal display unit 1 and the surface provided with a light shielding portion 4 of a transparent substrate 2 having a light shielding portion. Thereafter, a coating layer 7 of the ultraviolet curable resin composition having a light shielded region at the time of bonding cured is obtained by irradiating the light shielded region at the time of bonding with ultraviolet rays. Here, the irradiation dose of ultraviolet rays is adjusted by containing acyl phosphine oxide in the ultraviolet curable resin composition, thereby obtaining the coating layers 7 of cured product layers having a cured part present on the lower side (the side of the liquid crystal display unit 1 or the transparent substrate 2 having a light shielding portion) of the coating layer 7 and an uncured part present on the upper side (the opposite side to the side of the liquid crystal display unit 1 or the transparent substrate 2 having a light shielding portion) of the coating layer 7 . Meanwhile, the region exposed to light at the time of bonding is masked with an ultraviolet shielding plate 6 , whereby the resin composition in the region exposed to light is not cured when irradiation with ultraviolet rays is performed. [0119] (Process 2) [0120] Next, a liquid crystal display unit 1 and the transparent substrate 2 having a light shielding portion are bonded to each other in the form that the coating layers 7 face each other. The bonding can be performed in the air or in a vacuum. [0121] (Process 3) [0122] Next, the ultraviolet curable resin composition in the region exposed to light at the time of bonding is cured by irradiating the optical member obtained by bonding the transparent substrate 2 and the liquid crystal display unit 1 to each other with ultraviolet rays 9 from the side of the transparent substrate 2 having a light shielding portion. [0123] In this manner, an optical member illustrated in FIG. 4 can be obtained. [0124] Each of the embodiments described above is an embodiment explaining several embodiments of the method of producing an optical member of the invention with reference to an exemplary specific optical substrate. Each of the embodiments is explained using a liquid crystal display unit and a transparent substrate having a light shielding portion. In the producing method of the invention, however, various kinds of members to be described below can be used as an optical substrate instead of the liquid crystal display unit, and various kinds of members to be described below can also be used as an optical substrate instead of the transparent substrate. [0125] Not only that, as an optical substrate such as a liquid crystal display unit and a transparent substrate, an optical substrate, in which another optical substrate layer (for example, a film bonded using a cured product layer of an ultraviolet curable resin composition or another optical substrate layer) is further laminated to these various substrates, may be used. [0126] Moreover, all of the coating method of ultraviolet curable resin composition, the film thickness of cured product of resin, the irradiation dose and light source at the time of ultraviolet rays irradiation, a technique to irradiate the light shielded region selectively with ultraviolet rays, and a process to increase adhesion by applying pressure to the optical member, which are described in the section of the first embodiment, are not only applied to the embodiments described above but can also be applied to any of the producing methods included in the invention. [0127] Specific aspects of the optical member, including the liquid crystal display unit, capable of being produced by from the first embodiment to the fourth embodiment described above are represented below. [0128] (i) An aspect in which an optical substrate having a light shielding potion is at least an optical substrate selected from the group consisting of a transparent glass substrate having a light shielding portion, a transparent resin substrate having a light shielding portion, and a glass substrate having a light shielding portion and a transparent electrode formed thereon, another optical substrate bonded thereto is at least a display body unit selected from the group consisting of a liquid crystal display unit, a plasma display unit, and an organic EL display unit, and the optical member to be obtained is the display body unit having an optical substrate having a light shielding portion. [0129] (ii) An aspect in which one optical substrate is a protective substrate having a light shielding portion and the other optical substrate to be bonded thereto is a touch panel or a display body unit having a touch panel, and an optical member including at least two optical substrates bonded to each other is a touch panel having a protective substrate having a light shielding portion or a display body unit having the touch panel. [0130] In this case, either one or both of the surface provided with a light shielding portion of the protective substrate having a light shielding portion and the touch surface of the touch panel are preferably coated with an ultraviolet curable resin composition in Process 1. [0131] (iii) An aspect in which one optical substrate is an optical substrate having a light shielding portion and the other optical substrate to be bonded thereto is a display body unit, and an optical member including at least two optical substrates bonded to each other is a display body unit having an optical substrate having a light shielding portion. [0132] In this case, either one or both of the surface of the side provided with a light shielding portion of the optical substrate having a light shielding portion and the display surface of the display body unit are preferably coated with an ultraviolet curable resin composition in Process 1. [0133] Specific examples of the optical substrate having a light shielding portion may include a protective plate for display screen having a light shielding portion or a touch panel provided with a protective substrate having a light shielding portion. [0134] The surface of the side provided with a light shielding portion of an optical substrate having a light shielding portion is, for example, the surface of the side provided with a light shielding portion of a protective plate in a case in which an optical substrate having a light shielding portion is a protective plate for display screen having a light shielding portion. In addition, the surface of the side provided with a light shielding portion of an optical substrate having a light shielding portion means the substrate surface of a touch panel opposite to the touch surface of the touch panel since the surface having a light shielding portion of a protective substrate having a light shielding portion is bonded to the touch surface of the touch panel in a case in which an optical substrate having a light shielding portion is a touch panel having a protective substrate having a light shielding portion. [0135] The light shielding portion of an optical substrate having a light shielding portion may be at any position of the optical substrate, but is generally prepared in a frame shape on the periphery of an optical substrate of transparent platy shape or sheet shape. The width thereof is about from 0.5 to 10 mm, preferably about from 1 to 8 mm, and more preferably about from 2 to 8 mm. [0136] Next, the ultraviolet curable resin composition of the invention will be described. [0137] The ultraviolet curable resin composition used in the method of producing an optical member of the invention is not particularly limited as long as a resin is cured by irradiation with ultraviolet rays, but an ultraviolet curable resin composition (hereinafter, it is also referred to as “ultraviolet curable resin composition of the invention”) containing (A) a (meth)acrylate and (B) a photopolymerization initiator is preferably used. The ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator can contain other components capable of being added to an ultraviolet curable resin composition used for optics as an arbitrary component. [0138] Meanwhile, the phrase “capable of being added to an ultraviolet curable resin composition used for optics” means that an additive deteriorating the transparency of cured product to an extent that the cured product cannot be used for optics is not contained. [0139] A preferred average transmittance of a sheet is at least 90% at the light having a wavelength of from 400 to 800 nm when the sheet of cured product having a thickness of 200 μm after curing is prepared using the ultraviolet curable resin composition used in the invention. [0140] The compositional proportion of the ultraviolet curable resin composition is that (A) the (meth)acrylate is from 25 to 90% by weight and (B) the photopolymerization initiator is from 0.2 to 5% by weight with respect to the total amount of the ultraviolet curable resin composition, and other components are the balance. [0141] In the ultraviolet curable resin composition of the invention, any photopolymerization initiator generally used can be used as (B) the photopolymerization initiator. [0142] (A) The (meth)acrylate in the ultraviolet curable resin composition of the invention is not particularly limited, but any one selected from the group consisting of a urethane (meth)acrylate, a (meth)acrylate having a polyisoprene backbone, and a (meth)acrylate monomer is preferably used. A more preferred aspect is that the ultraviolet curable resin composition of the invention contains both of (i) at least either a urethane (meth)acrylate or a (meth)acrylate having a polyisoprene backbone, and (ii) a (meth)acrylate monomer, as (A) the (meth)acrylate. [0143] Meanwhile, the “(meth)acrylate” in the present specification means either one or both of methacrylate and acrylate. The same applies to “(meth)acrylic acid” or the like. [0144] In addition, (ii) a (meth)acrylate monomer described above is used in the meaning of a (meth)acrylate other than (i) described above. [0145] The urethane (meth)acrylate is obtained by reacting three of a polyhydric alcohol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate. [0146] Examples of the polyhydric alcohol include an alkylene glycol having from 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol; a triol such as trimethylolpropane and pentaerythritol; an alcohol having a cyclic backbone such as tricyclodecanedimethylol and bis-[hydroxymethyl]-cyclohexane; and a polyester polyol obtained by the reaction of these polyhydric alcohols and a polybasic acid (for example, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride); a caprolactone alcohol obtained by the reaction of a polyhydric alcohol and ε-caprolactone; a polycarbonate polyol (for example, a polycarbonate diol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate); or a polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and ethylene oxide modified bisphenol A). [0147] Polypropylene glycol is preferable as the polyhydric alcohol from the viewpoint of the compatibility and adherence with other (A) components, and polypropylene glycol having a weight average molecular weight of 2000 or more is particularly preferable from the viewpoint of the adherence between the substrate and the cured product layer or the cured product layers. The adhesive force of the cured product layer is increased if polypropylene glycol having a weight average molecular weight of 2000 or more is used, and hence the effect that the separation at the interface between the coating layers 7 of the ultraviolet curable resin composition having a light shielded region cured at the time of bonding, which are adhered to each other, by external pressure or an environmental change is prevented is improved when optical substrates such as a liquid crystal display unit and a transparent substrate are bonded to one another. In addition, the adhesive force of the cured product layer of resin 8 with respect to the optical substrates of the liquid crystal display unit 1 or the transparent substrate 2 having a light shielding portion is also further increased. At this time, the upper limit of the weight average molecular weight of the polypropylene glycol is not particularly limited, but is preferably 10000 or less and more preferably 5000 or less. [0148] Examples of an organic polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, or dicyclopentanyl isocyanate. [0149] In addition, as the hydroxyl group-containing (meth)acrylate, for example, a hydroxyl C2-C4 alkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; dimethylolcyclohexyl mono(meth)acrylate; hydroxycaprolactone (meth)acrylate; and hydroxy-terminated polyalkylene glycol (meth)acrylate can be used. [0150] The reaction to obtain the urethane (meth)acrylate is performed, for example, by the following manner. In other words, the polyhydric alcohol and the organic polyisocyanate is mixed such that an isocyanate group of the organic polyisocyanate per 1 equivalent hydroxyl group of the polyhydric alcohol is preferably from 1.1 to 2.0 equivalent and further preferably from 1.1 to 1.5 equivalent, and then the mixture is reacted at preferably from 70 to 90° C., thereby synthesizing a urethane oligomer. Subsequently, the urethane oligomer thus obtained and a hydroxy (meth)acrylate compound is mixed such that the hydroxyl group of the hydroxy (meth)acrylate compound per 1 equivalent isocyanate of the urethane oligomer is preferably from 1 to 1.5 equivalent, and then the mixture is reacted at from 70 to 90° C., thereby obtaining a urethane (meth)acrylate of the intended product. [0151] The weight average molecular weight of the urethane (meth)acrylate is preferably about from 7000 to 25000 and more preferably from 10000 to 20000. Increase in shrinkage is concerned if the weight average molecular weight is too low, and deterioration in curability is concerned if the weight average molecular weight is too high. [0152] With regard to the urethane (meth)acrylate in the ultraviolet curable resin composition of the invention, a kind of urethane (meth)acrylate can be used singly, or two or more kinds thereof can be mixed at an arbitrary proportion and used. The weight proportion of the urethane (meth)acrylate in the ultraviolet curable resin composition of the invention is generally from 20 to 80% by weight and preferably from 30 to 70% by weight. [0153] The (meth)acrylate having a polyisoprene backbone is a compound having a (meth)acryloyl group at a terminal or a side chain of a polyisoprene molecule. The (meth)acrylate having a polyisoprene backbone can be available, for example, as “UC-203” (manufactured by KURARAY CO., LTD.). The number average molecular weight of the (meth)acrylate having a polyisoprene backbone is preferably from 10000 to 50000 and more preferably about from 25000 to 45000 in terms of polystyrene. [0154] The weight proportion of the (meth)acrylate having a polyisoprene backbone in the ultraviolet curable resin composition of the invention is generally from 20 to 80% by weight and preferably from 30 to 70% by weight. [0155] As the (meth)acrylate monomer, a (meth)acrylate having one (meth)acryloyl group in the molecule can be suitably used. [0156] Here, a (meth)acrylate monomer indicates a (meth)acrylate other than the urethane (meth)acrylate, the epoxy (meth)acrylate to be described below, and the (meth)acrylate having a polyisoprene backbone. [0157] Specific examples of the (meth)acrylate having one (meth)acryloyl group in the molecule may include an alkyl (meth)acrylate having from 5 to 20 carbon atoms such as isooctyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, cetyl (meth)acrylate, isomyristyl (meth)acrylate, and tridecyl (meth)acrylate; a (meth)acrylate having a cyclic backbone and preferably a cyclic backbone having from 4 to 10 carbon atoms such as benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, acryloylmorpholine, phenyl glycidyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate, polypropylene oxide modified nonylphenyl (meth)acrylate, and dicyclopentadieneoxyethyl (meth)acrylate; an alkyl (meth)acrylate having from 1 to 5 carbon atoms, which has a hydroxyl group such as 2-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; a polyalkylene glycol (meth)acrylate such as ethoxydiethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, and polypropylene oxide modified nonylphenyl (meth)acrylate; and a phosphoric acid (meth)acrylate such as ethylene oxide modified phenoxylated phosphoric acid (meth)acrylate, ethylene oxide modified butoxylated phosphoric acid (meth)acrylate, and ethylene oxide modified octyloxylated phosphoric acid (meth)acrylate and preferably ethylene oxide modified-alkoxylated or phenoxylated phosphoric acid (meth)acrylate having from 4 to 10 carbon atoms. [0158] As the (meth)acrylate having one (meth)acryloyl group in the molecule, among them, a compound selected from a group consisting of an alkyl (meth)acrylate having from 10 to 20 carbon atoms, 2-ethylhexyl carbitol acrylate, acryloylmorpholine, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isostearyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and polypropylene oxide modified nonylphenyl (meth)acrylate is preferably used. Particularly, a compound selected from the group consisting of an alkyl (meth)acrylate having from 10 to 20 carbon atoms, dicyclopentenyloxyethyl (meth)acrylate, polypropylene oxide modified nonylphenyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate is preferably used, an alkyl (meth)acrylate having from 10 to 20 carbon atoms is more preferably used, and lauryl (meth)acrylate is further preferably used from the viewpoint of flexibility of resin. [0159] Meanwhile, as the (meth)acrylate monomer, at least one of an alkyl (meth)acrylate having from 1 to 5 carbon atoms, which has a hydroxyl group, and acryloylmorpholine is preferably used, and acryloylmorpholine is particularly preferably used from the viewpoint of improvement in adherence to glass. [0160] As the (meth)acrylate monomer, both of an alkyl (meth)acrylate having from 10 to 20 carbon atoms and an alkyl (meth)acrylate having from 1 to 5 carbon atoms, which has a hydroxyl group, or acryloylmorpholine are preferably contained, and both of lauryl (meth)acrylate and acryloylmorpholine are preferably contained. [0161] The composition of the invention can contain a multifunctional (meth)acrylate monomer other than the (meth)acrylate having one (meth)acryloyl group in the range that the characteristics of the invention are not impaired. [0162] Examples of the multifunctional (meth)acrylate monomer may include a bifunctional (meth)acrylate such as tricyclodecanedimethylol di(meth)acrylate, dioxane glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, alkylene oxide modified bisphenol A type di(meth)acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol di(meth)acrylate, and ethylene oxide modified phosphoric acid di(meth)acrylate; a trifunctional (meth)acrylate such as a trimethylol C2-C10 alkane tri(meth)acrylate such as trimethylolpropane tri(meth)acrylate, and trimethyloloctane tri(meth)acrylate, trimethylol C2-C10 alkane polyalkoxy tri(meth)acrylate such as trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane polypropoxy tri(meth)acrylate, and trimethylolpropane polyethoxy polypropoxy tri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, pentaerythritol tri(meth)acrylate, and alkylene oxide modified trimethylolpropane tri(meth)acrylate such as ethylene oxide modified trimethylolpropane tri(meth)acrylate and propylene oxide modified trimethylolpropane tri(meth)acrylate; and a tetrafunctional or more (meth)acrylate such as pentaerythritol polyethoxy tetra(meth)acrylate, pentaerythritol polypropoxy tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. [0163] In the invention, a bifunctional (meth)acrylate is preferably used in order to suppress cure shrinkage in a case in which the polyfunctional (meth)acrylate described above is concurrently used. [0164] With regard to these (meth)acrylate monomers in the ultraviolet curable resin composition of the invention, a kind of (meth)acrylate monomer can be used singly, or two or more kinds thereof can be mixed at an arbitrary proportion and used. The weight proportion of the (meth)acrylate monomer in the ultraviolet curable resin composition of the invention is generally from 5 to 70% by weight and preferably from 10 to 50% by weight. Deterioration in curability is concerned if the weight proportion is less than 5% by weight, and increase in shrinkage is concerned if the weight proportion is more than 70% by weight. [0165] In the aspect, in which the ultraviolet curable resin composition of the invention contains both of (i) at least either a urethane (meth)acrylate or a (meth)acrylate having a polyisoprene backbone, and (ii) a (meth)acrylate monomer, the total content of both (i) and (ii) is generally from 25 to 90% by weight, preferably from 40 to 90% by weight, and more preferably from 40 to 80% by weight with respect to the total amount of the resin composition. [0166] In the invention, a (meth)acrylate having a polypropylene oxide structure is particularly preferably used as (A) the (meth)acrylate from the viewpoint of excellence in stickiness after curing in the coating layer of ultraviolet curable resin composition, which is obtained through Process 1 and of which the light shielded region is selectively cured and the other part other than the light shielded region is uncured, and imparting strong adhesive force in the interface at the time of bonding as well. The adhesive force of the cured product layer is improved if a (meth)acrylate having a polypropylene oxide structure is used, and hence the effect that the separation at the interface between the coating layers 7 of the ultraviolet curable resin composition having a light shielded region cured at the time of bonding, which are adhered to each other, by external pressure or an environmental change is prevented is improved when optical substrates such as a liquid crystal display unit and a transparent substrate are bonded to one another. In addition, the adhesive force of the cured product layer of resin 8 with respect to the liquid crystal display unit 1 or the transparent substrate 2 having a light shielding portion is also further increased. [0167] As the (meth)acrylate having a polypropylene oxide structure among (A) the (meth)acrylates, a urethane (meth)acrylate having a polypropylene oxide structure and a (meth)acrylate monomer having a polypropylene oxide structure and exemplified. [0168] In the ultraviolet curable resin composition of the invention, it is more preferable that a urethane (meth)acrylate having a polypropylene oxide structure be contained as (A) the (meth)acrylate. [0169] Specific examples of the urethane (meth)acrylate having a polypropylene oxide structure include a urethane (meth)acrylate obtained by reacting three of a polypropylene glycol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate. [0170] Specific examples of the (meth)acrylate monomer having a polypropylene oxide structure include polypropylene glycol (meth)acrylate, polypropylene oxide modified nonylphenyl (meth)acrylate, polypropylene glycol di(meth)acrylate, and propylene oxide modified trimethylolpropane tri(meth)acrylate. [0171] In the ultraviolet curable resin composition of the invention, an epoxy (meth)acrylate can be used as (A) the (meth)acrylate in a range that the characteristics of the invention are not impaired. [0172] An epoxy (meth)acrylate has a function that increases curability, hardness of cured product, or cure rate. As the epoxy (meth)acrylate, any epoxy (meth)acrylate obtained by reacting a glycidyl ether type epoxy compound with (meth)acrylic acid can be used. [0173] As the glycidyl ether type epoxy compound in order to obtain an epoxy (meth)acrylate to be preferably used, a diglycidyl ether of bisphenol A or an alkylene oxide adduct thereof, a diglycidyl ether of bisphenol F or an alkylene oxide adduct thereof, a diglycidyl ether of hydrogenated bisphenol A or an alkylene oxide adduct thereof, a diglycidyl ether of hydrogenated bisphenol F or an alkylene oxide adduct thereof, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like can be exemplified. [0174] An epoxy (meth)acrylate is obtained by reacting these glycidyl ether type epoxy compounds with (meth)acrylic acid under the following conditions. [0175] The glycidyl ether type epoxy compound and (meth)acrylic acid are reacted at a ratio of from 0.9 to 1.5 mole, and more preferably from 0.95 to 1.1 mole of (meth)acrylic acid per 1 equivalent epoxy group of the glycidyl ether type epoxy compound. The reaction temperature is preferably from 80 to 120° C., and the reaction time is about from 10 to 35 hours. In order to promote the reaction, for example, a catalyst such as triphenylphosphine, TAP, triethanolamine, and tetraethyl ammonium chloride is preferably used. In addition, for example, p-methoxyphenol and methylhydroquinone can also be used as a polymerization inhibitor in order to prevent polymerization during reaction. [0176] As the epoxy (meth)acrylate suitably usable in the invention, a bisphenol A type epoxy (meth)acrylate obtained from a bisphenol A type epoxy compound is exemplified. The weight average molecular weight of the epoxy (meth)acrylate suitably usable in the invention is preferably from 500 to 10000. [0177] The weight proportion of the epoxy (meth)acrylate in the ultraviolet curable resin composition of the invention is generally from 1 to 80% by weight and preferably from 5 to 30% by weight. [0178] The content proportion of (A) the (meth)acrylate in the ultraviolet curable resin composition of the invention is from 25 to 90% by weight, preferably from 40 to 90% by weight, and more preferably from 40 to 80% by weight with respect to the total amount of the ultraviolet curable resin composition. [0179] In the ultraviolet curable resin composition of the invention, it is preferable to contain at least one selected from the group consisting of the urethane (meth)acrylate, the (meth)acrylate having a polyisoprene backbone, and the (meth)acrylate monomer as (A) the (meth)acrylate; it is more preferable that the content proportion of the urethane (meth)acrylate be from 20 to 80% by weight and preferably from 30 to 70% by weight, the content proportion of the (meth)acrylate having a polyisoprene backbone be from 20 to 80% by weight and preferably from 30 to 70% by weight, and the content proportion of the (meth)acrylate monomer be from 5 to 70% by weight and preferably from 10 to 50% by weight. [0180] In the ultraviolet curable resin composition of the invention, it is further preferable that either the urethane (meth)acrylate or the (meth)acrylate having a polyisoprene backbone be contained as (A) the (meth)acrylate and the content proportion thereof be from 20 to 80% by weight and preferably from 30 to 70% by weight, and the (meth)acrylate monomer be contained as (A) the (meth)acrylate and the content proportion thereof be from 5 to 70% by weight and preferably from 10 to 50% by weight. [0181] As (B) the photopolymerization initiator contained in the ultraviolet curable resin composition of the invention, any publicly known photopolymerization initiator can be used. [0182] Specific examples of (B) the photopolymerization initiator may include 1-hydroxycyclohexyl phenyl ketone (Irgacure (trade name, the same applies hereinafter) 184; manufactured by BASF), 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer (Esacure ONE; manufactured by Lamberti S. p. A.), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (Irgacure 2959; manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (Irgacure 127; manufactured by BASF), 2,2-dimethoxy-2-phenyl acetophenone (Irgacure 651; manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur (trade name) 1173; manufactured by BASF), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-one (Irgacure 907; manufactured by BASF), a mixture of oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester (Irgacure 754; manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl phenyl ethoxy phosphine oxide, bis(2,4,6-trimethyl benzoyl)-phenyl phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentyl phosphine oxide. [0183] Here, an acyl phosphine oxide compound such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide is preferably used in order to obtain a cured product layer having a cured part present on the optical substrate side and an uncured part present on the opposite side to the optical substrate side when the light shielded region of the ultraviolet curable resin composition after coating is selectively irradiated with ultraviolet rays. Among them, as (B) the photopolymerization initiator, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide is particularly preferable from the viewpoint of easy formation of the uncured part and the transparency of the cured product layer of resin. The irradiation dose of ultraviolet rays in Process 1 is preferably from 5 to 200 mJ/cm 2 and particularly preferably from 10 to 100 mJ/cm 2 in a case in which a cured product layer having a cured part present on the optical substrate side and an uncured part present on the opposite side to the optical substrate side is obtained in the coating layer 7 of the ultraviolet curable resin composition having a light shielded region cured at the time of bonding. [0184] In the ultraviolet curable resin composition of the invention, a kind of these (B) photopolymerization initiators can be used singly, or two or more kinds thereof can be mixed at an arbitrary proportion and used. The weight proportion of (B) the photopolymerization initiator in the ultraviolet curable resin composition of the invention is generally from 0.2 to 5% by weight and preferably from 0.3 to 3% by weight. The transparency and curability of the ultraviolet curable resin composition are favorable if the weight proportion thereof is in this range. However, deterioration in the transparency of cured product layer of resin is concerned if (B) the photopolymerization initiator is too much. In addition, the cure extent of the resin composition becomes insufficient if (B) the photopolymerization initiator is too little. [0185] The ultraviolet curable resin composition of the invention can contain a photopolymerization initiation auxiliary to be described below, a compound having a structure represented by Formula (1) to be described below, a softening component to be described below, and the additives to be described below as other components other than (A) the (meth)acrylate described above and (B) the photopolymerization initiator described above. The content proportion of other components with respect to the total amount of the ultraviolet curable resin composition of the invention is the balance obtained by subtracting the total amount of (A) the (meth)acrylate and (B) the photopolymerization initiator from the total amount of the ultraviolet curable resin composition. Specifically, the total amount of other components is from 0 to 74.8% by weight and preferably about from 5 to 70% by weight with respect to the total amount of the ultraviolet curable resin composition of the invention. [0186] In the ultraviolet curable resin composition of the invention, an amine capable of being a photopolymerization initiation auxiliary can also be concurrently used with (B) the photopolymerization initiator as one of other components. Examples of the usable amine include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, or p-dimethylaminobenzoic acid isoamyl ester. In a case in which a photopolymerization initiation auxiliary such as the amine is used, the content thereof in the ultraviolet curable resin composition of the invention is generally from 0.005 to 5% by weight and preferably from 0.01 to 3% by weight. [0187] A compound having a structure represented by Formula (1) can be contained in the ultraviolet curable resin composition of the invention if necessary. [0000] [0188] (In Formula (1), n represents an integer from 0 to 40, and m represents an integer from 10 to 50. R 1 and R 2 may be the same or different from each other. R 1 and R 2 are an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 1 to 18 carbon atoms, an alkynyl group having from 1 to 18 carbon atoms, and an aryl group having from 5 to 18 carbon atoms.) [0189] The compound having a structure represented by Formula (1) can be available, for example, as UNISAFE PKA-5017 manufactured by NOF CORPORATION (trade name, polyethylene glycol-polypropylene glycol allylbutyl ether). [0190] The weight proportion of the compound having a structure represented by Formula (1) in the ultraviolet curable resin composition of the invention is generally from 10 to 80% by weight and preferably from 10 to 70% by weight when the compound having a structure represented by Formula (1) is used. [0191] In the ultraviolet curable resin composition of the invention, a softening component other than those described above can be used if necessary. A publicly known softening component and plasticizer generally used in an ultraviolet curable resin can be used as the softening component other than those described above in the invention. Specific examples of the usable softening component include a polymer or oligomer other than the (meth)acrylate or the compound having a structure represented by Formula (1), an ester of phthalic acid, an ester of phosphoric acid, a glycol ester, an ester of citric acid, an ester of aliphatic dibasic acid, an ester of fatty acid, an epoxy plasticizer, castor oils, and a hydrogenated terpene resin. Examples of the polymer or oligomer may include a polymer or oligomer having a polyisoprene backbone, a polymer or oligomer having a polybutadiene backbone, or a polymer or oligomer having a xylene backbone, and any ester thereof. A polymer or oligomer having a polybutadiene backbone and any ester thereof is preferably used depending on the case. Specific examples of the polymer or oligomer having a polybutadiene backbone and an ester thereof include butadiene homopolymer, epoxy modified polybutadiene, butadiene-styrene random copolymer, maleic acid modified polybutadiene, and terminal hydroxyl group modified liquid polybutadiene. [0192] The weight proportion of the softening component in the ultraviolet curable resin composition is generally from 10 to 80% by weight and preferably from 10 to 70% by weight in a case in which the softening component is used. [0193] In the ultraviolet curable resin composition of the invention, an additive such as an antioxidant, an organic solvent, a coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, a light stabilizer (for example, a hindered amine compound, or the like), or a filler may be added if necessary. [0194] Specific examples of the antioxidant include BHT, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl.tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, octyl diphenylamine, 2,4-bis[(octylthio)methyl-O-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and dibutylhydroxytoluene. [0195] Specific examples of the organic solvent include an alcohol such as methanol, ethanol, and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, and xylene. [0196] Examples of the coupling agent include a silane coupling agent, a titanium-based coupling agent, a zirconium-based coupling agent, and an aluminum-based coupling agent. [0197] Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, and 3-chloropropyltrimethoxysilane. [0198] Specific examples of the titanium-based coupling agent include isopropyl(N-ethylamino-ethylamino)titanate, isopropyl triisostearoyl titanate, titanium di(dioctyl pyrophosphate)oxyacetate, tetraisopropyl di(dioctyl phosphite)titanate, and neoalkoxy tri(p-N-(β-aminoethyl)aminophenyl)titanate. [0199] Specific examples of the zirconium-based coupling agent and the aluminum-based coupling agent include Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxy tris(neodecanoyl) zirconate, neoalkoxy tris(dodecanoyl)benzenesulfonyl zirconate, neoalkoxy tris(ethylene amino ethyl)zirconate, neoalkoxy tris(m-aminophenyl)zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate. [0200] Specific examples of the polymerization inhibitor include p-methoxyphenol and methylhydroquinone. [0201] Specific examples of the light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetramethyl-4-piperidyl alcohol, 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate (Product name: LA-82 manufactured by ADEKA CORPORATION), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, a mixed ester product of 1,2,3,4-butane tetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, decanedioic acid bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecane-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-(meth)acrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl)ester, a reaction product of 1,1-dimethylethyl hydroperoxide and octane, N,N′,N″,N′″-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine, a polycondensate of dibutylamine.1,3,5-triazine.N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosane-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ester, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5,1,11,2]heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo-[5,1,11,2]-heneicosane-20-propanoic acid dodecyl ester/tetradecyl ester, propanedioic acid, [(4-methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, a higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, a hindered amine-based compound such as 1,3-benzenedicarboxamide and N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl), a benzophenone-based compound such as octabenzone, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl-butyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimide-methyl)-5-methyl-phenyl]benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, a reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and polyethylene glycol, a benzotriazole-based compound such as 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, a benzoate-based compound such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and a triazine-based compound such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol. A particularly preferred light stabilizer is a hindered amine-based compound. [0202] Specific examples of the filler include a powder such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, stellite, steatite, spinel, titania, and talc, or a bead obtained by the spheroidizing of these. [0203] The content proportion of the additive added if necessary with respect to the total amount of the ultraviolet curable resin composition is about from 0 to 3% by weight in total of the additives described above. The content proportion of various kinds of additives is from 0.01 to 3% by weight, preferably from 0.01 to 1% by weight, and more preferably from 0.02 to 0.5% by weight with respect to the total amount of the composition in a case in which the additives are used. [0204] The ultraviolet curable resin composition of the invention can be obtained by mixing and dissolving (A) the (meth)acrylate, (B) the photopolymerization initiator, and, if necessary, other components described above at from room temperature to 80° C. In addition, impurities may be removed by an operation such as filtration if necessary. [0205] It is preferable to adjust the blending ratio of the components appropriately with regard to the composition for adhesion of the ultraviolet curable resin composition of the invention such that the viscosity thereof is in a range of from 300 to 15000 mPa·s at 25° C. in consideration of the coating properties thereof. [0206] The cure shrinkage of the cured product of the ultraviolet curable resin composition of the invention is preferably 3.0% or less, and particularly preferably 2.0% or less. By virtue of this, the internal stress accumulated on the cured product of resin can be reduced, and thus occurring of distortion at the interface between the substrate and the cured product layer of the ultraviolet curable resin composition can be effectively prevented when the ultraviolet curable resin composition is cured. [0207] In addition, if the cure shrinkage is great, the display performance is significantly adversely affected from the time when a warp at the time of curing increases in a case in which the substrate such as glass is thin. The cure shrinkage is preferably small in extent from the viewpoint of this description as well. [0208] The cured product of the ultraviolet curable resin composition of the invention preferably has a transmittance of 90% or more in a wavelength region of from 400 to 800 nm when the cured product is formed into a film having a thickness of 200 μm. It is because that it is difficult for light to pass through the cured product in a case in which the transmittance is less than 90%, and thus decrease in visibility of the display image is concerned in a case in which the cured product is used in a display device. [0209] In addition, improvement in visibility of the display image is further expected if the transmittance in a wavelength region of from 400 to 450 nm is high. For this reason, the transmittance in a wavelength region of from 400 to 450 nm is preferably 90% or more when the cured product is formed into a film having a thickness of 200 μm. [0210] Several preferred aspects with regard to an ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator, which is used in the producing method of the invention, are described below. The “% by weight” in the content of respective components denotes the content proportion with respect to the total amount of the ultraviolet curable resin composition of the invention. [0211] (I) [0212] The ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator, in which (A) the (meth)acrylate is at least one (meth)acrylate selected from the group consisting of a urethane (meth)acrylate, a (meth)acrylate having a polyisoprene backbone, and a (meth)acrylate monomer. [0213] (II) [0214] The ultraviolet curable resin composition according to (I) described above, which contains both of (i) a urethane (meth)acrylate or a (meth)acrylate having a polyisoprene backbone, and (ii) a (meth)acrylate monomer as (A) the (meth)acrylate. [0215] (III) [0216] The ultraviolet curable resin composition according to (I) or (II) described above, in which the urethane (meth)acrylate or the (meth)acrylate monomer is a urethane (meth)acrylate having a polypropylene oxide structure or a (meth)acrylate monomer having a polypropylene oxide structure. [0217] (IV) [0218] The ultraviolet curable resin composition according to (I) or (II) described above, in which the urethane (meth)acrylate is a urethane (meth)acrylate obtained by reacting three of a polypropylene glycol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate. [0219] (V) [0220] The ultraviolet curable resin composition according to any one of (I) to (IV) described above, in which the weight average molecular weight of the urethane (meth)acrylate is from 7000 to 25000, and the number average molecular weight of the (meth)acrylate having a polyisoprene backbone is from 15000 to 50000. [0221] (VI) [0222] An ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator, in which 2,4,6-trimethyl benzoyl diphenyl phosphine oxide is contained as (B) the photopolymerization initiator, or the ultraviolet curable resin composition according to any one of (I) to (V) described above, in which 2,4,6-trimethyl benzoyl diphenyl phosphine oxide is contained as (B) the photopolymerization initiator. [0223] (VII) [0224] An ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator, which further contains other components other than (A) component and (B) component, or the ultraviolet curable resin composition according to any one of (I) to (VI) described above, which further contains other components other than (A) component and (B) component. [0225] (VIII) [0226] The ultraviolet curable resin composition according to (VII) described above, in which the content proportion of (A) a (meth)acrylate is from 25 to 90% by weight and the content proportion of (B) a photopolymerization initiator is from 0.2 to 5% by weight, and other components are the balance. [0227] (IX) [0228] The ultraviolet curable resin composition according to (VIII) described above, which contains (i) at least either a urethane (meth)acrylate or a polyisoprene (meth)acrylate at from 20 to 80% by weight, and (ii) a (meth)acrylate monomer at from 5 to 70% by weight as (A) the (meth)acrylate, and in which the sum of the two is from 40 to 90% by weight. [0229] (X) [0230] The ultraviolet curable resin composition according to any one of (VII) to (IX) described above, which contains a compound represented by Formula (1) at from 10 to 80% by weight as other components. [0231] (XI) [0232] An ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator or the ultraviolet curable resin composition according to any one of (I) to (X) described above, in which the cure shrinkage of the cured product of the ultraviolet curable resin composition is 3% or less. [0233] (XII) [0234] An ultraviolet curable resin composition containing (A) a (meth)acrylate and (B) a photopolymerization initiator or the ultraviolet curable resin composition according to any one of (I) to (XI) described above, in which the transmittance of a sheet which is a cured product of ultraviolet curable resin composition and has a film thickness of 200 μm is that the average transmittance in a wavelength region of from 400 to 450 nm is at least 90%, and the average transmittance in a wavelength region of from 400 to 800 nm is at least 90%. [0235] The ultraviolet curable resin composition of the invention can be suitably used as an adhesive to produce an optical member by bonding plural optical substrates to one another through a procedure including Process 1 to Process 3 and an arbitrary process 4. [0236] As the optical substrate used in the method of producing an optical member of the invention, a transparent plate, a sheet, a touch panel, a display body unit, and the like can be exemplified. [0237] The “optical substrate” in the present specification means both of an optical substrate, which does not have a light shielding portion on the surface, and an optical substrate, which has a light shielding portion on the surface. At least one of the plural optical substrates used is an optical substrate having a light shielding portion in the method of producing an optical member of the invention. [0238] The position of the shielding portion in the optical substrate having a light shielding portion is not particularly limited. As a preferred aspect, a case, in which a belt-shaped light shielding portion having a width of from 0.05 to 20 mm, preferably about from 0.05 to 10 mm, more preferably about from 0.1 to 6 mm is formed on the periphery of the optical substrate, is exemplified. The light shielding portion on an optical substrate can be formed by gluing tape, coating a coating, printing, or the like. [0239] In addition, in the method of producing an optical member of the invention, an optical substrate to be bonded to an optical substrate having a light shielding portion may be an optical substrate having a light shielding portion on the surface thereof or an optical substrate not having a light shielding portion. [0240] As the material of the optical substrate used in the invention, diverse materials can be used. Specific examples thereof include PET, PC, PMMA, a composite of PC and PMMA, glass, COC, COP, and a resin such as acrylic resin. As the optical substrate used in the invention, for example a transparent plate or a sheet, a sheet or transparent plate laminated with plural films such as a polarizing plate or sheets; a sheet or transparent plate not laminated; a transparent plate (an inorganic glass plate and processed goods thereof, for example, a lense, a prism, ITO glass) produced from an inorganic glass; and the like can be used. [0241] In addition, the optical substrate used in the invention includes a laminated body (hereinafter, it is also referred to as “functional laminated body”) formed of a plurality of functional plates or sheets such as a touch panel (a touch panel input sensor) or a display body unit to be described below in addition to the polarizing plate and the like described above. [0242] Examples of the sheet usable as the optical substrate used in the invention includes an icon sheet, a decorative sheet, and a protective sheet. Examples of the plate (transparent plate) usable in the method of producing an optical member of the invention include a decorative plate and a protective plate. As the material of these sheets and plates, the materials exemplified as the materials of the transparent plates and sheets above can be adopted. [0243] Examples of the material for the surface of the touch panel usable as the optical substrate used in the invention include glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP. [0244] The thickness of the optical substrate of a platy shape or sheet shape such as a transparent plate or a sheet is not particularly limited, and the thickness is generally from about 5 μm to about 5 cm, preferably from about 10 μm to about 10 mm, and more preferably about from 50 μm to 3 mm. [0245] As a preferred optical member obtainable by the producing method of the invention, an optical member, in which a transparent optical substrate, which has a light shielding portion and is in a platy shape or sheet shape, and the functional laminated body described above are bonded to each other using the cured product of the ultraviolet curable resin composition of the invention, can be exemplified. [0246] In addition, in the producing method of the invention, a display body unit with optical functional material (hereinafter, it is also referred to as “display panel”) can be produced by using a display body unit such as a liquid crystal display device as an optical substrate and an optical functional material as another optical substrate. Examples of the display body unit include a display device such as an LCD having a polarizing plate bonded to glass, an organic or inorganic EL display, EL lighting, electronic paper, and a plasma display. In addition, examples of the optical functional material include a transparent plastic plate such as an acrylic plate, a PC plate, a PET plate, and a PEN plate, tempered glass, and a touch panel input sensor. [0247] The refractive index of the cured product is more preferably from 1.45 to 1.55 since the visibility of display image is more improved in a case in which the ultraviolet curable resin composition of the invention is used as an adhesive for bonding optical substrates to one another. [0248] If the refractive index of the cured product is in the range, difference in refractive index with a substrate used as an optical substrate can be reduced, diffused reflection of light can be suppressed, and thus optical loss can be reduced. [0249] As preferred aspects of the optical member obtainable by the producing method of the invention, the following (i) to (vii) can be exemplified. [0250] (i) An optical member obtained by bonding an optical substrate having a light shielding portion and the functional laminated body to each other using the cured product of the ultraviolet curable resin composition of the invention. [0251] (ii) The optical member according to (i) above, in which the optical substrate having a light shielding portion is an optical substrate selected from the group consisting of a transparent glass substrate having a light shielding portion, a transparent resin substrate having a light shielding portion, and a glass substrate having a light shielding portion and a transparent electrode formed thereon, and the functional laminated body is a display body unit or a touch panel. [0252] (iii) The optical member according to (ii) above, in which the display body unit is any one of a liquid crystal display unit, plasma display unit, and an organic EL display unit. [0253] (iv) A touch panel (or a touch panel input sensor) obtained by bonding an optical substrate, which has a light shielding portion and is in a platy shape or sheet shape, to the surface of the touch surface side of the touch panel using the cured product of the ultraviolet curable resin composition of the invention. [0254] (v) A display panel obtained by bonding an optical substrate, which has a light shielding portion and is in a platy shape or sheet shape, onto the display screen of the display body unit using the cured product of the ultraviolet curable resin composition of the invention. [0255] (vi) The display panel according to (v) above, in which the optical substrate, which has a light shielding portion and is in a platy shape or sheet shape, is a protective substrate to protect the display screen of the display body unit, or a touch panel. [0256] (vii) The optical member, touch panel, or display panel according to any one of (i) to (vi) above, in which the ultraviolet curable resin composition is the ultraviolet curable resin composition according to any one of (I) to (XII) above. [0257] The optical member of the invention is obtained by bonding plural optical substrates selected from the respective optical substrates described above to one another through the method according to Processes 1 to 3 and Process 4 performed arbitrarily using the ultraviolet curable resin composition of the invention. In Process 1, the ultraviolet curable resin composition may be coated on only one surface of the surfaces facing each other via a cured product layer in two optical substrates to be bonded to each other, or may be coated on both of the surfaces. [0258] For example, in the case of the optical member according to (ii) above, in which the functional laminated body is a touch panel or a display body unit, the resin composition may be coated on only either one or both of either surface of the protective substrate having a light shielding portion, preferably the surface provided with the light shielding portion, and the touch surface of the touch panel or the display surface of the display body unit in Process 1. [0259] In addition, in the case of the optical member according to (vi) above, which is obtained by bonding a protective substrate to protect the display screen of the display body unit, or a touch panel to the display body unit, the resin composition may be coated on only either one or both of the surface provided with a light shielding portion of the protective substrate or the substrate surface opposite to the touch surface of the touch panel, and the display surface of the display body unit in Process 1. [0260] A display body unit including an optical substrate having a light shielding portion, which is obtained by the producing method of the invention can be incorporated into an electronic device such as a TV set, a small game console, a mobile phone, and a personal computer. EXAMPLES [0261] Hereinafter, the invention will be described further specifically with reference to Examples, but the invention is not limited to these Examples. [0262] Preparation of Ultraviolet Curable Resin Composition An ultraviolet curable resin composition A was prepared by heating and mixing 45 parts by weight of urethane acrylate (a reaction product obtained by reacting three components of polypropylene glycol (molecular weight of 3000), isophorone diisocyanate, and 2-hydroxyethyl acrylate at a mole ratio of 1:1.3:2), 25 parts by weight of UNISAFE PKA-5017 (Polyethylene glycol-polypropylene glycol allylbutyl ether, manufactured by NOF CORPORATION), 10 parts by weight of ACMO (acryloylmorpholine, manufactured by KOHJIN Holdings Co., Ltd.), 20 parts by weight of LA (lauryl acrylate, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), and 0.5 part by weight of Speedcure TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by LAMBSON) (Ultraviolet curable resin composition A). [0263] The following evaluations were performed using the ultraviolet curable resin composition A of the invention thus obtained. Example 1 [0264] As illustrated in FIG. 1( a ), the ultraviolet curable resin composition A thus prepared was coated on the display surface of a liquid crystal display unit 1 having an area of 3.5 inches and on the surface provided with a light shielding portion of a transparent glass substrate 2 having a light shielding portion 4 (width of 5 mm) such that the film thickness on each of the surfaces is 125 μm. Subsequently, each of the coating layers 5 thus obtained was irradiated with ultraviolet rays 9 having a cumulative amount of light of 2000 mJ/cm 2 from the atmosphere side using a high pressure mercury lamp (80 W/cm, ozone free) by interposing an ultraviolet shielding plate 6 in the region exposed to light at the time of bonding, and thus a coating layer in the light shielded region at the time of bonding was cured. [0265] Next, as illustrated in FIG. 1( b ), the liquid crystal display unit 1 and the transparent substrate 2 having a light shielding portion was bonded to each other in the form that the coating layers 7 , of which each of the light shielded regions was cured, face each other. Finally, as illustrated in FIG. 1( c ), the uncured coating layers were cured by irradiating the coating layers 7 with ultraviolet rays 9 having a cumulative amount of light of 2000 mJ/cm 2 from the side of the glass substrate 2 having a light shielding portion using a high pressure mercury lamp (80 W/cm, ozone free), thereby preparing the optical member of the invention (a liquid crystal display unit having a transparent glass substrate having a light shielding portion). Example 2 [0266] As illustrated in FIG. 2( a ), the ultraviolet curable resin composition A thus prepared was coated on a transparent glass substrate 2 which has an area of 3.5 inches and has a light shielding portion 4 (width of 5 mm) such that the film thickness of the resin composition is 250 μm. Subsequently, the coating layer 5 thus obtained was irradiated with ultraviolet rays 9 having a cumulative amount of light of 2000 mJ/cm 2 from the atmosphere side using a high pressure mercury lamp (80 W/cm, ozone free) by interposing an ultraviolet shielding plate 6 in the region exposed to light at the time of bonding, and thus a coating layer in the light shielded region at the time of bonding was cured. [0267] Next, as illustrated in FIG. 2( b ), the liquid crystal display unit 1 and the transparent substrate 2 having a light shielding portion was bonded to each other in the form that the coating layer 7 having a light shielded region cured in the transparent substrate 2 having a light shielding portion and the display surface of the liquid crystal display unit 1 face each other. Finally, as illustrated in FIG. 2( c ), the uncured coating layer was cured by irradiating the coating layer 7 with ultraviolet rays 9 having a cumulative amount of light of 2000 mJ/cm 2 from the side of the glass substrate 2 having a light shielding portion using a high pressure mercury lamp (80 W/cm, ozone free), thereby preparing the optical member of the invention (a liquid crystal display unit having a transparent glass substrate having a light shielding portion). Comparative Example 1 [0268] As illustrated in FIG. 3( a ), the ultraviolet curable resin composition A thus prepared was coated on each of the display surface of a liquid crystal display unit 1 and the surface provided with the light shielding portion of a transparent glass substrate 2 having a light shielding portion 4 (width of 5 mm) such that the film thickness on each of the surfaces is 125 μm. [0269] Next, as illustrated in FIG. 3( b ), the liquid crystal display unit 1 and the transparent substrate 2 having a light shielding portion was bonded to each other in the form that the coating layers 5 face each other. Finally, as illustrated in FIG. 3( c ), the coating layers were cured by irradiating the uncured coating layers with ultraviolet rays 9 having a cumulative amount of light of 2000 mJ/cm 2 from the side of the transparent glass substrate 2 having a light shielding portion using an extra-high pressure mercury lamp (TOSCURE 752, manufactured by TOSHIBA Lighting & Technology Corporation), thereby preparing the optical member of Comparative Example 1. [0270] (Determination of Cure Extent) [0271] The transparent substrate was detached from the optical member thus obtained, and then the cured product layer of resin in the light shielded region shielded from light by the light shielding portion, was washed away with isopropyl alcohol, thereby the uncured resin composition was removed. Thereafter, the cure extent was determined by confirming the cured state of the cured product layer of resin in the light shielded region. The evaluation of cure extent was performed based on the criteria below. Cure Extent: [0272] ◯ . . . Cured (traces that the uncured resin composition has been removed cannot be confirmed.) Δ . . . Uncured (cured product remains, but traces that uncured resin composition have been removed can also be confirmed.) X . . . Not cured at all (cured product does not remain at all.) [0000] TABLE 1 Example 1 Example 2 Comparative Example 1 Cure extent ◯ ◯ X [0273] From the result above, it is verified that the cured product layer of resin in the light shielded region exhibited high cure extent although the cured product layer of resin was shielded from ultraviolet rays by the light shielding portion on the protective substrate in the optical member prepared by the producing method of the invention. [0274] In addition, the following evaluations were performed using the ultraviolet curable resin composition A of the invention, which was obtained in the above. [0275] (Curability) [0276] Two pieces of slide glass having a thickness of 1 mm were prepared, and then the ultraviolet curable resin composition A thus obtained was coated on one piece of the two pieces so as to have a film thickness of 200 μm. The other piece of slide glass was bonded to the coated surface of the one piece. The resin composition was irradiated with ultraviolet rays having a cumulative amount of light of 2000 mJ/cm 2 using a high pressure mercury lamp (80 W/cm, ozone free) through the glass. The cured state of the cured product was confirmed by visual observation, and as a result, the cured product was completely cured. [0277] (Cure Shrinkage) [0278] Two pieces of slide glass, which were coated with a fluorine-based mold releasing agent and have a thickness of 1 mm, were prepared, and then the ultraviolet curable resin composition A thus obtained was coated on one piece of the two pieces so as to have a film thickness of 200 μm. Thereafter, the two pieces were bonded to each other such that the surfaces coated with mold releasing agent face each other. The resin composition was irradiated with ultraviolet rays having a cumulative amount of light of 2000 mJ/cm 2 using a high pressure mercury lamp (80 W/cm, ozone free) through the glass, thereby curing the resin composition. Thereafter, the two pieces of slide glass were separated from each other, thereby preparing a film of cured product for specific membrane gravity measurement. [0279] The specific gravity (DS) of the cured product was measured based on JIS K7112 B method. In addition, the liquid specific gravity (DL) of the ultraviolet curable resin composition was measured at 25° C. From the measurement result of DS and DL, the cure shrinkage was calculated by the following Expression. As a result, the cure shrinkage was less than 2.0%. [0000] Cure shrinkage (%)=( DS−DL )/ DS· 100 [0280] (Adhesiveness) [0281] A slide glass having a thickness of 0.8 mm and an acrylic plate having a thickness of 0.8 mm were prepared. The ultraviolet curable resin composition A thus obtained was coated on one of the two so as to have a film thickness of 200 μm, and then the other was bonded to the coating surface of the one. The resin composition was irradiated with ultraviolet rays having a cumulative amount of light of 2000 mJ/cm 2 using a high pressure mercury lamp (80 W/cm, ozone free) through the glass, thereby curing the resin composition. A sample for adhesiveness evaluation was prepared in this manner. This sample was left to stand at 85° C. under an environment of 85% RH for 250 hours. The flaking of cured product of resin of the slide glass or the acrylic plate was confirmed by visual observation in the sample for evaluation, and as a result, flaking did not occur. [0282] (Flexibility) [0283] The ultraviolet curable resin composition A thus obtained was sufficiently cured, and the durometer hardness E was measured by a method based on JIS K7215 using a durometer hardness tester (type E), thereby evaluating the flexibility. More specifically, the ultraviolet curable resin composition A was poured into a mold of cylindrical shape so as to have a film thickness of 1 cm, and then the resin composition was irradiated with ultraviolet rays, thereby sufficiently curing the resin composition. The hardness of the cured product thus obtained was measured using a durometer hardness tester (type E). As the result, the measured value was less than 10, and hence it is verified that the cured product exhibits excellent flexibility. [0284] (Transparency) [0285] Two pieces of slide glass, which were coated with a fluorine-based mold releasing agent and have a thickness of 1 mm, were prepared, and then the ultraviolet curable resin composition thus obtained was coated on one piece of the two pieces so as to have a film thickness of 200 μm. Thereafter, the two pieces were bonded to each other such that the surfaces coated with mold releasing agent face each other. The resin composition was irradiated with ultraviolet rays having a cumulative amount of light of 2000 mJ/cm 2 using a high pressure mercury lamp (80 W/cm, ozone free) through the glass, thereby curing the resin composition. Thereafter, the two pieces of slide glass were separated from each other, thereby preparing a cured product for transparency measurement. [0286] With regard to the transparency of the cured product thus obtained, the transmittance in wavelength regions of from 400 to 800 nm and from 400 to 450 nm was measured using a spectrophotometer (U-3310 manufactured by Hitachi High-Technologies Corporation). As the result, the transmittance at from 400 to 800 nm was 90% or more and the transmittance at from 400 to 450 nm was also 90% or more. REFERENCE SIGNS LIST [0287] 1 Liquid crystal display unit, 2 Transparent substrate having a light shielding portion, 3 Transparent substrate, 4 Light shielding portion, 5 Coating layer of ultraviolet curable resin composition, 6 Ultraviolet shielding plate (UV mask), 7 Coating layer of ultraviolet curable resin composition having a light shielded region cured at the time of bonding, 8 Cured product layer of resin, 9 Ultraviolet rays
The present invention relates to a method for producing an optical member wherein an optical substrate having a light-blocking part on the surface is bonded to an optical substrate for bonding. The method for producing an optical member uses a UV-curable resin composition and comprises specific (Process 1) through (Process 3). The present invention also relates to the use of a UV-curable resin composition comprising a (meth)acrylate (A) and a photopolymerization initiator (B) for the production method, and a UV-curable resin composition. It is possible to produce a bonded optical member having good curability and adhesiveness, such as a touch panel or display unit having an optical substrate comprising a light-blocking part, with good productivity but with little damage to the optical substrate. It is thereby possible to obtain an optical member having a high degree of resin curing at the light-blocking part and high reliability.
1
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The “toe alignment” of the front or rear wheels of a vehicle is defined as the angular relationship of the principal plane of the front or rear wheels to the vertical plane passing through the longitudinal axis of the vehicle. [0003] It is imperative, from a safety standpoint that the “toe in alignment” be within tolerance to assure driving stability, increased tire life and reduced fuel consumption because of reduced friction. Nonetheless, it is a common occurrence that one runs over a pot hole or hits a curb, the consequence being a potential misalignment, including toe in. [0004] It is acknowledged that it is impractical for most vehicle owners to own or operate an expensive alignment device. Indeed, such devices are found almost exclusively in professional shops. It is still essential to keep a check on “toe” since this is the most common failure of alignment. The question becomes one of how does the average, non professional, determine, at minimal cost, that his or her vehicle is out of alignment. [0005] Overview of the Applicable Art [0006] There has been found no device which is affordable and useable by an average, non professional driver to determine the existence of an alignment problem. There are, of course, devices such as that depicted in Bennett U.S. Pat. No. 1,675,481, in which a plurality of balls 15 separate upper and lower runner boards. A vehicle is driven on to the upper board where the alignment of each wheel is measured in turn. The Bennett device is clearly a professional device and far to sophisticated and expensive to be found in one's garage at home. [0007] There are several such, obviously professional, devices which inhabit professional shops, but there is no known device available to the average motorist, at least until the advent of the present invention. SUMMARY OF THE INVENTION [0008] The present invention relates, in a general sense, to a home testing device for determining the toe in of each wheel of a motor vehicle. [0009] It is an objective of the present invention to provide a motorist, consumer with such a device which technically understandable, and readily useable by a motorist with minimal to no experience in such testing devices. [0010] It is another objective, related to the foregoing, to provide a light weight, easily maintained, home testing device of the type described which is sufficiently inexpensive as to make it readily available to the average motorist, even one of modest resources. [0011] In summary, the overall object of this invention is to give a portable, durable, inexpensive, convenient and simple means by which the operator of a vehicle can check the “toe in” of a vehicle at their convenience, and at home. [0012] In the scheme of things, probably the single most important object of this invention is its simplicity of use, which can be understood by anyone who operates a vehicle. BRIEF DESCRIPTION OF THE DRAWINGS [0013] FIG. 1 , is an exploded view, in perspective, of a portable toe in testing device constructed in accordance with the present invention; [0014] FIG. 2 , is a perspective view of the device of FIG. 1 , shown assembled and ready for use; and [0015] FIG. 3 , is a partial sectional view of the device of FIG. 2 , taken along lines A-A; [0016] FIG. 4 is an exploded view, in perspective, of a slightly modified embodiment of the present invention; [0017] FIG. 5 is an assembled perspective view of the modified form of the invention as shown in FIG. 4 ; and, [0018] FIG. 6 is a partial sectional view taken along lines B-B of FIG. 5 , illustrating the interrelationship between the slide and the end plates thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0019] With reference now to the drawings, and initially to FIG. 1 , a portable toe in testing device is illustrated at 10 . [0020] The testing device 10 , in its most simple form, comprises a base plate 12 . A slide, in the nature of the plate 14 is provided and is adapted to overlay the base plate 12 . The surfaces of both plates are coated, or otherwise made of a low friction material, e.g., Teflon® or nylon®, although any material that meets the essential low friction criteria is within the contemplation of the invention. [0021] The base plate 12 is formed or affixed with end plates 16 and 18 respectively. The end plates are notched at 19 so as to partially overlay the free surface 21 of the base plate, and when the slide is inserted the notches restrict its movement to a transverse direction, inhibiting movement along its longitudinal axis. [0022] In order that a surface of the slide 14 can rest on the surface 21 with its motion relative thereto limited to transverse movement only, the ends 23 and 25 respectively of the slide are beveled, thus permitting the slide to be slipped under the end plates 16 and 18 , within the notches 19 with sufficient clearance to permit the slide 14 to move in a direction transverse to the longitudinal axis of the testing device, while inhibiting movement along that axis. The end plates serve as ramps as at 27 in order that a wheel can be readily driven over the device. [0023] A gauge 28 is mounted in the end piece 16 , where it senses movement of the slide as the vehicle is moved longitudinally, first across end piece 16 and continuing its movement across end piece 18 and away from the device. The needle 31 of the gauge 28 will set at its position of maximum deflection, thereby indicating the toe in of the wheel which has just moved across the testing device 10 . [0024] A transverse slot 34 is centrally disposed in the base plate and a fastener 36 is inserted through the slide and is secured in the slot 34 with sufficient, but limited, play as to permit the ready transverse movement of the slide relative to the base while holding the two together. It has been found that limited movement of about one-half inch is sufficient. [0025] FIGS. 4 through 6 illustrate a slightly modified relationship between the base plate 12 and slider 14 . In this modified form, the end plates 16 and 18 are not notched as they were in the FIG. 1 embodiment at 19 , but simply squared off. [0026] In the FIG. 4 embodiment, the slider is fashioned with at least four slots 40 . It will be seen that the orientation of the slots is transverse to the longitudinal axis of the portable toe in alignment device, each of the slots 40 being aligned in the same direction, i.e., transverse to the longitudinal axis of the device. The slots are uniformly spaced near the far corners of the plate, although the specific orientation may vary. [0027] Fasteners 42 are fitted with shims 44 and are fitted through the slots and into the base plate wherein fastener receptacles 46 are fitted. [0028] In the operation of each embodiment, the slide will move to the left or right and hold its adjusted position as the vehicle drives over the alignment device. The FIG. 4 embodiment provides for slightly less friction with the end plates 16 and 18 than would be existing in the FIG. 1 embodiment, although both devices will provide the user with a reading of the alignment of each wheel that is driven over the device. [0029] FIGS. 1 and 4 graphically illustrate the simplicity of using the alignment device. Initially, the operator of a vehicle simply drives straight and slowing across the device, then stops the car and picks up the light weight device 10 to read the results. If the gage 28 remains on center, it can be construed that the “toe in” of the car is according to specification. If the needle 31 of the gauge 28 has moved, the “toe in” is is either in or out, as the needle so indicates. [0030] It will be appreciated that the precise number of fasteners in either the FIG. 1 or FIG. 4 devices may vary without departure from the invention. [0031] While I have described successful structures for constructing my invention, it is possible in the art to make various modifications and still achieve the results desired, without departure from the invention as outlined in the claims below.
A portable, light weight device for determining the toe in alignment of a wheel on a motor vehicle in which a base plate functions in cooperation with a slide which has limited transverse movement relative to said base plate, the movement being generated by the position of the slide relative to the toe in of a tire as it moves across the alignment device.
6
The United States government has certain rights in this invention by virtue of grant No. P50 54502 awarded by the National Heart, Lung and Blood Institute of the National Institutes of Health to Naomi Esmon. BACKGROUND OF THE INVENTION The present invention is generally in the area of a modified protein C having enhanced anticoagulant activity. Protein C plays a major role in the regulation of blood coagulation. Patients deficient in protein C usually exhibit life threatening thrombotic-complications in infancy (Seligsohn et al., (1984) N. Engl. J. Med. 310, 559-562; Esmon, (1992) Trends Cardiovasc. Med. 2, 214-220) that are corrected by protein C administration (Dreyfus et al., (1991) N. Engl. J. Med. 325, 1565-1568). In addition, activated protein C (APC) can prevent the lethal effects of E. coli in baboon models of gram negative sepsis (Taylor et al., (1987) J. Clin. Invest. 79; U.S. Pat. No. 5,009,889 to Taylor and Esmon) and preliminary clinical results suggest that protein C is effective in treating certain forms of human septic shock (Gerson et al., (1993) Pediatrics 91, 418-422). These results suggest that protein C may both control coagulation and influence inflammation. Indeed, inhibition of protein S, an important component of the protein C pathway, exacerbates the response of primates to sublethal levels of E. coli and augments the appearance of TNF in the circulation (Taylor et al., (1991) Blood 78, 357-363). The mechanisms involved in controlling the inflammatory response remain unknown. Protein C is activated when thrombin, the terminal enzyme of the coagulation system, binds to an endothelial cell surface protein, thrombomodulin (Esmon, (1989) J. Biol. Chem. 264, 4743-4746; Dittman and Majerus, (1990) Blood 75, 329-336; Dittman, (1991) Trends Cardiovasc. Med. 1, 331-336). In cell culture, thrombomodulin transcription is blocked by exposure of endothelial cells to tumor necrosis factor (TNF) (Conway and Rosenberg, (1988) Mol. Cell. Biol. 8, 5588-5592) and thrombomodulin activity and antigen are subsequently internalized and degraded (Lentz et al., (1991) Blood 77, 543-550, Moore, K. L., et.al., (1989) Blood 73, 159-165). In addition, C4bBP, a regulatory protein of the complement system, binds protein S to form a complex that is functionally inactive in supporting APC anticoagulant activity in vitro (Dahlback, (1986) J. Biol. Chem. 261, 12022-12027) and in vivo (Taylor, et al., 1991). Furthermore, C4bBP behaves as an acute phase reactant (Dahlback, (1991) Thromb. Haemostas. 66, 49-61). Thus, proteins of this pathway not only appear to regulate inflammation, but they also interact with components that regulate inflammation, and they themselves are subject to down regulation by inflammatory mediators. It is therefore an object of the present invention to provide a modified protein C which is useful as an improved anticoagulant. It is a further object of the present invention to provide a method for treating patients with deficiencies in protein C and/or S. It is another object of the present invention to provide methods of modulating the inflammatory response involving protein C and activated protein C. SUMMARY OF THE INVENTION Modified Protein C molecules have been made which substitute the gamma carboxylglutamic acid (Gla) region of another Vitamin K dependent protein, most preferably prothrombin, for the native region of the Protein C. The modified or chimeric protein C has advantages over the wild-type protein C since it is less sensitive to inhibition by natural inhibitors of protein C (which would otherwise decrease the ability of the protein C to act as an anticoagulant) and which do not need the same cofactors or same amounts of cofactors, and can therefore be effective in patients with lowered levels of the cofactors such as protein S or the lipids present in elevated levels in platelets such as phosphatidyl ethanolamine (PE). As described in the examples, a chimeric protein C was designed after observing that supplementation of phosphatidylserine (PS) containing vesicles with PE enhances activated protein C (APC) anticoagulant activity. To determine the structural basis of the PE sensitivity, a chimeric molecule in which the Gla domain and hydrophobic stack (residues 1-46) of protein C were replaced with the corresponding region of prothrombin (PC-PT Gla) was constructed. The activated chimeric molecule is referred to as APC-PT Gla. APC inactivation of Factor Va was enhanced 10 fold by PE and 2 fold by protein S in either the presence or absence of PE. In purified systems, relative to the chimera, wild type APC inactivated factor Va more rapidly on PE containing vesicles and more slowly on vesicles lacking PE. With APC-PT Gla, inactivation of factor Va was only slightly enhanced by PE and was slightly inhibited by protein S. Prothrombin inhibited inactivation of factor Va by wild type APC much more effectively than the chimera, possibly accounting for the observation that the chimera exhibited approximately 5 fold more plasma anticoagulant activity than wild type APC under all conditions tested. These results demonstrate that the functional influence of PE on factor Va inactivation by APC is mediated by special properties unique to the Gla domain and that the Gla domain of protein C provides specialized functions to greatly enhance interaction with factor Va and protein S on PE containing membranes. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the anticoagulant activities of APC and APC-PTGla. Clotting time (seconds) is plotted against enzyme concentration (micrograms/ml) for APC-PT Gla in the presence of PE:PS:PC (open squares); APC-PT Gla in the presence of PS:PC (closed blocks); APC in the presence of PE:PS:PC (open circles); and APC in the presence of PS:PC (closed circles). FIGS. 2A and 2B are graphs showing the influence of an antibody to protein S, anti-protein S MAB S155, on the activity of wild-type APC and APC-PT Gla in normal plasma, plotting clotting time (seconds) against concentration of APC or APC-PT Gla (micrograms/ml). FIG. 2A graphs the activity of APC and APC-PT Gla at concentrations of between 0 and 5.0 micrograms/ml; FIG. 2B is an expanded view of the activities at concentrations of between 0 and 1.0 micrograms/ml. Wild-type APC in combination with PE, no mAb (closed circles); wild-type APC in combination with PS and anti-protein S mAb (no protein S) (open triangles); wild-type APC in combination with PE and anti-protein S mAb (closed triangles); APC-PT Gla in combination with PE, no mAb (closed upside down triangle); APC-PT Gla in combination with PS, anti-protein S mAb (open diamonds); and APC-PT Gla in combination with PE, and anti-protein S mAb (closed diamonds). FIGS. 3A and 3B are graphs comparing the relative activity of wild-type APC in combination with PS:PC, PC-PT Gla in combination with PS:PC, wild-type APC in combination with PE:PS:PC, and PC-PT Gla in combination with PE:PS:PC, in the presence (FIG. 3B) and absence (FIG. 3A) of prothrombin at a physiological concentration of 1.4 micromolar. The APC concentration required in the presence of protein S and vesicles without PE is defined as one. Relative activity is calculated as the concentration under standard conditions required to inhibit 50 activity in 30 minutes divided by the concentration under experimental conditions required to inhibit 50% activity in 30 minutes. DETAILED DESCRIPTION OF THE INVENTION Assembly of multiprotein enzyme complexes on negatively charged phospholipid membrane surfaces is critical to both the formation and regulation of the blood clotting process. Zymogen activations occur rapidly when the enzyme, usually a vitamin K dependent protein, binds to a cofactor, usually a non-vitamin K dependent protein, to activate a substrate, usually a vitamin K dependent protein (reviewed in Mann, et al. (1988) Ann. Rev. Biochem. 57, 915-956; Furie and Furie (1988) Cell 53, 505-518). The enzymes and substrates interact with the membrane reversibly, while the cofactors may either bind reversibly or be integral membrane proteins. The nature of the phospholipid head group appears to contribute to catalytic and binding efficiency with phosphatidylserine (PS) being generally accepted as the most important phospholipid (Mann, et al. (1988); Pei, et al. (1993) J. Biol. Chem. 268, 3226-3233). The vast majority of biophysical and kinetic studies of the assembly of the vitamin K dependent complexes have used membranes composed solely of phosphatidylcholine (PC) and PS (Mann, et al., Pei, et al., Castellino, F. J. (1995) Trends Cardiovasc. Med. 55-62; Nelsestuen, (1978) Biochemistry 17, 2134-2138). Recently, it was observed that phosphatidylethanolamine (PE), a major constituent of the outer leaflet of the membrane of activated platelets (Bevers, E. M., Comfurius, P., and Zwaal, R. F. A. (1983) Biochim. Biophys. Acta 736, 57-66), plays an important role in the function of one of these complexes, the activated protein C (APC) dependent inactivation of factor Va (Smirnov and Esmon (1994) J. Biol. Chem. 269, 816-819). In this case, the presence of PE or cardiolipin potently enhanced the rate of inactivation. Subsequently, roles for PE in factor VIII binding (Gilbert and Arena (1995) J. Biol. Chem. 270, 18500-18505), tissue factor-factor VIIa activation of factor X (Neuenschwander, et al. (1995) Biochemistry 34, 13988-13993) and prothrombin activation (Billy, et al. (1995) J. Biol. Chem. 270, 26883-26889; Smeets, et al. (1996) Thromb. Res. 81, 419-426) have been reported. In the case of prothrombin activation, with PE present, the amount of PS required to support prothrombin activation was reduced several fold. In the case of tissue factor, it was shown that the presence of PE enhanced activation primarily by decreasing the amount of PS required for optimal activation and this was largely a Km effect on the substrate. The impact of PE on the inactivation of factor Va was substantially greater than on the other systems. For prothrombin activation and tissue factor mediated factor X activation, the augmentation by PE could be overcome simply by increasing PS concentration whereas the PE impact on factor Va inactivation was not eliminated by high PS (Smirnov 1994). Protein C, like the other vitamin K dependent proteins, is composed of several domains (Furie 1988). These include the protease domain, two EGF like domains, an aromatic stack and the vitamin K dependent Gla domain containing the 4-carboxyglutamic acid (Gla) residues. These Gla residues are involved in Ca 2+ dependent membrane binding and are clustered within the amino terminal 48 residues of the vitamin K dependent plasma factors (Furie 1988, Castellino 19954, Mann, K. G., Krishnaswamy, S., and Lawson, J. H. (1992) Sem. Hematol. 29, 213-226). The sequences of these proteins within this region are highly conserved, but the number of Gla residues varies from 9 to 12 (Furie 1988). Since the Gla domains are implicated in the membrane binding and membrane dependent catalytic activity, it was postulated that the differences in PE dependent behavior between protein C and the other complexes might be mediated by the Gla domains. To test this possibility, a chimeric form of protein C in which the Gla domain has been exchanged with that of prothrombin was designed in an effort to evaluate the regions of the molecules involved in the PE dependent activities. The chimera was designed to be non-immunogenic in humans, as well as to have the advantageous properties demonstrated in the examples. Exons one to three of protein C were replaced with exons one to three of prothrombin. This region includes the signal peptide, the Gla domain and the aromatic stack region. The splice sites in both the protein C and the prothrombin are identical, so that no sequence changes were required and only human sequence present in the naturally occurring human proteins is present in the chimeras. The activation site in the protein C zymogen was unaffected by the change. The results of the studies reported below show that the substitution of the native Gla domain with the prothrombin Gla domain alters the activity of the protein C, decreasing the need for PE and protein S and reducing inhibition by prothrombin. The PE dependence of APC anticoagulant activity is clearly mediated in large part by the Gla domain of protein C. APC-PT Gla exhibited little dependence on the presence of PE in the liposomes in purified systems. Furthermore, the factor Va inactivating activity of the chimera was inhibited rather than stimulated by protein S. These differences were not due to defects in membrane binding since the chimera bound to membranes at least as well as wild type protein C and was more active than wild type of vesicles devoid of PE while being less active on vesicles containing PE. Much of this difference appears to lie in the capacity of protein S and factor Va to synergistically augment APC binding to vesicles, especially those containing PE. In particular, in the presence of factor Va, protein S failed to enhance binding of the chimera as it did in the case of wild type APC. In plasma, the chimera exhibited much greater anticoagulant activity than wild type APC on vesicles with or without PE. These differences appeared to be due, in part, to the decreased ability of prothrombin to block factor Va inactivation by the chimera. The PE effects on catalysis of the APC anticoagulant complexes have both a cell biology and pathophysiology ramification. PE has been reported to be present on the surface of unactivated cells (Wang, et al. (1986) Biochem. Biophys. Acta 856, 244-258) and, following activation, may constitute nearly 40% of the outerleaflet membrane phospholipid (Bevers, et al. 1983). Furthermore, PE has been reported to have a higher Km for the flipase and hence is likely to be more slowly transported to the inner membrane leaflet (Devaux (1991) Biochemistry 30, 1163-1173). Therefore, if the different coagulation complexes were to exhibit widely different PE:PS dependencies, this time dependent change in membrane composition could selectively favor clot promoting or clot inhibiting reactions. Although demonstrated by the substitution of the Gla region of the protein C with the Gla region of prothrombin, many of the other Vitamin K dependent clotting factors are equally well understood and their Gla regions could be inserted in place of the N-terminal regions of protein C to create a chimera having altered anticoagulant activity. Unlike some systems, the coagulation system is highly predictable based on in vitro results and the highly conserved structure within the clotting proteins provides a means for extrapolation among proteins. Other representative donor proteins include factor X and factor VII. The chimeras are made using the same techniques described in detail in the example. The DNA encoding the other Vitamin K dependent clotting factors is known and described in the literature. Pharmaceutical Compositions The protein is generally effective when administered parenterally in amounts above about 90 μg/kg of body weight, assuming 35 ml plasma/kg, approximately three to four micrograms protein C/ml plasma, and one to three micrograms chimeric protein C/ml plasma. Based on extrapolation from other proteins, for treatment of most inflammatory disorders, the dosage range will be between 20 and 200 micrograms/kg of body weight. The modified protein C is preferably administered in a pharmaceutically acceptable vehicle. Suitable pharmaceutical vehicles are known to those skilled in the art. For parenteral administration, the compound will usually be dissolved or suspended in sterile water or saline. Disorders to be Treated It should be possible to treat disorders where protein S is low, some forms of lupus, following stroke or myocardial infarction, after venous thrombosis and in disseminated intravascular coagulation, septic shock, adult respiratory distress syndrome, and pulmonary emboli using the modified protein C. Protein S levels are often low in these conditions, making APC less effective as an anticoagulant (see D'angelo, et al. (1988) J. Clin. Invest. 81, 1445-1454). Examples of these conditions include disseminated intravascular coagulation, during warfarin anticoagulation, and in thromboembolic disease. Since the chimera's optimal activity does not depend on normal levels of protein S in the patient, it is expected to be an active anticoagulant in conditions where the patient's own activated protein C or therapeutically administered protein C or activated protein C would be compromised. Note that for technical reasons, protein S concentrates useful for treatment have not been successfully prepared. Lupus anticoagulants and some antiphospholipid antibodies block the function of coagulation and anticoagulation complexes preferentially on PE containing membranes (Smirnov, et al. (1995) J. Clin. Invest. 95, 309-316; Rauch, et al. (1986) J. Biol. Chem. 261, 9672-9677). These antibodies are associated with an increased risk of thrombosis (Ginsberg, et al. (1993) Blood 81, 2958-2963; Triplett, D. A. (1993) Arch. Pathol. Lab. Med. 117, 78-88; Pierangeli, et al. (1994) Thromb Haemostas. 71, 670-674). In addition to therapeutic applications, the APC molecule with no PE dependence allows the exploration of the mechanisms of PE dependent lupus anticoagulant effects on the APC system in vitro and in vivo. The chimera is less sensitive to inhibition by lupus anticoagulants and hence can be used to identify pathogenic antibody populations that react with protein C. The present invention will be more fully understood by reference to the following non-limiting examples. The following abbreviations are used herein: APC, activated protein C; PC-PT Gla, a chimeric molecule in which the Gla domain and hydrophobic stack (residues 1-45) of protein C has been replaced with the corresponding region of prothrombin; PE, phosphatidylethanolamine; PS, phosphatidylserine; PC, phosphatidylcholine; Gla, 4-carboxyglutamic acid; X-CP, the factor X activator from Russell's viper venom; BSA, bovine serum albumin; TBS, 150 mM NaCl, 20 mM Tris-HCl, 0.02% sodium azide, pH 7.4; TBS-GOB, TBS containing 1 mg/ml gelatin, 1.6 mg/ml ovalbumin and 10 mg/ml BSA. EXAMPLE 1 Construction of a Chimeric Protein C-Prothrombin Protein Experimental Procedures Proteins and reagents. Human thrombin and prothrombin (Owen, et al. (1974) J. Biol. Chem. 249, 594-605), human APC (Esmon, et al. (1993) Meths. Enzymol. 222, 359-385), human protein S (Taylor, et al. (1991) Blood 78, 356-363), human factor Xa (Le Bonniec, et al. (1994) J. Biol. Chem. 267, 6970-6976), bovine factor Va (Esmon, C. T. (1979) J. Biol. Chem. 254, 964-973), and the factor X activator from Russell's viper venom (X-CP)(Esmon, C. T. (1973) (Ph.D. Dissertation), Washington University, St. Louis) were prepared as described. Meizothrombin labeled in the active site with fluorescein was prepared as described by Armstrong, et al. (1990) J. Biol. Chem. 265, 6210-6218; Bock (1988) Biochemistry 27, 6633-6639. Human factor Va was obtained from Hematologic Technologies. Bovine serum albumin (BSA), Russell's viper venom, ovalbumin, gelatin, MOPS, Tris-HCl and salts were obtained from Sigma. The chromogenic substrates Spectrozyme TH and Spectrozyme PCa were obtained from American Diagnostica (Greenwich, Conn.). The irreversible inhibitor of the serine proteases (p-amidinophenyl)methanesulphonyl fluoride was obtained from Calbiochem. 1-palmitoyl-2-oleoyl-sn-glycero-3 PS, 1-palmitoyl-2-oleoyl-sn-glycero-3 PC and 1,2-dilinoleoyl-sn-glycero-3-PE were obtained from Avanti Polar Lipids Inc. 1-Palmitoyl-2- 1- 14 C-oleoyl!PC was obtained from DuPont NEN. Factor V deficient human plasma was obtained from George King Bio-Medical, Inc. (Overland Park). Preparation of Phospholipid Vesicles. Sonicated vesicles were prepared as described (Smirnov 1994). Briefly, lipids were mixed in the weight proportions described below, dried under argon and lyophilized overnight to remove organic solvents. They were then reconstituted in 150 mM NaCl, 20 mM Tris-HCl, 0.02%, sodium azide, pH 7.4 (TBS) to 2 mg total lipid/ml and sonicated (Bronson Sonic Power Co, model 350) 15 min in an ice-water bath under argon flow, centrifuged at 8000 g for 15 min and filtered through a 0.22 μm filter. The vesicles were used immediately or stored at +20° C. Storage did not alter vesicle activity. Construction of the Protein C Prothrombin Gla Domain Chimera. The protein C chimera was constructed in which the first 3 exons of prothrombin (i.e. coding for the signal peptide, the Gla domain and the aromatic stack regions) replaced the corresponding regions of protein C. The relevant amino acid sequences for human prothrombin and protein C are: human prothrombin (Sequence ID No. 1): ANTFLxxVRKGNLxRxCVxxTCSYxxAFxALxSSTATDVFWA human protein C (Sequence ID No. 2): ANSFLxxLRHSSLxRxCIxxICDFxxAKxIFQNVDDTLAFWS where x means gamma carboxylglutamic acid. Mutagenesis was performed by polymerase chain reaction methodology. The wild type protein C cDNA (provided by Eli Lilly Research Laboratory) was ligated into the HindIII and Xbal sites of pRc/RSV (Invitrogen, Calif.) to form RSV-PC as described by Rezaie 1993. There is a unique BstEII restriction site in the protein C cDNA in the beginning of exon 4, which encodes the N-terminal EGF domain. Double digestion of RSV-PC with HindIII and BstEII removes the DNA sequences of the first 3 exons of protein C as well as the first codon of exon 4, which is an Asp. To exchange exons 1-3 of protein C with those of prothrombin, two PCR primers were synthesized. The forward prothrombin sense primer 5'-CGCTAAGCTTCCATGGCCCGCATCCGAGGCTT-3' (Sequence ID No. 3) starts from the initiation codon of the prothrombin cDNA (provided by Dr. Ross MacGillivray) and contains a HindIII restriction enzyme site at the 5'-end of the primer (underlined). The reverse prothrombin antisense primer 5'-GAGTGGTCACCGTCTGTGTACTTGGCCCAGAACA-3' (Sequence ID No. 4) starts from the nucleotide of exon 3 in the prothrombin cDNA and contains the native BstEII restriction enzyme site containing the missing Asp codon in the beginning of exon 4 of the protein C cDNA. Following PCR amplification of prothrombin cDNA with these two primers and double digestion with HindIII and BstEII, the DNA fragment was ligated into the identical sites of the wild type protein C expression vector described above. After sequencing, the mutant construction was transfected into human 293 cells and the chimeric protein C was purified from culture supernatants by immunoaffinity chromatography using the calcium dependent monoclonal antibody, HPC4, as described by Rezaie and Esmon (1993) J. Biol. Chem. 268, 19943-19948, Rezaie, A. R. and Esmon, C. T. (1992) J. Biol. Chem. 267, 26104-26109). The PC-PT Gla chimera was activated to form APC-PT Gla by thrombin in the presence of 2 mM EDTA and purified by Mono-Q FPLC chromatography (Pharmacia) essentially as described for wild type protein C by Esmon, C. T., et al., Methods. Enzymol. 222, 259-385 (1993). Gla residue determinations were performed by Dr. Betty Yan and Cindy Payne at Eli Lilly Research Laboratory. The Gla content per mole protein obtained were: 8.7±0.3 for protein C, 10.9±0.2 for prothombin, 9.5±0.2 for PC-PT Gla and 10.3±0.4 for APC-PT Gla. EXAMPLE 2 Determination of Protein C and Prothrombinase Activity of Chimeric Protein Methods and Materials Measurement of APC and Prothrombinase Activity in the Purified System. Factor Va inactivation was analyzed with a three stage assay essentially as described by Smirnov and Esmon (1994). Briefly, factor Va was inactivated by APC in the first stage. In the second stage, after inactivation of APC with (p-amidinophenyl)methanesulphonyl fluoride, residual factor Va activity was monitored by its activity in the prothrombinase complex in the presence of excess factor Xa and prothrombin. The resultant thrombin was measured in the third stage using a chromogenic assay. All reagents were diluted in TBS containing 1 mg/ml gelatin, 1 mg/ml and 10 mg/ml BSA (TBS-GOB). Percent factor Va inactivation was calculated by dividing thrombin formation in the presence of APC by thrombin formation in its absence and subtracting this value from 1. Enzyme was added at concentration of 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.15, 1 and 4 ng/ml. When held constant, the final concentration of reagents were 0.2 nM factor Va, 1 nM factor Xa, 1.4 μM prothrombin and 10 μg/ml phospholipid. Clotting Assays. Clotting assays were performed by a modification of the dilute Russell's viper venom test. Purified X-CP was employed instead of crude venom. All reagents were diluted in TBS containing 1 mg/ml gelatin. Assays were performed in 96-well plates. To serial dilutions of APC (30 μl) were added 10 μl of 60 μg/ml phospholipid, 10 μl of 20 ng/ml X-CP and 10 μl of normal pooled plasma. The entire mixture was incubated for 1 min. Clotting was initiated by addition of 25 μl of 20 mM CaCl 2 . The clotting time was determined on a Vmax Kinetic Microplate Reader. Adsorption of Liposomes onto Latex. A 10% suspension of latex beads (50 μl) was pelleted in Eppendorf tubes and washed 3 times with PBS by centrifugation at 8,000×g for 1 min and resuspended in 50 μl TBS, 5 mM CaCl 2 . Liposomes (100 μl at 1 mg/ml total phospholipid in TBS) were added and incubated 2 hr at 37° C. with shaking. After two washes, the beads were resuspended in TBS-GOB and further incubated 2 hr at room temperature with shaking. After 2 additional washes with TBS, the beads were resuspended in 500 μl TBS. Total phospholipid concentration was determined by counting the 14 C-PC tracer included in the phospholipid mixtures (Beckman Model LS 6000SE scintillation counter) and found to be 50 μg/ml of latex suspension for both PS:PC and PE:PS:PC adsorbed liposomes. The beads could be stored at 4° C. for at least 7 days without loss of adsorbed phospholipid. Fluorescent Labelling. Active site fluorescein labeled enzymes were prepared according to the method of Bock (1988). Briefly, to 300 μl of enzyme (1 mg/ml) were added 40 μl 1M HEPES, pH 7.4, 1 μl 0.2M EDTA and two times 5 μl of N-.sup.α (acetylthio)acetyl!-D-Phe-Pro-Arg-CH 2 Cl (4 mM), 10 min per incubation, to form ATA-FPR-enzyme. After overnight dialysis, 45 μl hydroxylamine (1M in 1M HEPES, pH 7.4) and 50 μl of 5-(iodoacetamido)fluorescein (Molecular probes, 1 mg/ml in 1M HEPES, pH 7.4) were added to the ATA-FPR-enzymes and incubated 1 h at 0° C. Free fluorescein was removed by gel filtration on a PD-10 column (Pharmacia), and the samples were then dialyzed overnight at 4° C. With this method, each molecule of labelled enzyme contains a single dye at the same location and thus, all of the fluorescent molecules behave equivalently. Binding of Fluorescein Labelled Proteins to Liposomes Adsorbed on Latex. Liposome adsorbed latex beads (0.5 μg total phospholipid/ml) were suspended in TBS-GOB containing 2.5 mM CaCl 2 . Appropriate protein(s) were added at the concentrations indicated and incubated at 25° C. for 20 min in the dark with occasional mixing. Binding was analyzed on a FACScan flow cytometer (Becton Dickinson). To determine the calcium independent, irreversible component of the fluorescent APC binding, 50 mM EDTA was added in 200 mM MOPS, pH 7.4 to a final concentration of 10 mM, and samples were re-analyzed after 20 min incubation in the dark. This component accounted for less than 20% of the observed binding. Binding parameters were determined by fitting the calcium dependent binding to the equation for single site binding model using the ENZFITTER™ program (Elsevier Biosoft, Cambridge, UK). Liposome-Protein Interactions Measured by Right Angle Light Scattering. Right angle light scattering was performed as described by Nelsestuen (1978) and Castellino (Zhang and Castellino 1993) on an SLM 8000 fluorimeter (SLM Instruments, Urbana, Ill.) with the wavelength set at 320 nm. The liposome concentration was 50 μg/ml. Binding experiments were performed in TBS, pH 7.4 containing 5 mM CaCl 2 . The prothrombin and protein C concentrations were varied from 0 to 3 μM, and the PC-PT Gla concentrations were varied from 0 to 1.2 μM. Binding parameters were determined by fitting the reversible calcium dependent binding to the equation for single-site binding model using the ENZFITTER program. Results PC-PT Gla could be activated to form an enzyme with amidolytic activity toward Spectrozyme PCa equivalent to wild type APC. The concentration dependence of inactivation of factor Va between APC and the APC chimera on vesicles with or without PE supplementation was then compared. On vesicles composed solely of PS:PC, the chimera was approximately 5 times more active than wild type APC. PE enhanced factor Va inactivation by the chimera very little (about 1.6 fold in this experiment) compared to approximately a 15 fold enhancement of APC. In addition, protein S (2.5 μg/ml protein S) inhibited factor Va inactivation by the chimera whereas protein S enhanced factor Va inactivation by APC. These effects were not PE dependent. Therefore, it appears that much of the PE dependence of APC is mediated by the Gla domain and that some portion of the Gla domain is important for protein S mediated effects in purified systems. To ascertain whether the differences in activity were reflected in differences in binding affinity to membranes, light scattering experiments were initially performed with prothrombin, protein C and PC-PT Gla on PS:PC vesicles containing either 20 or 50% PS. Prothrombin, protein C and PC-PT Gla were bound to liposomes (20%PS:80%PC liposomes) (50 μg/ml) in TES, pH 7.4 containing 5 mM CaCl 2 . Protein binding was measured by right angle light scattering. It was apparent that the amount of prothrombin bound to the vesicles containing 20% PS was much higher than the amount of protein C bound with the PC-PT Gla being somewhat greater than the protein C. The Kd values were similar for all proteins. Increasing the PS concentration to 50% increased the amount of protein C and chimera binding more than two fold, but had a relatively small effect on prothrombin binding. From these experiments it is apparent that the PC-PT Gla binds to membranes at least as well protein C, but the affinity is not significantly better than wild type and hence cannot account for the increased activity on PS vesicles. The differences in maximum binding between the protein C and prothrombin presumably reflects the maximum number of molecules bound per liposome and the approximately 20% larger molecular mass of prothrombin. It was possible that the differences in activity between wild type and the chimera reflect differences in interaction with other protein components, and therefore light scattering approaches could not be employed easily. Furthermore, PE containing vesicles are too large to utilize in light scattering approaches. Therefore, different binding methodologies had to be employed that would allow the presence of PE and/or other protein components. This was accomplished by flow cytometry. Liposomes adsorbed to latex were employed and binding was monitored as a function of increasing fluorescent enzyme concentration. The final concentration of phospholipid was 0.5 μg/ml, and, when present, protein S (pro S) was 100 nM and factor Va (FVa) was 10 nM. All flow cytometric measurements were done with the enzymes labeled in the active site with fluorescein. All light scattering experiments were performed with the zymogens except the meizothrombin experiments in which the enzyme activity was blocked with D-Phe-Pro-Arg chloromethylketone as described by Armstrong, et al. (1990). On PS:PC vesicles, the concentration dependence of binding of protein C by light scattering and the concentration dependence of APC binding to latex adsorbed vesicles was indistinguishable, thereby validating this approach. The data from the light scattering measurements and the flow cytometric analysis was plotted as a function of increasing protein concentration. The curves were overlayed after normalizing the curves to the maximum binding calculated with the Enzfitter program assuming a single class of binding sites. The Kd values for prothrombin and meizothrombin were also similar as determined by light scattering, and the meizothrombin binding was equivalent by the two methods, further validating this approach. The major feature distinguishing wild type and APC-PT Gla is the degree to which protein S and factor Va synergize to augment membrane binding. Comparison of the chimera and wild type APC reveals that the binding affinity of wild type APC is higher than that of the chimera on PE containing vesicles when both factor Va and protein S are present and weaker when binding is examined on phospholipid devoid of PE. Factor Va alone and protein S alone had relatively little influence on the binding affinity of wild type APC, but factor Va alone enhanced chimera binding to a greater extent than wild type, especially in the absence of PE. Their ability to anticoagulate plasma was then studied to determine whether these differences in properties between APC and the chimera were retained under more physiological conditions. Surprisingly, the chimera exhibited much higher anticoagulant activity than APC on vesicles with or without PE. Unlike the situation with purified proteins, in plasma the chimera was much more active than wild type APC on PE containing vesicles. The much greater anticoagulant activity of the chimera in plasma could be due either to producing interactions specific to the chimera or, more likely, resistance to inhibitory factors. One possible inhibitor is prothrombin which circulates at very high concentrations. In principal, prothrombin could interfere with APC more effectively than with the chimera. To test this possibility, and the potential effect of protein S on this interaction, factor Va inactivation was analyzed as follows: Inactivation of factor Va by APC occurring in 30 minutes in the presence of 2.5 μg/ml protein S on PS:PC vesicles was defined as the standard condition. The concentration of APC required to inactivate 50% of the factor Va under the standard conditions was assigned a relative activity of 1. The concentration of APC or chimera required to inhibit 50% of the factor Va under various experimental conditions (±prothrombin, ±protein S, ±PE in the vesicles) in the first stage of the assay was then determined. This value was divided into the APC concentration determined for the standard condition to determine the relative activity. Factor Va inactivation was performed as usual with the exception that 1.4 μM prothrombin was present in the first stage of the assays. Three concentrations of protein S: 0, 2.5 μg/ml, and 5 μg/ml were employed. Lipids were either PS:PC or PE:PS:PC. The relative activity was calculated as described above. Comparison of factor Va inactivation in the absence and the presence of prothrombin indicated that prothrombin inhibited APC inactivation of factor Va on either type of vesicle and independent of the presence of protein S. Prothrombin inhibited factor Va inactivation 5 fold in the absence of PE and nearly 100 fold in the presence of PE. In contrast, the chimera was much less sensitive to prothrombin, with inhibition of about 5 fold observed in the presence or absence of PE. This decreased sensitivity to prothrombin inhibition may account in part for the enhanced plasma anticoagulant activity of the chimera. EXAMPLE 3 Use of Chimeric Protein as a Research Reagent In plasma, protein S plays additional roles in the anticoagulant activity of APC. For instance, previous studies have shown that protein S can block the ability of factor Xa to protect factor Va (Solymoss, et al. (1988) J. Biol. Chem. 263, 14884-14890) from inactivation and that protein S can interfere directly with the assembly of the prothrombinase complex (Heeb, et al. (1993) J. Biol. Chem. 268, 2872-2877). To test the possibility that one or more of these influences of protein S were observed with the chimera on PE containing vesicles, protein S was blocked with an inhibitory monoclonal antibody and the anticoagulant activities of activated protein C and the chimera were examined in plasma. Plasma clotting was performed under standard conditions in the presence and absence of an inhibitory monoclonal antibody to protein S (300 μg/ml of the protein S inhibitory monoclonal antibody S155 present in the final clotting mixture). In plasma, the anticoagulant activity of the chimera remained relatively insensitive to protein S (i.e., the anticoagulant activity was not affected by antibody on vesicles devoid of PE (20%PS:80%PC liposomes) and only slightly reduced on vesicles containing PE (50%PE:20%PS:30%PC liposomes)). The anticoagulant activities of APC and the chimera were examined for Protein S dependence. Thus, protein S functions in plasma appear to be largely dependent on specific properties contributed by the protein C Gla domain. The teachings of the references cited herein are specifically incorporated herein. Modifications and variations of the present invention will be obvious to those skilled in the art from the foregoing detailed description and are intended to be encompassed by the following claims. __________________________________________________________________________SEQUENCE LISTING(1) GENERAL INFORMATION:(iii) NUMBER OF SEQUENCES: 4(2) INFORMATION FOR SEQ ID NO:1:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 42 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(ix) FEATURE:(A) NAME/KEY:(B) LOCATION: 6, 7, 14, 16, 19, 20, 25, 26, 29, 32(D) OTHER INFORMATION: /note= "where Xaa means gammacarboxylglutamic acid"(ix) FEATURE:(A) NAME/KEY:(B) LOCATION:(D) OTHER INFORMATION: /note= "partial sequence of humanprothrombin"(xi) SEQUENCE DESCRIPTION: SEQ ID NO:1:AlaAsnThrPheLeuXaaXaaValArgLysGlyAsnLeuXaaArgXaa151015CysValXaaXaaThrCysSerTyrXaaXaaAlaPheXaaAlaLeuXaa202530SerSerThrAlaThrAspValPheTrpAla3540(2) INFORMATION FOR SEQ ID NO:2:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 42 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(ix) FEATURE:(A) NAME/KEY:(B) LOCATION: 6, 7, 14, 16, 19, 20, 25, 26, 29(D) OTHER INFORMATION: /note= "where Xaa means gamma(ix) FEATURE:(A) NAME/KEY:(B) LOCATION:(D) OTHER INFORMATION: /note= "partial sequence of humanprotein C"(xi) SEQUENCE DESCRIPTION: SEQ ID NO:2:AlaAsnSerPheLeuXaaXaaLeuArgHisSerSerLeuXaaArgXaa151015CysIleXaaXaaIleCysAspPheXaaXaaAlaLysXaaIlePheGln202530AsnValAspAspThrLeuAlaPheTrpSer3540(2) INFORMATION FOR SEQ ID NO:3:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 32 nucleic acids(B) TYPE: nucleic acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: synthetic DNA(ix) FEATURE:(A) NAME/KEY:(B) LOCATION:(D) OTHER INFORMATION: /note= "forward prothrombin senseprimer"(xi) SEQUENCE DESCRIPTION: SEQ ID NO:3:CGCTAAGCTTCCATGGCCCGCATCCGAGGCTT32(2) INFORMATION FOR SEQ ID NO:4:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 34 nucleic acids(B) TYPE: nucleic acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: synthetic DNA(ix) FEATURE:(A) NAME/KEY:(B) LOCATION:(D) OTHER INFORMATION: /note= "reverse prothrombin antisenseprimer"(xi) SEQUENCE DESCRIPTION: SEQ ID NO:4:GAGTGGTCACCGTCTGTGTACTTGGCCCAGAACA34__________________________________________________________________________
Modified Protein C molecules have been made which substitute the gamma carboxylglutamic acid (Gla) region of another Vitamin K dependent protein, most preferably prothrombin, for the native region of the Protein C. The modified or chimeric protein C has advantages over the wild-type protein C since it is less sensitive to inhibition by natural inhibitors of protein C (which would otherwise decrease the ability of the protein C to act as an anticoagulant) and which does not need the same cofactors or same amounts of cofactors, and can therefore be effective in patients with lowered levels of the cofactors such as protein S or the lipids present in activated platelets such as phosphatidyl ethanolamine (PE).
2
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wire bonding apparatus. 2. Prior Art One type of wire bonding apparatus includes a heating block, which is used to heat a workpiece, and a bonding horn which is positioned above this heating block so as to hold the capillary. Thus, the bonding horn is caused to undergo thermal expansion by the radiant heat from the heating block, and this results in a drop of the precision of the bonding position. The structure disclosed, for example, in the Japanese Utility Model Application Publication (Kokoku) No. 5-396732 has been proposed as a means to prevent thermal expansion of the bonding horn. In this structure, a heat-shielding plate which is semicircular in cross section is installed so that the plate covers the circumferential surface of the lower part of the bonding horn. In addition, it is designed so that cooling air is blown between the bonding horn and the heat-shielding plate. Further to the heating block, a wire bonding apparatus is generally equipped with: (a) an X-axis motor and Y-axis motor which drive an XY table and a bonding head in the X and Y directions, (b) a bonding horn which holds the capillary, (c) a Z-axis motor which causes the lifter arm to which the bonding horn is attached to pivot or move vertically, and (d) a bonding-load linear motor which applies a bonding load to the capillary so that the capillary presses the ball or wire against the bonding point. The wire bonding apparatus of this type is disclosed, for example, in the Japanese Patent Application Laid-Open (Kokai) Nos. 4-317342 and 4-320350. A wire bonding apparatus further includes a detection camera which detects the workpiece. Two types of cameras are known presently. In one type, a mirror tube which has a workpiece detection part is installed horizontally in an offset position with respect to the capillary, the detection camera is attached to the mirror tube, and the mirror tube is fastened to the bonding head. In another type, the detection camera is fastened to a camera supporting arm so as to be at an offset position with respect to a capillary, and the camera supporting arm is fastened to the bonding head. With the thus installed cameras, the bonding point is first detected by the detection camera, then the bonding coordinates are corrected, and then the capillary is driven in the X and Y directions and also in the Z direction. Wire bonding is performed after these movements. In the prior art described above, countermeasures are taken only against the thermal expansion of the bonding horn that is caused by the radiant heat of the heating block. In other words, no consideration is given to the fact that the mirror tube and the camera supporting arm are also caused to thermally expand. The mirror tube and camera supporting arm are positioned above the heating block; therefore, they can easily undergo thermal expansion as a result of the thermal expansion of the heating block. When the mirror tube and camera supporting arm thus undergo thermal expansion, the position of the point which is detected as the bonding point tends to shift, resulting in that a positional discrepancy occurs relative to the capillary. When a relative positional discrepancy thus occurs between the detected point and the capillary, the precision of the bonding position drops. Furthermore, in the prior art described above, no consideration is given to other heat-emitting sources than the heating block. Accordingly, the bonding horn and the mirror tube or camera supporting arm may expand due to thermal expansion caused by heat emitted from the bonding horn, Z-axis motor and bonding-load liner motor, resulting in that positional discrepancies are generated in the capillary and workpiece detection part. In other words, even if thermal expansion of the bonding horn caused by the heating block is prevented in the conventional apparatuses, such is usually insufficient. Meanwhile, the heat generated by the X-axis motor and Y-axis motor generally have almost no effect on the bonding horn, mirror tube or camera supporting arm. SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide a wire bonding apparatus in which thermal expansion of the bonding horn and mirror tube or camera supporting arm is prevented so that discrepancies in the bonding position are reduced, thus improving the bonding precision. The object of the present invention is accomplished by a unique structure for a wire bonding apparatus that includes (i) a bonding horn which holds a capillary at one end, and (ii) a detection camera which detects the workpiece, so that the pads of semiconductor pellets on a workpiece are connected to the leads of lead frames via wires that pass through the capillary, and the unique structure includes: an adiabatic plate installed beneath the bonding horn so as to block the radiant heat of the heating block which heats the workpiece, and a cooling air supply means which blows cooling air onto the bonding horn and the mirror tube of the camera or the camera supporting arm which supports the camera. The object of the present invention is further accomplished by a unique structure for a wire bonding apparatus that includes (i) a bonding horn which holds a capillary at one end, and (ii) a detection camera which detects the workpiece, so that the pads of semiconductor pellets on a workpiece are connected to the leads of lead frames via wires which pass through the capillary, and the unique structure includes: an adiabatic plate installed beneath the bonding horn so as to block the radiant heat of the heating block which heats the workpiece, a cooling air supply means which blows cooling air onto the bonding horn and the mirror tube of the camera or the camera supporting arm which supports the camera, and a cooling air supply means which blows cooling air onto the Z-axis motor and the bonding-load linear motor. With the structures above, the heat radiated from the heating block onto the bonding arm is blocked by the adiabatic plate. The heat emitted by the bonding horn and by the mirror tube or camera supporting arm is controlled by the cooling air blown out by the cooling air supply means. As a result, the bonding horn and the mirror tube and camera supporting arm show little expansion that is caused by thermal expansion. Accordingly, there is little shift in the bonding position, and the precision of the bonding position is improved. Furthermore, the Z-axis motor and the bonding-load linear motor are also cooled by cooling air supplied by the cooling air supply means. Accordingly, the precision of the bonding position is improved even further. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of one embodiment of the wire bonding apparatus of the present invention. DETAILED DESCRIPTION OF THE INVENTION One embodiment of the present invention will be described below with reference to FIG. 1. A bonding arm 2 for holding a capillary 1 at one end is attached to a lifter arm 3. The lifter arm 3 is provided on a bonding head 4 so that the lifter arm can pivot or move vertically. The pivot or vertical movement of the lifter arm 3 is effected by a Z-axis motor 5 which is installed on the bonding head 4. The coil side of a bonding-load linear motor 6 which applies a bonding load for causing the capillary 1 to press the ball or wire against the bonding point is fastened to the lifter arm 3, and the magnet side of the bonding-load linear motor 6 is fastened to the bottom part of the bonding head 4 or to the upper surface of an XY table (not shown). A mirror tube 7 which is used to detect a workpiece is installed horizontally and fastened to the bonding head 4. The detection part which detects the workpiece is provided on the undersurface of one end of the mirror tube 7, and a detection camera 8 which is provided on the bonding head 4 is connected to the other end of the mirror tube 7. The bonding head 4 is fastened to the surface of the XY table (not shown). The structure described above is well known, and therefore, a further description will be omitted. A radiant heat shielding plate 10 is installed beneath the bonding horn 2. The shielding plate 10 is positioned so as not to interfere with the bonding horn 2 even when the bonding horn 2 is moved downward. The radiant heat shielding plate 10 is fastened to the front surface of the bonding head 4. A pair of horn cooling pipes 11 and 12 are installed on both sides of the bonding horn 2. The pipes 11 and 12 respectively have air blowing section 11a and 12a that run along the bonding horn 2. Numerous air blowing holes (not shown) which blow air toward the bonding horn 2 are formed in the air blowing section 11a and 12a of the horn cooling pipes 11 and 12. In addition, a mirror tube cooling pipe 13 is installed on one side of the mirror tube 7. The cooling pipe 13 has an air blowing section 13a that runs along the mirror tube 7. The mirror tube cooling pipe 13 is fastened to the side surface of the bonding head 4. Numerous air blowing holes 13b which blow air to the mirror-tube 7 are formed in the air blowing part 13a of the cooling pipe 13. The Z-axis motor 5 is installed on the bonding head 4 with an adiabatic plate 14 in between. A plurality of Z-axis motor cooling pipes 15 are installed above the Z-axis motor 5. The cooling pipes 15 have air blowing holes 15a which face the heat-generating section of the Z-axis motor 5. The Z-axis motor cooling pipes 15 are provided on a fixed part of the apparatus (not shown). A linear motor cooling pipe 16 which has an air blowing part 16a is installed above the bonding-load linear motor 6. The linear motor cooling pipe 16 is fastened to the side surface of the bonding head 4. Numerous air blowing holes (not shown) which blow air toward the bonding-load linear motor 6 are formed in the air blowing part 16a. In the Figure, the reference numeral 17 is an illuminating tube; and pipes (not shown) which supply cooling air from cooling air sources (not shown) are connected to the horn cooling pipes 11 and 12, mirror tube cooling pipe 13, Z-axis motor cooling pipes 15 and linear motor cooling pipe 16. Next, the operation of the above described embodiment will be described. During the wire bonding operation, cooling air is blown out from the horn cooling pipes 11 and 12, mirror tube cooling pipe 13, Z-axis motor cooling pipes 15 and linear motor cooling pipe 16. The heat generated from the bonding horn 2 is controlled (or cooled) by the cooling air blown out from the horn cooling pipes 11 and 12, the heat emitted by the mirror tube 7 is controlled by the cooling air blown out from the mirror tube cooling pipe 13, the heat emitted by the Z-axis motor 5 is controlled by the cooling air blown out from the Z-axis motor cooling pipes 15, and the heat emitted by the bonding-load linear motor 6 is controlled by the cooling air blown out from the linear motor cooling pipe 16. In addition, the transmission of radiant heat from the heating block (not shown) to the bonding horn 2 is blocked by the radiant heat shielding plate 10. In addition, the transmission of heat emitted by the Z-axis motor 5 to the bonding head 4 is controlled by the adiabatic plate 14. As seen from the above, the bonding horn 2 and mirror tube 7 undergo little thermal expansion because of the cooling air blown thereto, and therefore, they show little expansion or elongation. As a result, no bonding position shifts occur, and the precision of the bonding position is improved. The inventor conducted several tests, and the test results indicate that the factors having the greatest affect onto the expansion of the bonding horn 2 and the mirror tube 7 are the radiant heat from the heating block and the heat generated by the ultrasonic oscillation of the bonding horn 2. Thus, as seen from the above, with the radiant heat shielding plate 10, horn cooling pipes 11 and 12 and mirror tube cooling pipe 13, an extremely great cooling (or non-expansion) effect was obtained. An even more superior effect was obtained in the tests when the Z-axis motor cooling pipes 15 and linear motor cooling pipe 16 were installed. In the above embodiment, the mirror tube 7 is installed on the bonding head 4. However, it goes without saying that the present invention is applicable to apparatuses of the type in which the detection camera 8 is provided on the bonding head 4 via a camera supporting arm. In such a case, the mirror tube cooling pipe 13 is a camera supporting arm cooling pipe, and the camera supporting arm is cooled. As seen from the above, according to the present invention, an adiabatic plate which blocks the radiant heat from the heating block that heats the workpiece is installed beneath the bonding horn, and cooling air supply means are also provided so as to blow cooling air onto the bonding horn and onto the mirror tube of the detection camera or a camera supporting arm which supports the detection camera. Accordingly, these element can stay not-heated, and discrepancies in the bonding position which are generally caused by heat is reduced, and the bonding precision is improved.
A bonding apparatus used in manufacturing, for example semiconductor devices, including an adiabatic plate provided beneath a bonding horn for blocking the radiant heat from a heating block that heats up a workpiece. The apparatus further includes horn cooling pipes and a mirror tube cooling pipe for blowing cooling air onto a bonding horn and onto a mirror tube of a detection camera or a detection camera supporting arm.
7
CROSS REFERENCE TO RELATED APPLICATION The present application is a continuation-in-part of prior U.S. patent application Ser. No. 08/590,687 filed on Oct. 26, 1995, now abandoned. TECHNICAL FIELD The present invention relates to dielectric spectroscopy and more particularly to time-domain dielectric spectroscopy. BACKGROUND OF THE INVENTION Dielectric spectroscopy (DS) is one of several methods used for physical and chemical analysis of materials. Most advanced among the methods are chromatographic, spectroscopic, mass-spectrometric, thermodynamic and electric. All of the foregoing methods are characterized by high precision and accuracy with the exception of thermodynamic and electric which are of relatively low accuracy. Electric methods are able to identify the basic characteristics of a substance, such as tgσ and ε. However, the dielectrics of different classes may share identical values for tgσ and ε, making it impossible to identify a substance based on these parameters alone. Although DS has been under continued development it does not currently enjoy substantial or significant use since it requires a great deal of complex and expensive equipment operated by highly skilled technicians. Additionally, information on dielectric materials could only be obtained over limited frequency ranges. Known to the art are several time-domain spectroscopy (TDS) methods. For example, Waldmeyer and Zschokke-Granacher disclose a single reflection time-domain reflectometry method (J.Phys.D:Appl.Phys. 8:1513-1519, 1975). This method may be utilized to obtain the frequency spectrum of the permittivity of materials. In practice, the voltage step pulse of a step generator is propagated along a coaxial transmission line where it is at least partially reflected by the test material. The permittivity of the material is determined from the following expression: ε*(s)= (2V.sub.o /s)U.sub.s (s)-1!.sup.2 where V o /s represents the ideal step function of voltage and U s (s) is the falling and reflecting pulse of the voltage. Another method by Kaatze and Giese (J.Phys.E:Sci.Instrum. 13:133-141, 1980) relies on observations of a sample's response to exciting step voltage pulses. In some basic aspects this method resembles the Fourier Transform technique. Voss and Happ (Phys.D:App.Phys. 17:981-983, 1984) describe a method which uses voltage pulses and allows separation of the test signal from the response in time. The dielectric function g(T) of solids and liquids can be determined from the reflection response. Frame and Fouracre (Phys.D:Appl.Phys. 18:99-102, 1985) use exponential and t -n power law response. The decay current as a function of time is generally found to be of the form: I(t)=Kt.sup.-n where K and n are constants, that is the dielectric response function of the form: ƒ(t)=Kt.sup.-n /C.sub.o V.sub.o where C o is the capacitance of the sample and V o is the applied voltage. The complex susceptibility as a function of frequency is: ##EQU1## Baba and Fujimura (Jap.Journ.App.Phys. 26(3)479-481, 1987) used reflected waves from the surface of the dielectric under test and obtained relaxation parameters of dielectric ε o ; ε.sub.∞ ; t o with the Fourier transform technique. In the method of Hart and Coleman (IEEE Transactions on Electrical Insulation 24(4)627-634, August 1989), a voltage pulse of known shape is applied to the object and the resulting current form measured. Fourier transformation of the time variation of the object's conductance yields the dielectric spectrum. Feldman et al. (Colloid Polym. Sci 270:768-780, 1992) considered the TDS method to be based on the reflectometry principle in time-domain in order to study heterogeneities in the coaxial lines according to the change of the test signal shape. Until the line is homogeneous this pulse is not changed; when heterogeneity is introduced, for example by the presence of a dielectric, the signal is partly reflected from the air-dielectric interface, while the remainder of the signal passes through it. Skodovin et al (J Colloid Interface Sci 166:43-50, 1994) introduced a method of total reflection in which the sample cell is placed at the open end of a coaxial line. The shapes of reflected step pulses from a cell filled with a sample and from a cell filled with a reference liquid were recorded. Via a Fourier transform, the dielectric spectrum of the sample is given by: ε*(ω)=ε'(ω)-iε"(ω)-iσ/.omega.ε.sub.o. All of the reviewed methods of the time-domain dielectric spectroscopy are different from the proposed method. They use a reflection time-domain method for observation of the response of the dielectric sample to exciting step voltage pulses of picoseconds duration. The positive charge center in an atom of the substance is displaced in relation to the negative charge center when an electric field is placed across an atom as shown in FIG. 1. This is known as polarization. From Frohlich H. (1958) "Theory of Dielectrics" the linear approximation of the dielectric polarization P (electric dipole movement of the volume unit) is proportional to the electric field tension E in the sample: (1) P=.sub.χ E where proportional coefficient .sub.χ is called the dielectric susceptibility. When an external electric field is applied the dielectric polarization reaches its equilibrium value, not instantly, but over a period of time. By analogy, when the electric field is broken suddenly, the polarization decay caused by thermal motion follows the same law as the relaxation or decay function: (2) α(t)=P(t)/P(o). The value of the displacement vector D (t) in the electric field E (t) may be written: ##EQU2## where ε.sub.∞ is the high frequency limit of complex dielectric permittivity ε*(ω); Φ(t-t') is the dielectric response function. The dielectric response function is: Φ(t)=ε.sub.∞ +F(t) (4) where F(t)=(ε s -ε.sub.∞) 1-α (t)!, ε s is the static dielectric permittivity. The dielectric response function may be written as follows: Φ(t)=ε.sub.∞ +(ε.sub.s -ε.sub.∞) 1-α(t)!. (5) The complex dielectric permittivity ε*(ω) is an analog of the dielectric response function in the time-domain: ##EQU3## where L is the operator of the Fourier-Laplace transform. If the relaxation function is: α(t)≅exp(-t/τ.sub.m) (7) where τ m represents the dielectric relaxation time, then the relation first obtained by Debye is true for the frequency domain: ε*(ω)-ε.sub.∞ !/ (ε.sub.s -ε.sub.∞)=1/(1+iωτ.sub.m). (8) For most of the investigated dielectrics experimental results cannot as a rule, be described by such a relation. This relation is true only for ideal or close to ideal real dielectrics. The spectral function of the complex dielectric permittivity ε*(ω) can be substituted by the dielectric response function in time-domain. This means that time-domain response function of the dielectric, i.e. the current under step-function field, is derived by the Fourier transform from the frequency domain function. These functions are exponential, and may be presented as follows: ω.sup.n-1 ⃡t.sup.-n ( 9) ω.sup.m ⃡t.sup.-(m+ 1) where ω is frequency, t is time, n and m are constants, ⃡ is direct and inverse Fourier transform. This is the mathematical basis for substitution of complex dielectric permittivity ε*(ω) in frequency-domain, with the dielectric response function Φ(t) in time-domain. As shown in Jonscher AK "Dielectric Relaxation in Solids", the dielectric relaxation process is accompanied by decay current i(t) which is proportional to the dielectric response function: i(t) ∝Φ (t). (10) Furthermore in Jonscher AK "Dielectric Relaxation in Solids" the universal dielectric response function is: ##EQU4## where K 1 ; K 2 ; n; m are constants, that characterize the microscopic properties of the dielectric. A graph of the decay current is presented in FIG. 2. In order to get the most complete characteristics of the dielectric, the absorption phenomena will be used. The absorption phenomena is a self-relaxation process after a quick discharge of the dielectric. The absorption phenomena may be described by the following approximate expression: V.sub.a (t)=a t.sup.b e.sup.ct ( 12) Where t is time, a, b, c, are absorption parameters, and a>0; 0>b>1; c<0; e=2.718. The apparatus presented in this invention goes through the series of steps (OA, AB, BC, CO) to arrive at the absorption curve DEFI. (FIG. 3) The dielectric is charged on OA interval up to V CH volts, then on AB interval, the dielectric is kept under the same voltage, (V CH ). Next the dielectric is discharged on BC interval until 0 volts is achieved. At last, the dielectric is kept at 0 volts on CD interval. DEFI interval is an actual absorption phenomenon. The FI interval is the dielectric response function course. The proposed apparatus forms this curve, and also calculates a unique set of a, b, c, m, and n parameters for the dielectric under measurement. PROPHETIC EXAMPLES A persistent problem in fuel marketing is the practice among dishonest wholesale and retail vendors of diluting gasoline or diesel fuel with water, or representing fuels to be of higher octane or of different composition than is actually the case. A vendor wishing to assure a high-quality product engages an exemplary embodiment of a TDS device of the present invention which fits between the supplier's fuel dispenser and the mouth of vendor's underground tank. As fuel is being introduced through the dispenser the TDS device calculates the dielectric characteristics of the fuel. Fuel which does not conform with specifications may then be refused. Such a device also reduces the possibility of inadvertent introduction of one type of fuel into a tank intended for another type of fuel. A consumer wishing to assure a high-quality product engages a TDS device which either fits between the dispenser nozzle and the mouth of the vehicle's fuel tank, or is permanently mounted on the vehicle with a remote display within the vehicle. This low-cost device gives a rapid reading of the octane level of the fuel being pumped. If the octane is not as represented, the purchaser disengages and purchases fuel elsewhere. Laboratory supply companies are expected to deliver precise molar concentrations of highly purified laboratory chemicals. Drug manufacturers likewise are held to high levels of precision and purity in drug formulation. A TDS device of the present invention may be employed to assure samples do not fall outside accepted levels of concentration and can readily identify the presence of impurities. Paints have a relatively limited shelf life due to changes in chemical composition over time. Exposure to extreme temperatures can speed this process. A TDS profile obtained on a can of paint will determine whether the material meets specifications before it is applied. Medical applications of TDS sampling include urinalysis and serum analysis, e.g. in the rapid and accurate detection of sugar and insulin levels for diabetics. The purity of drinking water is of constant concern. TDS evaluation will allow identification of significant levels of impurities and can be programmed to reveal the presence of specific contaminants such as lead. Conversely, the value of fine crystal is gauged in part on the basis of lead content. A TDS profile on a sample of glassware will reveal whether the lead content is as high as represented, with no harm to the sampled article. Virtually all legitimate credit cards are produced by a single entity which employs a distinctive plastic in the manufacture of the cards. This plastic has a unique dielectric profile. A vendor wishing to verify the legitimacy of a credit card may employ a TDS device which scans credit cards before a purchase is registered. Forged cards will not conform with the expected dielectric profile and can be refused. Soil samples can be assayed with TDS to determine the presence of trace minerals for mining applications, as well as to determine the presence of specific contaminants for detoxification efforts. The efficacy of insulating devices and materials can be assayed with TDS. The quality of capacitors, transformers, generators and electromotors can be measured against the performance of a TDS counterpart. Gaseous applications of TDS sampling include emission monitoring in industrial stacks and vehicles. SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to provide a novel method and device for time-domain dielectric spectroscopy. Another object is to provide an electric method of TDS which is highly accurate and precise. Another object is to make use of the unique polarization characteristics of subject materials to identify said materials. Yet another object is to provide a method of TDS wherein dielectric response function is measured after charging/discharging of the dielectric sample, absorption phenomena are assessed, and the resulting qualities are compared with known values to identify a sample. A further object is to provide a compact and portable method and device for TDS. Still another object is to provide an inexpensive method and device for TDS which requires little technical skill to operate. These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 depicts the logarithm of the static atomic polarization of a number of elements, illustrating the unique position of each element; FIG. 2 demonstrates the logarithmic analysis of an exemplary analyte by the instant invention; FIG. 3 is a charge and absorption curve of an exemplary analyte by the instant invention; FIG. 4 is a block scheme of an exemplary apparatus of the instant invention; FIG. 5 is a block scheme of a sample cell of an exemplary apparatus of FIG. 4; FIG. 6 is an exemplary dielectric absorption curve; FIG. 7 is an exemplary dielectric response function; FIGS. 8A through 8E are an exemplary electrical scheme of a preferred embodiment of the instant invention; FIGS. 9A and 9B are flow diagrams of an exemplary process for determining time-domain dielectric spectroscopy; FIG. 10 illustrates an exemplary, portable TDS device for consumer use in monitoring fuel content by inserting a gas nozzle through the TDS device and thereby measuring fuel characteristics; FIG. 11 demonstrates the device of FIG. 10 in use during refueling of a vehicle; and FIG. 12 illustrates an exemplary TDS device for retailer use in monitoring fuel content during delivery by a wholesaler to an underground holding tank. DETAILED DESCRIPTION OF THE INVENTION A block diagram of the device is presented in FIG. 4. The device consists of a constant voltage source 10, which is connected by a first terminal 11 through normally open (N.O.) switch 20 to the input terminal 41 of the sample cell 40. A second terminal 12 is connected through N.O. switch 30 to the other input terminal 42 of the sample cell 40. The shield of the sample cell 40 is grounded. The output terminal 43 of the sample cell 40 is connected through N.O. switch 50 to the ground, and at the same time to the input terminal 72 of the low-noise amplifier 70. The output terminal 44 of the sample cell 40 is connected through N.O. switch 60 to the ground, and at the same time to the input terminal 71 of the low-noise amplifier 70. The output 73 of the low-noise amplifier 70 is connected to the input of analog to digital converter (ADC) 80. An output (81) of ADC 80 is connected to the input of microcontroller unit (MCU) 90. Display 100 and keyboard 110 are connected to the first 91 and second 92 outputs of MCU 90, respectively. Switches 20, 30, amplifier 70, and ADC 80 are controlled by MCU 90 through the control bus 120. The sample cell 40 consists of four electroconductive surfaces. The one pair of these surfaces forms external electrodes which have input terminals 41 and 42, the other pair form internal electrodes which have output terminals 43 and 49. The equivalent electric scheme of the sample cell is presented in FIG. 5. The capacitors C1, C2, C3 are equal. The total value of these capacitors are chosen for gasoline measurement near 100 pF. All of these electrodes are enclosed into metallic box which serves as a shield. The measured substance is placed between these four electrodes. The four electrodes design helps to eliminate the harmful polarization of the internal electrodes. The device works in several phases. The first phase is forming of the absorption curve on the sample cell 40. At this phase amplifier 70 is set at a gain which equals 1. Switches 20 and 30 are closed for 100 ms. As a result, the device forms charge intervals OA and AB (FIG. 3) after switches 20 and 30 are opened. Switches 50 and 60 are closed for 5-10 ms. Thus BC and CD intervals are formed. Finally switches 50 and 60 are opened, and the absorption curve DEFI (FIG. 3) begins to form. The evidence of this registers on terminals 43 and 44 in the form of an electrical signal. This analog signal is inputted to amplifier 70 through inputs 71 and 72. After the initial amplification, the analog signal is transmitted to ADC 80 through 73. The analog signal is converted into digital code in ADC 80. ADC 80 samples absorption voltage discretely every t s (sample time interval) FIG. 6. MCU 90 finds the maximum of the absorption voltage from the samples received from ADC 80, and sets the gain on amplifier 70 through bus 120 using the following criteria: G=0.9 V.sub.s /V.sub.max (13) where G is amplifier gain, Vs is saturation voltage of the amplifier, V max is maximum voltage of the absorption curve. The first phase is repeated again, but with the gain of the amplifier 70 set correspondingly to criteria (13). In order to calculate the parameters a, b, c, m, n from the absorption curve as shown in FIG. 6, the device finds the t max which is time from beginning of the absorption curve (point D) to the maximum of the absorption voltage (V max ), and t inf (inflection point time). Assume that absorption curve of FIG. 6 consists of I points which are measured every sample time interval (t s ). MCU 90 calculates first derivatives in each point 0, 1, 2, 3 . . . i, i+1 . . . I, then finds the minimal value of the first derivative using the following criteria: V'.sub.k =|ΔV.sub.k /t.sub.s |=min (14) where V' k is first derivative; ΔV k =V i -V i+1 ; V i is voltage in point i; V i+1 is voltage in point (i+1); t s is the sample time interval; k=1,2,3 . . . I-1. When the minimum of the first derivatives is found, the following expression defines t max : t.sub.max =t.sub.s k. (15) From t max MCU 90 calculates the parameter c: c=1/t.sub.max. (16) The inflection point of the absorption curve DEFI is point where the second derivative of the absorption curve is equal zero. The second derivative may be found from: V".sub.n =|(V'.sub.k -V'.sub.k+1)/t.sub.s.sup.2 |=min(17) where V" n is second derivative; V' k is first derivative in the point; V' k+1 is first derivative in (k+1) point; t s is the sample time interval; n=1, 2, 3 . . . I-2. When the minimum of the second derivatives is found, the following expression defines t inf : t.sub.inf =n t.sub.s. (18) The MCU 90 calculates parameter b from the following expression: ##EQU5## From (19) we have two values of the parameter b, using the following criteria MCU 90 selects one value of b: 0<b<1. (20) Furthermore, the MCU 90 calculates parameter a: a=V.sub.max /e t.sub.max.sup.b (21) where V max is the maximum value of the absorption curve, e=2.718. The next step is the calculation of parameters m and n from the dielectric response function. The proposed device measures voltage on the FI interval of FIG. 3. This voltage is proportional to the decay current in dielectric of equation (10) if the amplifier 70 has constant input impedance. The decay current is proportional to the dielectric response function and may be written from (11): ##EQU6## where Z is impedance of the amplifier 70, K 1 and K 2 are constants. If Z is constant, then: ##EQU7## Where V(t)=i(t) Z, C 1 =K 1 Z, and C 2 =K 2 Z. The MCU 90 produces the decimal logarithm of the V(t) from (23): ##EQU8## The graph of the dielectric response function is shown in FIG. 7. The FG and HI intervals may be approximated by two straight lines with slope coefficients n and (m+1) from (24). In real measurement we have the GH curve interval shown in FIG. 7. In order to decrease the approximation errors for FG and HI intervals shown in FIG. 7 MCU 90 leaves out all points which belong to the GH interval, and satisfy the next criteria: |(Δlog.sub.10 V.sub.i -Δlog.sub.10 V.sub.i+1)/log.sub.10 t.sub.s |>2 e.sub.n G (25) where i is previous the point and (i+1) of next point, i=1, 2, 3 . . . I, where I is the total number of the points that belong to the dielectric response function of FIG. 7, e n is the noise of the amplifier 70, G is the gain of the amplifier 70. The n and m parameters (slope coefficients) may be found by MCU 90 using the following expression: n=(P X Y!- X! Y!)/(P Y.sup.2 !-( Y!).sup.2) (26) m=(Q X Y!- X! Y!)/(Q Y.sup.2 !-( Y!).sup.2) (27) where P and Q are the numbers of points that belong to the FG and HI intervals shown in FIG. 7 respectively and where: ##EQU9## and where the description (P;Q) in the summation symbol means to use P for (26) and Q for (27). Finally, MCU 90 had found all parameters: a, b, c, m, n which are the unique characteristics of dielectric. The electrical principal scheme of the preferred embodiment is shown in FIGS. 8A-8E. Suitable components for constructing the apparatus are set forth in Table 1 below: TABLE 1______________________________________COMPONENTLOCATION DESCRIPTION SOURCE______________________________________S1 Quad SPST Switches LF13202 National Semi- conductorU1 Programmable Gain Instrumentation Burr- Amplifier PGA204 BrownU2 Analog-To-Digital Converter AD7893 Analog DeviceU3 Microcontroller Unit MSM80C51F OKIU4, U6 Hex Contact Bounce Eliminator MC14490 MotorolaU5 Hex Non-Interfering Buffer MC14050 MotorolaU7 10 Line-to-4 Line BCD Priority Harris Encoder CD40147BU8 Voltage Reference MC1403 MotorolaU9 Voltage Regulator LM317L National Semi- conductorU10 DC-to-DC Converter PPD1R5-12-1212 Lambda LCD, DMC-50448N Optrex Keyboard, 83AC1-103 GrayhillBT1 Battery, CR2025 PanasonicR1 Potentiometer, Series 3266, 200K BournsR2 Resistor, 220 Ohm ± 1%, 1/4 W, Metal Film YageoR3 Resistor, 2K ± 1%, 1/4 W, Metal Film YageoR4 Resistor, 8.2K ± 5%, 1/4 W, Carbon Film YageoC1 Capacitor, 0.01 uF, 16 V, Polyester PanasonicC2, C4, C7, Capacitor, l0 uF, 50 V, Tantalum PanasonicC9, C11, C15C3, C5, C6, Capacitor, 0.1 uF, 50 V, Ceramic Disc PanasonicC8, C10, C12C13, C14 Capacitor, 10 pF, 50 V, Ceramic Disc PanasonicC16 Capacitor, 1 uF, 63 V, Monolithic Ceramic PanasonicD1 Diode, 1N914 National Semi- conductorY1 Microprocessor Crystal, 12 MHz CTS______________________________________ COMPARISON OF THE KNOWN ART WITH THE PRESENT INVENTION Sanders' U.S. Pat. No. 5,461,321 describes the measurement of the value of a capacitance. Blackwell's U.S. Pat. No. 3,784,905 describes the measurement of a dielectric strength. Bungay's U.S. Pat. No. 4,429,272 describes the measurement of a change in the dielectric constant of a fluid. Ludlow's U.S. Pat. No. 3,753,092 describes the measurement of small changes in the dielectric constant of insulating liquids. Day's U.S. Pat. No. 4,777,431 describes the measurement of the dielectric properties of a material by applying time-varying voltage (e.g. an AC signal) to a dielectric material and measuring the amplitude of the current and its phase, relative to the input voltage. Capots' U.S. Pat. No. 4,433,286 describes the measurement of the conductance and capacitance of a material. Bechtel's U.S. Pat. No. 5,394,097 describes the measurement of the real and imaginary parts of permittivity in dielectric materials. The present invention describes the measurement of the absorption function parameters a,b,c and the dielectric response function parameters m and n. SUMMARY Known art inventions are quite different from the present invention in that they measure the characteristics of the dielectric during charge/discharge cycle or under alternating current. Thus, the measurements take place on the OABC interval (FIG. 3) for the known art. The present invention, on the other hand, measures dielectric absorption and response function parameters on the DEFI interval (FIG. 3), and makes it possible to identify dielectrics more precisely than any other previously mentioned measurement known in the art. Finally, two exemplary applications of the device are represented by FIGS. 10 through 12. In FIG. 10 the device represented 200 consists of a housing 210 with a display window 220. Transecting the housing is a cylinder 230 of sufficient size to accommodate the dispensing nozzle 250 of a typical gas station fuel dispenser. A sample cell (see FIGS. 4 and 5) is disposed within the cylinder 230 so as to come in contact with the fuel as it is being dispensed into a vehicle or fuel receptacle through nozzle 250. All other components depicted in FIG. 4 are disposed within housing 210 such that display 100 (FIG. 5) is visible through display window 220. It is anticipated that this device is programmed to assess octane levels and fuel purity with the display 100 registering octane levels. A consumer may use such a device when fueling a vehicle as shown in FIG. 11. The more sophisticated device 300 represented in FIG. 12 consists of a somewhat larger housing 310 with a display window 320. Transecting the housing is a cylinder (not shown) of sufficient size to accommodate the dispensing nozzle 350 of a typical bulk fuel dispenser. A sample cell as shown in FIGS. 4 and 5 is disposed within the cylinder so as to come in contact with the fuel as it is being dispensed into a subterranean storage tank (not shown). All other components depicted in FIG. 4 are disposed within housing 310 such that display 100 FIG. 4 is visible through display window 320. It is anticipated that this device is programmed to assess octane levels and fuel purity with the display 100 registering a number of different parameters for the monitoring of fuel quality and content by retailers.
A time-domain dielectric spectroscopy device and method are described wherein measurements are taken of the absorption and dielectric response function of a dielectric material in order to identify dielectric materials.
6
CROSS-REFERENCE TO RELATED APPLICATIONS The present invention is related to the application entitled "Improved Method and Article of Manufacture for Resynchronizing Client/Server File Systems and Resolving File System Conflicts" application No. 08/572,926, filed on Dec. 12, 1995. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process and article of manufacture for managing computer file system transactions and, in particular, for managing a disconnected computer file system. Still more particularly, the present invention relates to the management and optimization of a transaction log for collecting disconnected file system transactions for re-execution when the file system is connected. 2. Background and Related Art Distributed computer systems allow a number of computer "clients" to access a server and to share files on that server. The client workstation is typically connected to the server through some form of network. Laptop computers provide a mobile computing environment to people who must travel in their work or take work with them to customer or work sites. Laptop computers can be connected into a network through either a wired connection, a dial-in connection or some form of optical or radio connection. Infrared connection between a laptop computer and a server is particularly easy to use as the laptop computer must simply be placed in the line of sight of the server infrared sensor. Any distributed computer environment has the possibility of network interruption and temporary disconnection. Mobile computing using laptop computers increases the frequency of disconnection and includes disconnected operation as a normal operating mode. Disconnected operation is facilitated by a file caching facility. The CODA system developed by Carnegie Mellon University provides file caching for the Andrew File System (AFS.) CODA provides a mechanism for caching data on a client computer. Changes to the data are logged on the client computer then replayed to the server. Changes that conflict with the current state of the server computer are flagged and their application deferred. Logging operations in CODA are described in: KISTLER, J. J. DISCONNECTED OPERATIONS IN A DISTRIBUTED FILE SYSTEM. PhD Thesis, Carnegie Mellon University, School of Computer Science, 1993. Section 6.2 "Transaction Logging" pp. 120-133; and KISTLER, J. J., AND SATYANARAYANAN, M. "Disconnected Operation in the Coda File System." ACM TRANSACTIONS ON COMPUTER SYSTEMS 10, 1 (February 1992) Section 4.4.1 "Logging". Another file system for disconnected operations is the Mobile File Sync system from IBM Corp. This system is described in U.S. patent application Ser. No. 08/206,706 file Mar. 7, 1994 and bearing attorney docket number AT994-014. Mobile file systems allow the user to connect to a remote server, access files, disconnect and yet still maintain access to the same accessed files. Disconnected file access is supported by caching a copy of the file on the local client machine when it is connected to the remote server. Changes made to the disconnected file system by the user are tracked and re-executed or replayed to the server when a connection is re-established with the remote server. The mobile file system must record all transactions that modify the disconnected file system. A logging process is used to track all file system modifications on the cached client and then supports replay of the transactions onto the server. The logging process applies special rules to reorder and optimize the transaction log. Optimization is required to minimize the storage consumed by the transaction log and to minimize the amount of time required to replay and resynchronize the client with the server file system. A technical problem therefore exists of providing a set of optimization rules that minimize the log size and replay time without sacrificing the ability to accurately track file system modifications. SUMMARY OF THE INVENTION The present invention is directed to providing a process and article of manufacture for constructing and optimizing a disconnected file system transaction log. The present invention constructs the log by grouping the transactions for efficient and accurate playback to the server. The file system transactions are identified by a file identifier or FID that is dynamically expanded into the full path name of the file during replay. Dynamic file identifier (FID) expansion reduces the amount of information collected for each transaction and allows greater optimization of the transaction log than is possible with prior art logging methods. The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of a preferred embodiment of the invention, as illustrated in the accompanying drawing wherein like reference numbers represent like parts of the invention. BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a block diagram of a network system according to the present invention. FIG. 2 is a block diagram of a computer system according to the present invention. FIG. 3 is a diagram of the transaction log according to the present invention. FIG. 4 is a diagram illustrating the mapping of file identifier (FID) to full path name according to the present invention. FIG. 5 is a flowchart of the novel transaction log optimization according to the present invention. DETAILED DESCRIPTION The present invention operates in a networked computer system such as that shown generally at 100 in FIG. 1. A network 102 connects a number of workstations 104, 108, 112. One of the workstations, e.g. 104, may function as a server. The network 102 can be any known local area network or wide area network such as a token ring or Ethernet network managed by a protocol such as NetBIOS or TCP/IP. Each workstation may or may not contain permanent storage such as hard disks 106, 114, 110. Workstation 112 is shown as being a disconnectable workstation. This workstation is connected through an interface such as an infrared interface. It could also be connected using dial telephone lines. Workstation 112 operates frequently in a disconnected mode and must synchronize with server 104 and the file system contained on permanent storage 106. Each computer system contains elements similar to those shown in FIG. 2. This configuration is shown as an example only and any other computer configuration could be employed without departing from the invention. Computer system 200 has a processor element 204 that contains one or more central processing units (CPUs.) Memory 202 is provided to store programs and data. I/O controller 208 controls the communication between the computer system and peripheral devices such as the display screen 220, keyboard 218, pointing device 216, and fixed and removable storage, 210 and 212. Removable storage can be any device such as a diskette drive for magnetic or optical disks 214. The computer system for the present invention can be any computer system having these basic components. The preferred embodiment uses an IBM Personal Computer or IBM PS/2® system. The invention can also be practice on an IBM RISC System/6000®. The present invention operates in conjunction with an operating system such as the IBM OS/2® operating system, the Microsoft Windows® operating system or the IBM AIX® operating system. Each of these operating systems supports a file system with defined rules for file system management. The present invention is implemented as part of the logging process in the disconnected client workstation. The logging process records information about each user transaction that modifies the file system structure or content. These transactions can include replacing a file, deleting or removing a file, or creating a new directory or file. These transactions are continuously added to the transaction log to form a chain of transactions to be replayed on the server when a connection is established. The following is a list of transactions supported by the OS/2 operating system file system: CREATE Creates a new file. STORE Stores data into a pre-existing file. REMOVE Erases a file. MKDIR Creates a new directory. RMDIR Removes a directory. RENAME Renames a file or directory possibly changing its path. Each new transaction may be (1) appended to the log, (2) inserted into the log, or (3) optimized out of the log and possibly canceling prior transactions. The following list better describes these three logging operations and the conditional rules governing their execution. FIG. 3 illustrates a transaction log according to the present invention. The transaction log is maintained preferably in the memory or permanent storage of the client computer system. A transaction log maintained in memory must be periodically copied to persistent storage to ensure that no data is lost. 1. LOG ENTRY APPENSION All transactions other than RENAME are appended to the transaction log under normal circumstances (i.e. CREATE, MKDIR, REMOVE, RMDIR, and STORE.) The executing order of these transactions is maintained in the log because each transaction is added chronologically to the end of the log file, e.g. 304. The log entry for each of these transactions contains a dynamic path for the target (i.e. file or directory) of the transaction. A dynamic path is one which is expanded during the REPLAY process. This dynamic path is represented internally as a FID (file identifier). The file identifier (FID) associated with the transaction is expanded dynamically during the REPLAY process to generate the absolute path of the target file or directory thus allowing the transaction to be replayed on the server, e.g. 402. The file identifier (FID) is expanded through a series of searches on the hierarchy of file system objects composing the mobile file system. The use of dynamic path expansion in the present invention is much more efficient for log processing and easier to maintain than the hard-coded path names used in prior art systems. For instance, if a new file "bar" was created on the client by a CREATE transaction in the directory "m:\foo", then a new file identifier (FID) "X" would be allocated representing the new file "m:\foo\bar". If at a later point in time, directory "foo" were changed by the user to "boo" with a RENAME transaction, the log entry for CREATE would NOT need to be updated since the file identifier (FID) "X" would automatically expand to "m:\boo\bar" during the REPLAY process. This design also allows for some RENAME transactions to be optimized out of the log. This will be discussed below in LOG OPTIMIZATION. 2. LOG ENTRY INSERTION The RENAME transactions are the only transactions which are inserted into the log rather than appended too it. Each RENAME transaction will be inserted at the beginning of the log following the last RENAME transaction inserted e.g., 302. This maintains the chronological ordering of the RENAME transactions and also ensures that all RENAME transactions will be REPLAYED before any other transaction types. It is necessary for RENAME transactions to be REPLAYED first since the file system component names on the server must be modified to match those on the client before any additional components may be added or original components deleted. This is required because the path names for all transactions other than the RENAME transaction are expanded dynamically. Therefore, each component name within the expanded path for a single transaction will represent the latest name assigned by the client during disconnection via a RENAME transaction. For instance, suppose a new file "bar" were created on the client via a CREATE transaction in the directory "m:\foo". Then a new file identifier (FID) "X" would be allocated representing the new file "m:\foo\bar". Again suppose at a later point in time, directory "foo" were changed by the user to "boo" with a RENAME transaction. If the CREATE and RENAME transactions had been appended to the log in the order in which they occurred, then the CREATE transaction would be REPLAYED first and the file identifier (FID) "X" would expand to "m:\boo\bar"; however, the directory "m:\boo" does not yet exist on the server since the RENAME transaction has not yet changed "m:\foo" to "m:\boo". Therefore, the dynamic expansion of component names forces us to insert RENAME transactions before other transaction types so that, in this case, the directory "m:\foo" is renamed to "m:\boo" before an attempt is made to create the file "m:\boo\bar" on the server. Also, by their very nature, RENAME transactions are the only transactions whose path names are not expanded dynamically. These transactions have both a source and target path name which are; hard-coded within the transaction itself. The source path name must be hard-coded. If not, then during REPLAY an attempt would be made to rename the file or directory onto itself since both source and target are associated with the same file identifier (FID) and would expand to the same name. The target path name must also be hard-coded so that it matches the naming tree on the server during REPLAY. For instance, suppose that while disconnected from the server, the user renames file "m:\foo\bar" to "m:\foo\bat". Again suppose, that at some later point in time the user renames the parent directory "m:\foo" to "m:\boo". At the time when the first RENAME transaction is replayed, if the target path name was expanded dynamically then an attempt would be made to rename "m:\foo\bar" too "m:\boo\bat". This transaction would fail since "m:\boo" does not yet exist on the server until the following RENAME transaction were replayed to rename "m:\foo" to "m:\boo". 3. LOG OPTIMIZATIONS Optimization of the transaction log helps reduce transaction log space requirements and improve the performance of the REPLAY process as the mobile file system attempts to synchronize both the server and client file system images. It does so by reducing the total number of transactions in the log. Optimization occurs as a new log entry is examined for entry. New transactions can sometimes (1) be ignored, (2) modify existing transactions, or (3) cancel out existing transactions. The following is list of cases in which these types of log optimizations can occur (refer to FIG. 5 for a flowchart of the process of log optimization): a. STORE OPTIMIZATION If a STORE transaction is encountered with a file identifier (FID) which matches an already existing STORE transaction in the log then the STORE transaction in the log can be effectively replaced by deleting the old transaction and then appending the new transaction to the log. In other words, if the contents of a file are stored more than once then only the last store is necessary for REPLAY since it will supersede all previous stores too the same file. b. MKDIR/RMDIR OPTIMIZATION If a RMDIR (remove directory) transaction is encountered with a file identifier (FID) which matches an already existing MKDIR (make directory) transaction in the log then the MKDIR transaction in the log may be deleted and the RMDIR transaction ignored. In other words, if the user is removing a directory which was created while disconnected, then the two transactions cancel each other out and it is not necessary to log either one of them. There is no reason to make directories on the server if we are only going to remove them. The fact that the RMDIR is being logged implies that the directory is empty. If not, then an error would have been returned to the user. Therefore, there are no additional log optimizations to be made such as removing any files created in the directory. c. CREATE/REMOVE OPTIMIZATION If a REMOVE transaction is encountered with a file identifier (FID) which matches an already existing CREATE transaction in the log then the CREATE transaction in the log may be deleted and the REMOVE transaction ignored. In other words, if the user is deleting a file which was created while disconnected, then the two transactions cancel each other out and it is not necessary to log either one of them. There is no reason to create files on the server if we are only going to delete them. d. STORE/REMOVE OPTIMIZATION If a REMOVE transaction is encountered with a file identifier (FID) which matches an already existing STORE transaction in the log then the STORE transaction in the log may be deleted and the REMOVE transaction appended. In other words, if the user is deleting a file whose contents was modified while disconnected, then the STORE transaction is canceled out and it is not necessary to log that transaction. There is no reason to change the contents of a file on the server if we are only going to delete it. e. MKDIR/RENAME OPTIMIZATION If a RENAME transaction is encountered with a file identifier (FID) which matches an existing MKDIR transaction in the log then the RENAME transaction may be ignored. The reasoning for this, is that the RENAME transaction has already changed the name of the directory on the client. Therefore, when the MKDIR transaction's dynamic path name is expanded during REPLAY, it will already evaluate to the new name. Thus, there is no reason to rename the directory again on the server. For example, suppose the user creates a directory "foo" on the client while disconnected via a MKDIR transaction. Then a new file identifier (FID) "X" would be allocated representing the new directory "m:\foo". Again suppose at a later point in time, directory "foo" were changed by the user to "boo" via a RENAME transaction. At that time the RENAME transaction can be optimized out of the log. During the REPLAY process, the MKDIR transaction would be REPLAYED and file identifier (FID) "X" would be expanded to create the directory "m:\boo". At this point the final desired result has been achieved. REPLAYING the RENAME transaction would have only been superfluous. f. CREATE/RENAME OPTIMIZATION If a RENAME transaction is encountered with a file identifier (FID) which matches an already existing CREATE transaction in the log then the RENAME transaction may be ignored. The reasoning for this, is that the RENAME transaction has already changed the name of the file on the client. Therefore, when the CREATE transaction's dynamic path name is expanded during REPLAY, it will already evaluate to the new name. Thus, there is no reason to rename the file again on the server. For example, suppose the user creates a file "bar" on the client while disconnected via a CREATE transaction. Then a new file identifier (FID) "X" would be allocated representing the new file "m:\bar". Again suppose at a later point in time, file "bar" were changed by the user to "bat" via a RENAME transaction. At that time the RENAME transaction can be optimized out of the log. During the REPLAY process, the CREATE transaction would be REPLAYED and file identifier (FID) "X" would be expanded to create the file "m:\bat". At this point the final desired result has been achieved. REPLAYING the RENAME transaction would have only been superfluous. g. RENAME/RENAME OPTIMIZATION If a RENAME transaction is encountered with a file identifier (FID) which matches an already existing RENAME transaction in the log then the hard-coded target path of the RENAME transaction already in the log may be replaced with the new target path from the pending RENAME transaction and the pending RENAME transaction may then be discarded. The reasoning for this, is that a single RENAME transaction is all that is ever required per source file or directory. Renaming a file or directory multiple times can always be reduced to a single RENAME transaction. When this optimization takes place, the new target path must be propagated throughout the log to all subsequent ordered RENAME transactions. This is necessary, since RENAME transactions have hard-coded paths instead of dynamic paths. For each consecutive RENAME transaction following the updated transaction, both the source and target paths must be checked for sub-strings equivalent to the old target path which was modified. If located, then the old target path sub-string must be substituted with the new target path sub-string. Consider the following example: Transaction Log (Original) RENAME Fid=112 Old="m:\foo" New="m:\boo" RENAME Fid=114 Old="m:\boo\bar" New="m:\boo\bat" STORE Fid=114 (Expands dynamically to "m:\boo\bat") New Transaction RENAME Fid=112 Old="m:\boo" New="m:\zoo" Transaction Log (Updated) * RENAME Fid=112 Old="m:\foo" New="m:\zoo" * RENAME Fid=114 Old="m:\zoo\bar" New="m:\zoo\bat" STORE Fid=114 (Expands dynamically to "m:\zoo\bat") * denotes transactions which were updated In this example the new RENAME transaction has the same FID=112 as a RENAME transaction already existing in the log. Therefore, the target path of the transaction in the log "m:\boo" is replaced with the new target path "m:\zoo". Now, the new RENAME transaction may be discarded but it is still necessary to propagate the new target path to the remaining RENAME transactions residing in the log thus far. By searching for the old target sub-string "m:\boo" in the remaining RENAME transactions, we find a match for Fid=114. We then replace the sub-string "m:\boo" with "m:\zoo" in both the source and target path of this RENAME transaction and continue searching until we encounter the first transaction which is not a RENAME. At that point the search is terminated, since all RENAME transactions are grouped at the beginning of the log. In this case, the STORE for Fid=114 was encountered which terminated the search. Note that the STORE transaction need not be modified since its path is expanded dynamically during REPLAY. It will be understood from the foregoing description that various modifications and changes may be made in the preferred embodiment of the present invention without departing from its true spirit. It is intended that this description is for purposes of illustration only and should not be construed in a limiting sense. The scope of this invention should be limited only by the language of the following claims.
A process and article of manufacture for optimally logging and replaying file system transactions from a mobile file system. The process logs file system transactions in chronological order except for file and directory object renaming transactions that are logged before all other transactions. Each transaction log entry includes a transaction type and file identifier that is expanded dynamically during the replay cycle. The dynamic expansion of the identifier reduces the number of log entries required where file or directory objects are renamed. The transaction log is optimized as each transaction is inserted or appended on the client. The optimization process eliminates transactions that are rendered invalid or superfluous by the most recent transaction. The dynamic expansion feature allows RENAME transactions to be optimized because MKDIR and CREATE transactions automatically are expanded to the new file system object name, eliminating the need to log the RENAME transaction. Successive RENAME transactions are folded into a single RENAME transaction to reduce log size and playback resource requirements.
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PRIORITY CLAIM This is a U.S. national stage of application No. PCT/DE02/03643, filed on Sep. 25, 2002. Priority is claimed on that application and on the following application(s): Country: Germany, Application No.: 101 47 018.5, Filed: Sep. 25, 2001. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention pertains to a sludge extractor with a receiving tank, on which are mounted a suction connection for a suction element, which draws in a sludge-containing liquid, and a discharge connection for a discharge element, which discharges the sludge-containing liquid, the extractor also being equipped with a motor to drive a suction device in such a way that a negative pressure, which keeps a vacuum valve on the discharge element closed, is created in the receiving tank. 2. Description of the Prior Art A sludge extractor of this type is known from DE 199 42 187 A1. The suction process is begun by turning on the motor. The receiving tank fills up slowly with sludge-containing liquid until the liquid reaches the level of the vacuum valve. The vacuum valve is closed because of the prevailing negative pressure. When a the liquid reaches a certain limit in the receiving tank, a ball valve closes, as a result of which the motor begins to run audibly faster. This is a sign to the user that it's time to turn off the motor. Turning off the motor has the effect of eliminating the negative pressure in the receiving tank. The internal pressure now being produced by the sludge-containing liquid has the effect of opening the vacuum valve, and the sludge-containing liquid can now escape through the discharge element until the receiving tank is empty again. Then the user can turn the motor on again to repeat the process as often as necessary. A sludge extractor of this type therefore suffers from the disadvantage that the receiving tank, which fills up relatively quickly, can only be emptied discontinuously, by turning off the motor. A procedure of this type leads to many interruptions in the suction process itself, and many users find this annoying. SUMMARY OF THE INVENTION The task of the present invention is therefore to create a sludge extractor which is able to perform wet-vacuuming continuously. The task is accomplished according to the invention in that, when the sludge-containing liquid reaches a predetermined level in the receiving tank, the negative pressure acting on the vacuum valve is weaker than the pressure acting on the vacuum valve as a result of the sludge-containing liquid. The sludge extractor according to the invention offers the advantage that suction can be carried out continuously without the need to turn the unit off repeatedly during the course of the vacuuming process. BRIEF DESCRIPTION OF THE DRAWINGS An embodiment of the present invention is described in greater detail below on the basis of the drawings: FIG. 1 shows a schematic diagram of a sludge extractor according to the present invention; and FIG. 2 shows a schematic diagram, in cross section, of the sludge extractor according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An inventive sludge extractor 1 ( FIG. 1 ) comprises a housing 1 . 1 , on which a suction connection 1 . 2 for a suction element 3 and a discharge connection 1 . 3 for a discharge element 5 are formed. The housing 1 . 1 is also designed with a cover 1 . 4 in its upper area, i.e., the area at the opposite end from the bottom. The cover 1 . 4 is fastened detachably to the lower housing 1 . 1 . At the bottom, the housing 1 . 1 is provided with a base element 1 . 5 . The central area of the interior of the housing 1 . 1 is designed as a receiving tank 1 . 6 for the sludge-containing liquid, usually a mixture of sludge and water or materials of similar consistency. The suction connection 1 . 2 is located in the upper part of the receiving tank 1 . 6 , and the discharge connection 1 . 3 is located in the lower part of the receiving tank 1 . 6 . Above the receiving tank 1 . 6 , that is, above the area of the housing 1 . 1 which can be filled with sludge and water, a motor 1 . 7 , preferably an electric motor, is mounted, which drives a generally known suction device 1 . 8 such as an air-drawing vane element ( FIG. 2 ). While the device is being driven, air is drawn from the receiving tank 1 . 6 and conveyed to the outside via air outlet openings 1 . 9 in the upper area of the housing. As a result, a negative pressure is created in the receiving tank 1 . 6 and in the suction element 3 . The motor 1 . 7 has a drive shaft 1 . 10 for the suction device 1 . 8 . The free end 1 . 11 of this shaft extends to a point near the bottom of the interior of the receiving tank 1 . 6 . The suction device 1 . 8 or pump is mounted at the free end 1 . 11 of the drive shaft 1 . 10 . The suction device 1 . 8 is seated in a flow channel 1 . 12 , which establishes a direct connection to the discharge connection 1 . 3 . In the immediate vicinity (in the present embodiment, below) of the suction device 1 . 8 , a first liquid inlet 1 . 13 a is provided, through which the indrawn sludge-containing liquid is admitted. Between the suction device 1 . 8 and the discharge connection 1 . 3 , a second liquid inlet 1 . 13 b is provided in the suction channel 1 . 12 , via which the vacuum valve 5 . 2 in the discharge connection 1 . 3 can be decoupled. The drive shaft 1 . 10 is supported in a sealed, protective housing 1 . 14 . In the area of the maximum level MAX for water or sludge, a safety valve 1 . 15 is provided, which closes the air outlets 1 . 9 when the maximum water level is reached. The safety valve 1 . 15 is a float valve. In the present embodiment, the drive shaft 1 . 10 and its protective housing 1 . 14 are mounted in the center of the receiving tank 1 . 6 . In other embodiments, the drive shaft 1 . 10 could also be mounted off-center in the receiving tank 1 . 6 . The safety valve 1 . 15 is concentric with respect to the drive shaft 1 . 10 . Also concentric with respect to the drive shaft 1 . 10 and its protective housing 1 . 14 is a prefilter 1 . 16 . The prefilter 1 . 16 is installed near the inside wall of the receiving tank 1 . 6 and serves to keep coarse material such as leaves, small twigs, gravel, etc., away from the suction device 1 . 8 . There is a certain gap between the inside circumference of the prefilter 1 . 16 and the protective housing 1 . 14 of the drive shaft 1 . 10 . The upper suction connection 1 . 2 is located at the level of the maximum water or fill level. The flow route is limited on the inside by a wall 1 . 17 of the centrally mounted safety valve 1 . 15 , so that the incoming sludge-containing liquid is diverted downward into the prefilter 1 . 16 adjacent to the safety valve and then emerges from this filter on all sides or at least radially toward the inside. The safety valve 1 . 15 is limited laterally on the outside by the wall 1 . 17 and on the inside by the protective housing 1 . 14 . In the enclosed space of the safety valve 1 . 15 , a ring-shaped float 1 . 18 is provided, which, at low water or fill levels, closes off an opening 1 . 19 at the bottom (the dotted line outline of float 1 . 18 in the figure shows the position at low water levels). As the water or fill level rises, the sludge-containing liquid rises through the opening 1 . 19 and lifts the ring-shaped float 1 . 18 until the ring-shaped float 1 . 18 closes off the air outlet 1 . 9 the solid line outline of float 1 . 18 in the figure shows the position proximate the MAX fill level). The suction element 3 ( FIG. 1 ) is fastened detachably to the suction connection 1 . 2 in the generally known manner and is equipped optionally with a radio-control switch 3 . 2 in a gripping area 3 . 1 . In addition, a suction line 3 . 3 is formed on the free end of the suction element 3 , onto which a suction nozzle (not shown) can be placed. The suction element 3 can be a hose or a pipe. A discharge element 5 is mounted detachably in the generally known manner on the discharge connection 1 . 3 and has a vacuum valve 5 . 2 at its free end 5 . 1 . The discharge element 5 can also be a hose or a pipe. The vacuum valve 5 . 2 can also be installed in the discharge connection 1 . 3 or in any other desired position between the discharge connection 1 . 3 and the free end 5 . 1 . The device functions as follows. The suction line 3 . 3 and optionally the suction nozzle of the suction element 3 hangs down into the water, near the bottom of the pond. The suction process is begun by turning on the motor 1 . 7 , which can be done, for example, by radio control switch 3 . 2 . Via the suction line 3 . 3 , sludge is sucked from the bottom of the pond. The sludge thus passes through the suction element 3 and into the receiving tank 1 . 6 . The receiving tank 1 . 6 fills up slowly with sludge as far as the level of the vacuum valve 5 . 2 . The vacuum valve 5 . 2 is kept closed by the prevailing negative pressure. When the liquid reaches a predetermined level in the receiving tank 1 . 6 , i.e., the level at which the pressure being exerted via the liquid inlet 1 . 13 on the vacuum valve 5 . 2 is greater than the negative pressure keeping the vacuum valve 5 . 2 closed, the vacuum valve 5 . 2 opens automatically, so that the sludge-containing liquid can flow out continuously through the discharge opening 1 . 3 . A discharge element 5 such as a hose can be connected to the discharge opening 1 . 3 by means of a standard commercial quick-connect device; the free end 5 . 1 of this hose can be placed anywhere desired such as at a place where the sludge is to be dumped. In addition to radio-control operation switch 3 . 2 , a switch arrangement is also provided directly on the sludge extractor 1 in order to turn the sludge extractor on and off. In other exemplary embodiments, two separate motors can be provided, so that a suction device near the bottom and another suction device relatively far away from the bottom can each be operated by its own motor. The cover 1 . 4 , the motor 1 . 7 , the drive shaft 1 . 10 , and the suction device 1 . 8 can be assembled as a unit and mounted so that they can be removed all at once. The prefilter 1 . 16 can also be removed as a unit. The unit and the prefilter can thus be easily detached from the receiving tank 1 . 6 for the purpose of cleaning.
A sludge extractor with a receiving tank, on which a suction connection for a suction element, which draws in a sludge-containing liquid, and a discharge connection for discharge element, which discharges the sludge-containing liquid, are mounted, and with a motor for driving a suction device in such a way that a negative pressure is created in the receiving tank, which negative pressure keeps a vacuum valve on the discharge element closed, is characterized in that the negative pressure acting on the vacuum valve is lower than the pressure which acts on the vacuum valve as a result of the sludge-containing liquid when a predetermined fill level is reached by the sludge-containing liquid in the receiving tank.
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